Pigment dye in the form of 5,6-dihydroxyindoline polymer, the method of production thereof and cosmetic compositions based on it

 

(57) Abstract:

The subject invention are new compounds in the form 5,6 - dihydroxyindoline of the polymer is a product of the interaction of 5,6 - dihydroxyindole and at least one sulfur-containing compound selected from N-acetylcysteine and sulfur-containing peptides with hydrophilic groups and soluble in aqueous and/or aqueous-alcoholic medium. The subject invention also is a method of obtaining these compounds, as well as cosmetic composition based on them. 3 S. and 14 C.p. f-crystals, 2 tab.

The invention relates to new compounds present in the form of 5,6-dihydroxyindoline polymers, a method of receiving and containing cosmetic compositions.

Milanovie compounds commonly known in the form of insoluble pigments. In this case we are talking about pigments, which are the basis of dyes for hair, skin or hair of a human or animal origin. These compounds are synthesized, in particular by oxidation of indole derivatives such as 5,6-dihydroxy-indole. They tend to use in cosmetics due to the fact that they are very close to the natural pigments.

This is Due to their insolubility, the use of these pigments can create some problems in the use of dispersant to obtain cosmetic compositions having good homogeneity.

Some authors, such as ORL OW, OSBER and PAWELECK [Pigment Cell Researeh, 5, S. 113-121 (1992)], describe a method of obtaining melanophore pigment, soluble in water at pH above 5, 5,6-dihydroxy-indole-2-carboxylic acid (DHICA), used individually or in a mixture of 5,6-dihydro-indole (5,6-DH1). These soluble milanovie pigments undoubtedly easier to use than insoluble pigments, since there is no need to use dispersant, however, they do not always retain satisfactory solubility after freeze-drying and re-dissolving.

On the other hand, in the patent WIPO 92/16189 to obtain soluble melanophore pigment in the aqueous solution at a pH value varying from 5 to 9, from DHlCA, if necessary associated with 5,6-DH1 and/or sulfur-containing compounds. According to this document, the presence of sulfur-containing compounds allows to obtain soluble pigments having more variety of color. However, these compounds, although they are soluble, do not have satisfactory CRA is-indole polymer, which is soluble in aqueous or aqueous-alcoholic medium while maintaining satisfactory coloring ability of the polymer.

Therefore, the object of the invention is the connection being in the form of 5,6-dihydroxy-indole polymer, substituted hydrophilic groups connected with the above polymer using a sulfur-containing residue, and the number of hydrophilic groups is selected so as to obtain the compound, soluble in water and/or aqueous-alcoholic medium.

The polymer according to the invention is soluble in water and/or aqueous-alcoholic medium having a pH value of not more than 7, i.e., neutral pH, then acidic pH, and keeps good solubility in water and/or aqueous-alcoholic medium even after lyophilization and storage. In addition, this soluble polymer 5,6-dihydroxyindole is black and has good absorption in the visible region. It is comparable, even better, the coloring ability in relation to such soluble Milanovich polymers of the prior art. Moreover, it is very stable when stored after lyophilization and can be re-dissolved.

The subject of the invention is also a method of obtaining new 5,6-dihydroxyindoline th compounds with hydrophilic groups;

to this solution was added 5,6-dihydroxyindole and the reaction is carried out to obtain the target soluble polymer 5,6-dihydroxyindole, and the amount of sulfur-containing compounds are chosen so that the final resulting compound was soluble in water and/or aqueous-alcoholic medium.

The connection according to the invention, therefore, is in the form of polymer 5,6-dihydroxyindole, substituted hydrophilic groups associated with the above polymer using a sulfur-containing residue.

This connection may be a reaction product between 5,6-dihydroxyindole and at least one sulfur-containing compound with hydrophilic groups.

The above sulfur-containing compound is preferably chosen among compounds containing at least one sulfur atom and which may not participate in the cyclization with the formation of benzothiazine when interacting with 5,6-dihydroxyindole.

In fact, benzothiazine are intermediate compounds in the synthesis of pheomelanin (melanin red colors that are photosensitizing against the skin). According to the invention, the cyclization to benzothiazine not proishozhdenie according to the invention can be called, in particular, sulfur-containing peptides with hydrophilic groups, such as reduced glutathione or N-acetyl-cysteine. The amount of sulfur-containing compounds present in the reaction time, is chosen so as to obtain the target compound, soluble in water and/or aqueous-alcoholic media. The concentration used sulfur-containing compounds is preferably about 0.001 to 1 wt%, based on the total weight of the reaction medium.

Sulfur-containing compound prefer to pre-dissolve in water and alcohol, even in organic medium, and the above solution is pH-value at least equal to 5. In fact, it was found that when the pH is below 5, 5,6-dihydroxyindole cannot react with sulfur-containing compound. For pH control, you can use classic acidifying or alkalizing agents, such as hydrochloric acid and sodium hydroxide.

the pH Value of the solution is preferably 5 to 10, in particular 6 - 8.

The concentration used 5,6-dihydroxyindole may vary within wide limits and is preferably about 0.001 to 10 wt%, based on the total weight of the reaction medium.

5,6-Dihydr the e above the 0oC, for example, at 30 - 40oC. Even more preferably, the reaction temperature is 36 - 38oC.

The reaction time required to obtain the target soluble compounds may be of the order of 6 to 72 hours

The reaction medium can also contain pH regulators, called "buffers", which can be called sodium phosphate.

So get melanova connection being in the form of a polymer 5,6-dihydroxyindole, substituted hydrophilic groups associated with the above polymer due to sulfur-containing residue, and the number of hydrophilic groups is chosen so that the above-mentioned compound was soluble in water and/or aqueous-alcoholic medium.

The solubility of this melanopogon connection in the above environment is preferably usually 50-100 mg/ml

You can use this connection in the form of the resulting aqueous or aqueous-alcoholic solution or in the form of a concentrate or in dried form, for example, by lyophilization, to obtain a powdered product that can be used in cosmetic compositions.

The subject of the invention is also the use of Milanovich connect osmeticheskie composition, containing 5,6-dihydroxyindoline dye in an amount of 0.01-5% by weight of the composition and cosmetic additives target (EP patent 379409, class A 61 K 7/021, 1990).

Proposed milanovie soluble compounds can be entered as they are received, either in concentrated and/or liofilizovannyh form in various types of cosmetic compositions, such as, for example, compositions for makeup, skin, eyelashes or eyebrows, the composition for protecting the human epidermis against UV radiation and/or compositions for dyeing hair.

In these compositions the concentration Milanovich compounds can vary from 0.001 to 5 wt.%, calculated on the total weight of the composition.

When the composition is used for makeup, skin, eyelashes or eyebrows, for example, as a cream for the treatment of epidermis, liquid, powder, lipstick, eyeshadow, blush for cheeks tinted pencil, called "the pencil to summarize the eye or mascara to the eyelashes and eyebrows, they can be in solid, liquid or pasty form, anhydrous or water, for example, in the form of an emulsion oil-in-water or water-in-oil dispersion, more or less concentrated lotions, or powders (powder). These compositions have the advantage costi.

If the composition is used for protecting the human epidermis against UV radiation, they are so-called solar composition and they are normally in the form of emulsions, such as creams and lotions, ointments, gels, solid sticks or aerosol foam. The emulsion can also contain anionic, cationic, nonionic, importanne, zwitterionic surface-active agents and mixtures thereof.

If the composition is used for dyeing hair, they can be in the form of a shampoo, lotion, gel or mouthwash, applied before or after shampooing, before, during or after a Perm or straightening lotion for TouchUp or treatment hair lotion or gel for brushing or styling hair, hair spray composition for permanent or straightening hair.

Compositions for make-up and solar compositions can contain, in addition, at least one additive selected among fatty substances, organic solvents, silicones, thickeners, softening agents, sun filters, antispyware, hydrating (wetting) agents, perfumes, preservatives, antioxidants, fillers, pigments, complexing agents, agents for processing, takikawa agents.

Of fatty substances include oils, waxes, fatty acids, fatty alcohols, vaseline, paraffin and lanolin, hydrogenated or acetylated. Oil in particular, you can choose among animal, vegetable, mineral or synthetic oils and should be called gidrirovannoe palm oil, gidrirovannoe castor oil, vaseline oil, paraffin oil and porcelanowe oil. Waxes in particular may be selected from among animal, vegetable, mineral or synthetic waxes; in particular it should be called beeswax, Carnauba wax, kandellilsky wax, sugar cane wax, Japan wax, maltes, montanuy wax, microcrystalline waxes, paraffins and silicone waxes.

Of the pigments can be called nacreous and/or giving pearly luster pigments, which allow to vary the coloration obtained with Milanovich soluble compounds according to the invention or to increase protection of the skin against ultraviolet radiation. In this latter case, you can use metallic pigments such as the oxides of titanium, zinc, cerium or zirconium.

The connection according to the invention can also be combined with such a connection, ka is but the invention contain free amines, they can help establish links between the skin and/or hair through such connections as ON. You can also obtain a composition for colouring skin and/or hair.

Example 1. 10 mmol of reduced glutathione contribute in a buffer solution with a pH of 7.5. Bring the pH to 7 by adding sodium hydroxide. Enter 10 mmol of 5,6-DH1 in the form of a powder, and the reaction mixture stirred for 48-72 h at 37oC. the compound Obtained not decanted by centrifugation speed-15,000 rpm./min for 10 minutes It can be filtered through a filter with a pore size of 0.22 μm and enters agarosegel in the amount of 1%.

A filtered connection lyophilizer by known methods.

Immediately after lyophilization, the connection is again dissolved in water, when it is at a concentration of 50 mg/ml

After storage for 6 weeks at 4oC, it liofilizirovannoe compound is also soluble in water at a concentration of 50 mg/ml

Example 2. 5 mmol of reduced glutathione injected into the buffer solution with a pH of 7.5. Bring the pH to 7 by adding sodium hydroxide. Add 10 mmol of 5,6-DH1 in the form of a powder, and the reaction mixture stirred for 48-72 h at 37 minutes It can be filtered through a filter with a pore size of 0.22 μm and enters agarosegel in the amount of 1%.

A filtered connection lyophilizer by known methods. Immediately after lyophilization, the connection is again dissolved in water to a concentration of 50 mg/ml

Example 3. 15 mmol of reduced glutathione injected into the buffer solution with a pH of 7.5. Bring the pH to 7 by adding sodium hydroxide. Add 20 mmol of 5,6-DH1 in the form of a powder and the reaction mixture stirred for 48 - 72 h at 37oC.

The compound obtained is not decanted by centrifugation speed-15,000 rpm. /min for 10 minutes It can be filtered through a filter with a pore size of 0.22 μm and enters agarosegel in the amount of 1%.

A filtered connection lyophilizer by known methods. Immediately after lyophilization, the connection is again dissolved in water to a concentration of 50 mg/ml

Example 4. Measure the optical density at 475 nm and 600 nm of various compounds according to the invention, dissolved in water. This measurement is carried out for several concentrations. Thus determine the mass absorption coefficient, which represents the slope is 1:

,

b) for compounds of example 2 is obtained values of the mass ratio in the same manner as that for compound 1:

,

C) for compounds of example 3 values smaller:

.

This is probably related to the introduction of larger quantities of glutathione in the polymer 5,6-DH1: for the same mass fraction of indole residues responsible for the absorption in the visible region, less. The stronger absorption in the visible region, the darker the color obtained melanopogon connection and the better his painting ability.

Example 5. A specific amount obtained according to example 1 compound is placed in water at 37oC for 30 minutes, the Sample is divided into two parts, of which one is subjected to filtration through a filter with a pore size of 0.45 μm or 0.22 μm.

Both parts of the sample is then brought to a concentration of 1 mg/ml and again incubated at 37oC to dissolve the possible remaining particles. Comparing the optical density at 600 nm and 475 mn. Believe that the filterability reflects the solubility in the chosen concentration.

Note that

for a concentration of 50 mg/ml does not hold the connection by filtering;

for concentration 1T, if the filter is replaced by a centrifugation speed-15,000 rpm./min for 10 min After filtration through a pore size of 0.22 μm Recuperat 87% of the compound.

Therefore, we can assume that this compound has a solubility limit in water of about 100 mg/ml

Example 6. Compare the light absorption of the compound obtained in example 1, with the connection according to the prior art, obtained by polymerization DHICA, at a concentration of 10 mmol.

Absorption spectra recorded for a solution with a concentration of 50 µmol in the form of indole residues in water.

Get the following results (see tab. 1)

Perform the same measurement for the connection according to the invention, obtained from 5 mmol of 5,6-DH1 and 5 mmol of glutathione, compared with the compound obtained from 5 mmol DHICA. Get the following results (see tab. 2).

Therefore, ascertain that the compounds according to the invention absorb more light in the visible region than compounds of the prior art. This is reflected in a stronger, more intense coloring, when using the composition comprising the compound according to the invention.

Formulations of cosmetic compositions below %
The mixture of wax - 16

Phase IN:

Hydroxyethylcellulose - 0,2

The compound obtained in example 1 - 5

Water up to 100

Phase:

Triethanolamine - 3

Phase D:

Acacia - 5,8

Heat phase a to 120oC, then homogenized apparatus Moritz. Heat phase b + C + D up to 80oC and emuleret with phase A. Again homogenized apparatus Moritz, up until the mixture becomes uniform mass. Cool with slow stirring. Receive ink pleasant color, with good cosmetic properties.

Example 8. Composition blush eyeshadow.

Get the song blush eyeshadow of the following components, percent:

Powder phase

Talc - 100

Mica - 22

Oxychloride of bismuth - 8

The zinc stearate - 3

Nylon-12 - 20

Connection example 1 - 1

Iron oxides - 3

Fat binder

Liquid paraffin - 3

Monistat of isopropyl - 3

Getting blush eyeshadow: milled powder phase, add a binder and crushed again. The mixture is pressed into the metal cups. Get blush eyeshadow with good cosmetic properties.

1. Pigment dye in the form of 5,6-dihydroxyindoline politicalwire fact, the polymer is a product of the interaction of 5,6-dihydroxyindole and at least one sulfur-containing compound selected from N-acetylcysteine and sulfur-containing peptides with hydrophilic groups, and the number of hydrophilic groups is chosen in such a way as to obtain a pigment dye, soluble in water and/or aqueous-alcoholic medium.

2. Dye under item 1, characterized in that it is soluble in water and/or aqueous-alcoholic medium having a pH of not more than 7.

3. Dye PP.1 and 2, characterized in that its solubility in the environment ranges from 50 to 100 mg/ml

4. Dye PP.1 to 3, characterized in that the sulfur-containing compound is restored glutathione.

5. Dye PP. 1 to 4, characterized in that it is in the form of aqueous or aqueous-alcoholic solution and in the form of a concentrate or powder.

6. A method of obtaining a pigment dye in the form of 5,6-dihydroxyindoline polymer, substituted hydrophilic groups connected to the above-mentioned polymer through a sulfur-containing residue, wherein the prepared water and/or water-alcohol solution having a pH of not less than 5, of the sulfur-containing solution of 5,6-dihydroxyindole and carry out the reaction to obtain the target compound, moreover, the amount of sulfur-containing compound is chosen so that the target compound was dissolved in water and/or aqueous-alcoholic medium.

7. The method according to p. 6, characterized in that the sulfur-containing compound selected from compounds containing at least one atom of sulfur and do not result in cyclization to benzothiazine when interacting with 5,6-dihydroxyindole.

8. The method according to p. 6 or 7, characterized in that the sulfur-containing compound is restored glutathione.

9. The method according to one of paragraphs.6 to 8, characterized in that the concentration of sulfur containing compounds with hydrophilic groups of 0.001 - 1 wt.% in relation to the total weight of the reaction medium.

10. The method according to one of paragraphs.6 to 9, characterized in that the concentration of 5,6-dihydroxyindole of 0.001 - 10 wt.% in relation to the total weight of the reaction medium.

11. The method according to one of paragraphs.6 to 10, characterized in that the 5,6-dihydroxyindole injected in powder form.

12. The method according to one of paragraphs.6 to 11, characterized in that the reaction is carried out at a temperature above 0oWith, mostly 30 to 40oC.

13. The method according to one of paragraphs.6 to 12, in which the pH of the reaction Crewe 5,6-dihydroxyindoline and cosmetic additives target, characterized in that as a pigment dye it contains dye PP.1 - 5 at a concentration of 0.001 - 5 wt.% by weight of the total composition.

15. The composition according to p. 14, characterized in that it is used for makeup, skin, eyelashes and eyebrows, to protect the skin of the person from UV rays and/or for coloring hair and skin.

16. The composition according to PP. 14 and 15, characterized in that it has the form of an emulsion, dispersion, more or less thick lotion, stack, powder, anhydrous paste or foam, aerosol or without it.

17. The composition according to PP.14 to 16, characterized in that it additionally contains dihydroxyacetone.

 

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