GB1581377A

GB1581377A - Coloured cosmetic preparations

Info

Publication number: GB1581377A
Application number: GB49359/77A
Authority: GB
Original assignee: F Hoffmann La Roche AG
Current assignee: F Hoffmann La Roche AG
Priority date: 1976-11-29
Filing date: 1977-11-28
Publication date: 1980-12-10
Also published as: SE7713458L; FR2371917A1; AT362881B; ES464542A1; IT1143699B; BR7707945A; JPS5369839A; AR217657A1; BE861261A; DE2752320A1; ATA850377A

Description

(54) COLOURED COSMETIC PREPARATIONS (71) We, F. HOFFMANN-LA ROCHE & CO., AKTIENGESELL SCHAFT, a Swiss Company, of 124-184 Grenzacherstrasse, Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to cosmetic preparations. More particularly, the invention is concerned with coloured pulverous cosmetic preparations which are especially suitable as a dry shampoo.

The commercially available dry shampoos are powder mixtures which consist of various components such as wheat starch, rice starch, maize starch, kaolin, talcum, metal stearates and carbonates as well as colloidal silicic acid, and siliceous earth.

These dry shampoos are produced by mixing varying amounts of the aforementioned components in suitable mixing drums The action of the aforementioned dry shampoos is based on an absorptive capacity towards fatty substances produced by the sebaceous glands, which substances, because of their spreading capability, are distributed over the surface of the skin and the hair, whereby various components (e.g. the starches) for the main part agglomerate with the fatty substances. Residues of these dry shampoos always remain to some extent on the scalp and hair. Since the components used are mostly white, these residues remain clearly visible, especially on brunette to black hair. Depending on the structure of the hair, these residues can never be brushed out completely. Such residues upset the desired cosmetic effect and act unaesthetically.

It is therefore not surprising that attemfpts have already been made to provide coloured dry shampoos using coloured starch as the colour carrier and adsorption agent. Since, as already mentioned, starches agglomerate with fats instead of only adsorbing to these, dry shampoos containing starch have the disadvantage that it is necessary to add still further substances having high adsorption capabilities (e.g. silica gel). Moreover, starches are nutrient substrata for bacteria as soon as they are saturated with impure fats or atmospheric moisture.

In accordance with the present invention there is now provided a cosmetic preparation which does not possess the aforementioned disadvantages.

More particularly, the present invention is concerned with a cosmetic preparation which contains coloured pulverous cellulose as the adsorption agent In accordance with a particularly preferred embodiment of the present invention, the cellulose has a particle size between 5 and 40 clam, preferably between 10 and 30 ,,us.

The present invention is also concerned with a process for the manufacture of the pulverous cosmetic preparations aforesaid, which process comprises colouring the cellulose and drying the coloured cellulose and, if desired, adding the coloured and dried cellulose to an active substance and/or adjuvant.

Substances which are used for the colouring of the cellulose are substances which are neither water-soluble nor solvent-soluble. The amount of colour-imparting substance added to the cellulose lies between 0.1 and 8 weight percent based on the weight of cellulose depending on the desired colouring.

Metal compounds, especially metal oxides, are suitable colour-imparting substances which can be used in the present invention. Especially suitable metal oxides are iron oxides and manganese oxides. In this case, a suitable metal salt is dissolved in an organic solvent such as alcohol or acetone and mixed with the cellulose. After several hours, the metal salts are converted with a suitable reagent (e.g. a reducing agent or an oxidising agent) into water-insoluble coloured pigments, preferably oxides or mixtures of oxides. The substrate coloured in this manner is subsequently dried.

Especially suitable metal salts are iron salts such as, for example, iron chlorides and iron sulphates and manganese salts such as potassium permanganate and manganese (II) sulphate.

Suitable reagents for the conversion of metal salts into water-insoluble coloured pigments are oxygen, hydrogen peroxide, carbamide peroxide, methanol and ethanol.

Oxidation pigments are also suitable as colour-imparting substances. In this case, there is first produced a mixture of pigment-forming acid addition salts of aromatic amines, reducing agents and substances serving for the control of the desired nuance.

Subsequently, the acid addition salts of aromatic amines are converted with organic bases such as triethanolamine or monoethanolamine into the corresponding free bases, the resulting mixture is dissolved in alcohol in the presence of a suitable wetting agent if desired or necessary and mixed with cellulose. After several hours, the pigment is formed on the substrate by oxidation with a customary oxidising agent such as, for example, hydrogen peroxide, carbamide peroxide or oxygen, and the substrate coloured in this manner is dried.

Especially suitable acid addition salts of aromatic amines are, for example, ptoluylenediamine sulphate, 4,4'-diaminodiphenylamine sulphate, 2,5-diaminoanisole sulphate, m-phenylenediamine sulphate and asymmetric m-toluylenediamine sulphate.

Sodium sulphite can be used as the reducing agent. Other reducing agents which are especially preferred are dihydroxybenzenes (e.g. pyrocatechin or resorcinol) and/or hydroquinone and/or trihydroxybenzenes (e.g. pyrogallol), since these simultaneously contribute to the control of the nuance.

Examples of further substances serving for the control of the nuance are nitrated or aminated aromatic hydrocarbons such as p-amino-o-cresol, 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine and 4-nitro-2-aminophenol.

The coloured, pulverous cosmetic preparations of this invention can also contain other active substances such as, for example, bactericidal agents and/or substances such as biotin, panthenol derivatives and/or plant extracts. The amount of bactericidal agent present in the cosmetic preparations advantageously amounts to 0.01 to 5 weight percent based on the cellulose. When a cosmetic preparation of this invention is used as a dry shampoo, the amount of bactericidal agent preferably amounts to 0.01 to 0.1 weight percent based on the cellulose. When a cosmetic preparation of this invention is used as an antiseptic powder, the amount of bactericidal agent preferably lies between 2 and 5 weight percent based on the cellulose.

Thus, for example, coloured cellulose can be separately or jointly impregnated with the active substance solution of a quaternary ammonium salt or 1 - (3 - chloroallyl) - 3,5,7 - triaza - 1 - azonia admantane (Dowicil) (Registered Trade Mark) and subsequently carefully dried while stirring. As the quaternary ammonium salts there are suitable, for example, those of the following general formula

R1 0 R4-N-R2 Halogen (I) R3 wherein R1 represents a methyl group, R2 represents an alkyl or aryl group, R3 represents an alkyl or aryl group, R4 represents an alkyl, aryl, aralkyl or glycidyl group and Halogen represents fluorine, chlorine, bromine or iodine.

The term "alkyl" as used herein includes straight-chain and branched-chain hydrocarbon groups containing up to 20 carbon atoms. The term "aryl" means an aromatic ring system containing from 6 to 12 carbon atoms, preferably phenyl. The term "Halogen" preferably denotes chlorine or bromine.

Quite particularly suitable quaternary ammonium salts are the following: Methyltriphenylammonium chloride or bromide, dimethyldiphenylammonium chloride or bromide, trimethylphenylammonium chloride or bromide, glycidyldiphenylmethylammonium chloride and distearyldimethylammonium chloride.

The pulverous cosmetic preparations provided by the present invention can contain adjuvants such as perfumes, plant extracts, vitamins and vitamin derivatives and also customary cosmetic powder bases.

The amount of perfume in a cosmetic preparation of this invention advantageously amounts to 0.1 to 0.3 weight percent.

Although the cosmetic preparations of this invention are particularly suitable as dry shampoos, they can, however, also be used for other purposes such as, for example, as a basis for make-up or as coloured antiseptic powders.

The present cosmetic preparations can be applied in various ways depending on the purpose of use; for example, in the form of a powder, spray, paste or cream.

In the case of a dry shampoo, a powder or spray form is preferred.

A dry shampoo advantageously contains coloured cellulose as the only adsorption agent and (apart from propellant gas which may be present) only small amounts of additives. The amount of these additives (usually perfume and a bactericidal agent) does not generally exceed 0.5 weight percent.

The amount of coloured cellulose in a make-up or in an antiseptic powder can be varied according to desire, but advantageously lies between 5 and 99.5% based on the total weight of the cosmetic preparation.

The following Examples illustrate the present invention: Example 1.

To a sulphonation flask provided with a stirrer, reflux condenser, thermometer and dropping funnel are added 1.2 g of 2,5-diaminotoluene sulphate, 0.4 g of pyrogallol, 0.4 g of pyrocatechin, 0.4 g of resorcinol, 0.4 g of hydroquinone, 0.2 g of 4-nitro-2-aminophenol, 0.6 g of 2-nitro-p-phenylenediamine, 2.0 g of 2,6-diaminotoluene sulphate, 2.0 g of 4,4'-diaminodiphenylamine sulphate and 4.0 of anhydrous sodium carbonate.

To the resulting mixture are added 9.0 g of ethanol (94 /O) and 10.0 g of monoethanolamine, and the resulting mixture is stirred for 0.5 hour. After approximately 0.5 hour, 300 ml of acetone are added. Subsequently, 100 g of cellulose (up to 30 r*m) are added to the solution obtained. The mixture is allowed to absorb up the cellulose with constant stirring at unchanged temperature for 3-4 hours.

Subsequently, the mixture is oxidised with 20 ml of hydrogen peroxide (30%) which is slowly added dropwise. The mixture obtained is left to react for a further 12-14 hours with constant stirring until the pigment is completely oxidised.

After filtration under suction, the filter cake is washed with acetone until the mother liquor is colourless and is then dried at 700C.

There is obtained a homogeneous dark brown colouring of the substrate, the pigment produced being water-resistant and oil-resistant.

Example 2.

100 g of pure microcrystalline cellulose (up to 30 llm) and 4 g of powdered potassium permanganate are suspended in 500 ml of acetone for 24 hours at room temperature with constant stirring in a sulphonation flask provided with a thermo meter, reflux condenser and stirrer. Subsequently, 4 ml of a 10% solution of carb amide peroxide in acetone are then slowly added dropwise and the mixture is stirred at room temperature for 2 hours. The product obtained is filtered under suction.

The filter cake is dried at 80"C in a dry cabinet, there being obtained a homogeneously coloured medium-brown cellulose.

Example 3.

The procedure described in Example 2 is repeated using hydrogen peroxide in place of carbamide peroxide. There is likewise obtained a homogeneously coloured medium-brown cellulose.

Example 4.

The procedure described in Example 2 is repeated using 50 ml of methanol in place of 4 ml of a 10% solution of carbamide peroxide. There is likewise obtained a homogeneously coloured medium-brown cellulose.

Example 5.

The procedure described in Example 2 is repeated using 50 ml of ethanol in place of 4 ml of a 10% solution of carbamide peroxide. There is likewise obtained a homogeneously coloured medium-brown cellulose.

Example 6.

The procedure described in Example 2 is repeated using 2 g of potassium permanganate in place of 4 g of potassium permanganate. There is obtained a homogeneously blonde (light brown) cellulose.

Example 7.

A cellulose coloured in analogy to the procedure described in Example 2 is impregnated up to saturation with a solution of 1 - (3 - chloroallyl) - 3,5,7 - triaza 1 - azonia - adamantane chloride (Dowicil). It is subsequently dried at 40"C while stirring.

In this manner there is obtained a coloured dry shampoo in powder form provided with a bactericidal compound (Dowicil).

Example 8.

A coloured dry shampoo in spray form can contain the following ingredients: Coloured cellulose (in accordance with Example 2) 10 g Propellant gas 90 g Perfume 0.05 g Quaternary glycidyltrimethylammonium chloride 0.01 g Example 9.

A cellulose coloured in analogy to the procedure described in Example 2 is impregnated up to saturation with a 3% solution of glycidyldiphenylmethylammonium chloride. It is subsequently carefully dried at 40"C while stirring.

In this manner there is obtained a coloured antiseptic powder which optically cannot be distinguished from the customary uncoloured white antiseptic powder.

Examples 1012.

Make-up creams can contain the following ingredients, the figures representing weight per cent:

Example Ingredient 10 11 12 Cetylstearyl alcohol 5.0 - 10.0 Non-ionic emulsifier 5.0 5.0 5.0 Ethyleneglycol stearate 15.0 10.0 5.0 Paraffin oil 10.0 5.0 15.0 Magnesium stearate 5.0 10.0 15.0 Coloured cellulose 20.0 15.0 15.0 dl-a-Tocopherol acetate 0.5 0.5 0.5 Distilled water 37.0 52.0 32.0 Sorbitol syrup (glycerine) 1.5 1.5 1.5 Perfume and preserving agent q.s. 1.0 1.0 1.0 100.0 100.0 100.0 WHAT WE CLAIM IS: 1. A cosmetic preparation containing coloured pulverous cellulose, wherein the cellulose is coloured with a colour-imparting substance which is neither water-soluble nor soluble in organic solvents.

2. A cosmetic preparation according to claim 1, wherein the cellulose has a particle size of 5 40 ssm.

3. A cosmetic preparation according to claim 2, wherein the cellulose has a particle size of 10-30 Fm.

4. A cosmetic preparation according to any one of claims 1 to 3 inclusive, wherein the colour-imparting substance is an oxidation pigment.

5. A cosmetic preparation according to any one of claims 1 to 3 inclusive, wherein the colour-imparting substance is a metal oxide.

6. A cosmetic preparation according to claim 5, wherein the metal oxide is a manganese oxide.

7. A cosmetic preparation according to claim 5, wherein the metal oxide is an iron oxide.

8. A cosmetic preparation according to any one of claims 1 to 7 inclusive which contains one or more perfumes.

9. A cosmetic preparation according to any one of claims 1 to 8 inclusive which contains one or more bactericidal agents.

10. A cosmetic preparation according to claim 9, wherein said bactericidal agent is a quaternory ammonium salt of the general formula

R4 N. R2 Halogen (I) wherein R' represents a methyl group, R2 represents an alkyl or aryl group, R" represents an alkyl or aryl group, R4 represents an alkyl, aryl, aralkyl or glycidyl group and Halogen represents fluorine, chlorine, bromine or iodine.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Example Ingredient 10 11 12 Cetylstearyl alcohol 5.0 - 10.0 Non-ionic emulsifier 5.0 5.0 5.0 Ethyleneglycol stearate 15.0 10.0 5.0 Paraffin oil 10.0 5.0 15.0 Magnesium stearate 5.0 10.0 15.0 Coloured cellulose 20.0 15.0 15.0 dl-a-Tocopherol acetate 0.5 0.5 0.5 Distilled water 37.0 52.0 32.0 Sorbitol syrup (glycerine) 1.5 1.5 1.5 Perfume and preserving agent q.s. 1.0 1.0 1.0 100.0 100.0 100.0 WHAT WE CLAIM IS:

1. A cosmetic preparation containing coloured pulverous cellulose, wherein the cellulose is coloured with a colour-imparting substance which is neither water-soluble nor soluble in organic solvents.

11. A dry shampoo which contains a cosmetic preparation according to any one

of claims 1 to 10 inclusive.

12. A coloured antiseptic powder which contains a cosmetic preparation according to anv one of claims 1 to 10 inclusive.

13. A make-up which contains a cosmetic preparation according to any one of claims 1 to 10 inclusive.

14. A process for the manufacture of a cosmetic preparation as claimed in any one of claims 1 to 10 inclusive, which process comprises colouring the cellulose, the amount of colour imparting substance being between 0.1 and 8% of the weight of the cellulose and drying the coloured cellulose and, if desired, adding the coloured and dried cellulose to an active substance and/or adjuvant.

15. A process according to claim 14, wherein there is produced a mixture of pigment-forming acid addition salts of aromatic amines, reducing agents and substances serving for the control of the desired nuance, the acid addition salts are converted with an organic base into the corresponding free bases, the resulting mixture is dissolved in alcohol, cellulose is added, the resulting suspension is oxidized and the substrate obtained is dried.

16. A process according to claim 14, wherein a metal salt is dissolved in a solvent, the solution obtained is mixed with the cellulose and the metal salt is converted into a coloured pigment with an oxidising or reducing agent

17. A process according to claim 16, wherein potassium permanganate is used as the metal salt.

18. A process according to any one of claims 14 to 17 inclusive, wherein one or more perfumes are added.

19. A process according to any one of claims 14 to 18 inclusive, wherein one or more bactericidal agents are added.

20. A process according to claim 19, wherein said bactericidal agent is a quaternary ammonium salt of the general formula

R1 0 R4NR7R2 Halogen (T) L R3 ~ wherein R1 represents a methyl group, R2 represents an alkyl or aryl group, R9 represents an alkyl or aryl group, R4 represents an alkyl, aryl, aralkyl or glycidyl group and Halogen represents fluorine, chlorine, bromine or iodine.

21. A process for the manufacture of a cosmetic preparation as claimed in any one of claims 1 to 10 inclusive, substantially as hereinbefore described with reference to the foregoing Examples.

22. A cosmetic preparation according to any one of claims 1 to 10 inclusive, when manufactured by the process claimed in any one of claims 14 to 21 inclusive.

23. A method for the removal of fat from and for the cleansing of hair, which method comprises applying to the hair a coloured pulverous hair-treatment agent having a dry shampoo action, said agent containing coloured pulverous cellulose wherein the celllose is coloured with a colour imparting substance which is neither water-soluble nor soluble in organic solvents.