WO2013184031A1

WO2013184031A1 - Hair colouring formulation

Info

Publication number: WO2013184031A1
Application number: PCT/RU2013/000422
Authority: WO
Inventors: Olga Ivanovna CHISTYAKOVA
Original assignee: "UNICOSMETIC" LLC
Current assignee: "UNICOSMETIC" LLC
Priority date: 2012-06-07
Filing date: 2013-05-22
Publication date: 2013-12-12
Anticipated expiration: 2014-12-07
Also published as: DE112013002843T5; PL410391A1; RU2493814C1; EA201491074A1

Description

HAIR COLOURING FORMULATION

This is an invention in the cosmetics industry, namely production of hair dye formulations constituting consistent creamy water-oil type emulsified preparations and containing dyeing components (oxidation dyes and direct dyes).

This invention belongs to ammonia-free formulations which do not damage hair structure while providing deep and lasting dyeing of all hair types, including grey hair.

Hair dye formulations may have liquid or creamy consistency. Liquid formulations are used primarily for hair tinting, since the small amount of the dyeing preparation retained by the hair is insufficient for producing intensive color [US 7198651, A 61 K 7/13; US 7241318, A 61 K 7/13]. Creamy formulations are more convenient for use. Thickening is achieved by addition of cellulose granules [US 7204856, A 61 K 7/13]; cationic cellulose derivative - mix of Polyquaternium- 10 and acrylamide/ammonium acrylate-13 and polyacrylate-13 ' copolymer [US 1813264, A 61 K 8/81]; associative anionic thickening polymer produced from acrylic acid, alkyl acrylate and copolymerized poly ethylene monomer; alkyl- modifled cationic thickening polymer produced from hydroxy ethyl cellulose and non ionic polyurethane polymer. [US 7300470, A 61 K 7/13. Emulsified preparations, e.g. preparations containing higher molecular weight alcohols C12 - C20, glycerol monostearate, potassium salts of fatty acids [US 7204859, A 61 K 7/13; EP 1813263, A 61 8/81] are commonly used. However, the use of creamy formulations has a slower rate of cuticle exposure and keratin swelling required for enlargement of submicroscopic keratin pores and keratin hydration with water and water-based solutions of dyeing agents, and to this effect alkali agents are added to such formulations. Such agents catalyze the saponification of the fat layer on the hair, thus providing water access to keratin surface and facilitating keratin swelling. The diameter of polymer macromolecules increases by 18-20% and allows diffusion of dye molecules within the fiber; the size of dye molecules does not exceed 6A.

The majority of the described patents offer oxidation dyes for deep and lasting (permanent) hair dyeing. This is determined by the following requirements to hair dyes: 1) the dyeing process must take a short period of time at room temperature and may not result in hair fiber or scalp damage; 2) hair dyes must produce natural hair colur with minimum scalp pigmentation; 3) limited dyeing process duration requires application of preparations with high concentration of the colouring agent; 4) colouring agent diffusion in human hair is slower than in wool keratin, which requires smaller size and molecular weight pigments. Only oxidation colouring agents meet these specifications. [Yoko K., Yoshikatsu Yo. Proposed hair dyeing pattern// J. Cosmet. Sci. 2009. Vol. 31, No. 3. Page 273],

Being referred to as dyeing agents, actually they constitute intermediate material product in dye synthesis inside hair fiber producing water-insoluble pigment accounting for high permanence of the dye. Similarly to photographic process, these preparations are referred to as developing solutions. They include benzene and naphthalene aromatic o- and p-diamines, o- and p-aminophenols and their derivatives, similar pyridine, pyrimidine and other heterocycle derivatives.

After oxidation of these compounds, e.g. with hydrogen peroxide, persulfates, perborates, potassium or sodium bichromate and chlorate, they transform into quinone amides, and then into indamines or indanilines.

Fig. 1

Further oxidation results in phenazine structures consisting of multiple hetero rings:

Fig.2

Since these reactions result in a mix of multiple products, the hair is dyed into muted, diffused tones completely imitating natural colors - blond, brown and chestnut.

Developing solutions, or color bases are generally applied in combination with so-called color components. These include m-diamines, m-aminophenols, phenols, naphthols, pyrazolones, β-diketones and their derivatives. When alone, these compounds have no dyeing effect, yet in reaction with the developing solution they expand the color range of dyeing preparations, e.g. p- phenylenediamine and in combination with m-toluylendiamine produces red phenazine dye, while in combination with 2,4-diaminoanisol it produces purple- blue indamine:

Fig. 3

Direct dyes - nitro acid, base (cationic), active or disperse - are added to dye preparations for achieving the desired share, yet they are mostly retained on hair surface due to hydrogen binding and Van der Waals and London forces, without deep penetration due to the large size of the molecules and low diffusion rate, and, consequently wash out quickly.

Ammonium has been used for decades as an alkaline agent for hair structure opening [FR 2856292, A 61 K 7/13; UA 70370, A 61 K 7/13]. This provides lasting and effective hair dyeing, specifically on problem hair, yet eventually the hair becomes thinner, fragile and split. Therefore, recently a tendency to produce low ammonium content or ammonia-free dyes with the same dyeing quality developed.

There exists a hair dyeing product containing oxidation dyes and oxidizing agent in a cosmetically approved water medium at base pH level wherein the alkaline agent is composed of a combination of sodium metasilicate and a small amount of ammonium which does not exceed 1.6%. The authors state that this type of product features a less obvious ammonium odor and lower risk of scalp allergic response while producing the required level of hair dyeing intensity. Apart from the above components, hair dye may contain various traditional hair dye additives, such as anionic, cationic and non-ionic surfactants, fatty alcohols, fatty acids, anionic, cationic, non ionic, amphoteric or zwitterionic polymers and their combinations, organic thickeners and polymer thickeners, antioxidants and deoxidants, passivators, UV-filtering agents, waxes, flavours, conditioners, dispersants, pearling agents, keramides, botanical, mineral and synthetic oils, vitamins or provitamins, i.e. panthenol, and opacifiers [RU 2283643, A 61 K 8/25; A 61 K 8/19; A 61 K 8/23; A 61 Q 5/10].

This invention is most similar the present formulation. The development task and positive result of the present hair dye formulation consist in an ammonia-free hair dye formulation where the alkaline medium with pH = 10-10,5 is produced with buffer solution of aminomethylpropanol and ammonium sulfate, which ensures deep and intensive hair dyeing without damage and allergic response, itching or tingling and absence of acrid ammonium odor.

The present hair dyeing solution consists of two phases - Phase A and Phase B - stored separately from each other and mixed immediately prior to use. Phase A is a creamy substance consisting of an oil-water emulsion and containing oxidation dyes and/or their salts in alkali medium and direct dyes. Phase B is an oxidizing agent consisting of hydrogen peroxide water solution with 3,5 pH. The distinctive feature of the present invention consists in ammonia-free production of Phase A alkali medium, from mix of 0,5 to 0,6% aminomethylpropanol with 0,5-1,5% ammonium sulfate. This mix produces buffer solution for pH = 10-10,5 range, thus providing intensive and damage-free hair dyeing. Furthermore, this formulation is free from acrid ammonium odor and does not cause skin itching or tingling.

Apart from the above components, the present dye composition includes standard cosmetic cream components:

Phase A: thickener - cetearyl alcohol - 6,0-10,0% emulsifiers: glycerol monostearate, ceteareth-30,

cocamide MEA, PEG-40 hydrogenated

castor oil - 7,5-25,0% organic solvent: hexyldecanol,

hexyld decil laurate, propylene glycol,

etoxydiglycol - 3,5-1 1,0% conditioning agent: quaternium -70,

hydrolyzed keratin, avocado oil, dimethicone - 2,3 - 12,0% deoxidant: sodium sulfite, sodium erythorbate - 0,3 - 1,4% perfume - 0,2 - 0,5% preservative: methylparaben, propylparaben, ethylpa- raben in phenoxyethanol - 0,1 - 0,6% chelating agent - tetrasodium ethylene diamine- tetraacetate - 0,01 - 0, 1 % provitamins and vitamins: panthenol, olive

leaf extract - 0,5 - 3,0% mica, titanium dioxide - 0,5 - 0,8% water up to 100%

Oxidation dye content in the patent formulation ranges from 0,0001% to 3,0% These are dye developing agents: o- and p-phenylenediamines and aromatic o- and p- aminophenols (benzene, naphthalene, anthraquinone) and nitrogenated hetero cycles (pyrazole, pyrimidine, pyridine etc.). Pigmentation components - m- aminophenols, aromatic and heterocyclic di- and trihydroxy derivatives, their nitro-, chloro-, metoxy- and etoxy derivatives etc.

The hair dye formulation may also contain up to 0,4% direct action dyes (acidic, base (cationic), active, dispersed).

Phase B:

Hydrogen peroxide oxidation agent, prepared separately and packaged in special bottles. Ingredients:

hydrogen peroxide 1 ,5 - 12,0%

cetearyl alcohol 2,0 - 4,0%

ceteareth-20 1,0 - 5,0%

cetrimonium chloride 1 ,0 - 3,0%

phosphorous acid (cone.) 0,1 - 0,5%

tetrasodium ethylendiamine tetraacetate

(EDTA) 0,05 - 0,3%

sodium stannate 0,015- 0,1 %

Table 1

Example 1

Phase A formula - "Copper brown"

Item Description % content no.

1 Cetearyl alcohol 6,5

2 Glyceryl stearate 3,0

3 PEG-40 hydrogenated castor oil 3,2 Ceteareth-30 3,5

Cocamide MEA 5,0

Avocado oil 2,0

Quaternium-70 0,5

Hexyldecanol, hexyl decyl laurate 3,0

Phenyl trimethicone 0,4

Bis (Ci3-Ci₅alcoxy) PG amodimethicone 0,4

Dimethicone 1 ,0

Etoxydiglycol 3,0 tetrasodium ethylendiamine tetraacetate 0,05

Sodium sulfate 0,4

Sodium erythorbate 0,8

Panthenol 2,0

Keratin hydrolyzate 0,3

Olive leave extract in propylene glycol 0,7

Mica, titanium dioxide 0,5

Ammonium sulfate 1,3

Methylparaben, propylparaben, ethylpa- 0,1 raben in phenoxyethanol

Perfume 0,4

Toluene-2,5 diamine sulfate 1,2 m-Aminophenol 0,1 p-Aminophenol 0,7

4-Amino-2-hydroxytoluene 0,1

2-Amino-6-chloro-4-nitrophenol 0,3

Resorcine 0,4

Aminomethylpropanol 3,2

Water up to 100 Table 2

Example 2

Phase A formula - "Copper brown"

Item Description % content no.

1 Cetearyl alcohol 9,0

2 Glyceryl stearate 5,1

3 PEG-40 hydrogenated castor oil 4.6

4 Ceteareth-30 3.3

5 Cocamide MEA 5.0

6 Avocado oil 0.6

7 Quaternium-70 0.5

8 Hexyldecanol, hexyl decyl laurate 3.0

9 Phenyl trimethicone 0.8

10 Bis (Ci₃-Ci₅alcoxy) PG amodimethicone 1.0

1 1 Dimethicone 1.0

12 Etoxydiglycol 3.0

13 tetrasodium ethylendiamine tetraacetate 0.05

14 Sodium sulfate 0.1

15 Sodium erythorbate 0.1

16 Panthenol 0.5

17 Keratin hydrolyzate 0.3

18 Olive leave extract in propylene glycol 0.3

19 Mica, titanium dioxide 0.5

20 Ammonium sulfate 1.5

21 Methylparaben, propylparaben, ethylpa- 0.1 raben in phenoxyethanol

22 Perfume 0.4

23 Toluene-2,5 diamine sulfate 1.5

24 m-Aminophenol 0.19

25 Resorcine 0.4

26 2-methylresorcine 0,15

27 Aminomethylpropanol 2.8

28 Water up to 100

Table 3

Example 3

Phase A formula - "Dark blond"

Item Description % content no.

1 Cetearyl alcohol 8.5

2 Glyceryl stearate 5.2

3 PEG-40 hydrogenated castor oil 3.4

4 Ceteareth-30 3.2

5 Cocamide MEA 2.5

6 Avocado oil 0.65

7 Quaternium-70 1.1

8 Hexyldecanol, hexyl decyl laurate 2.4

9 Phenyl trimethicone 0.3

10 Bis (Ci3-Ci₅alcoxy) PG amodimethicone 0.5

1 1 Dimethicone 2.0 12 Etoxydiglycol 3.1

13 tetrasodium ethylendiamine tetraacetate 0.1

14 Sodium sulfate 0,25

15 Sodium erythorbate 0,5

16 Panthenol 2,2

17 Keratin hydrolyzate 0,3

18 Olive leave extract in propylene glycol 0,65

19 Mica, titanium dioxide 0,5

20 Ammonium sulfate 1,3

21 Methylparaben, propylparaben, ethylpa- 0.5

raben in phenoxyethanol

22 Perfume 0.5

23 p-Phenylenediamine 0,6

24 m-Aminophenol 0.055

25 Resorcine 0.32

26 2-amino-3-hydroxyethylaminoanisole sulfate 0,014

27 Aminomethylpropanol 3,0

28 Water up to 100

Hair dye preparation

1. Creamy product (phase A) Fatty phase melting.

Fat components - high molecular weight alcohol, cocamide MEA, quaternium-70, avocado oil, hexydecanol, hexyl decyl laurate, glyceryl stearate, PEG-40 hydrogenated castor oil and ceteareth-30 are heated to molten state at 45-55°C and stand at this temperature for 30 min. Water solution of the colorants.

The required amount of water is heated to 45-55°C and mixed with the salt ingredients - sodium erythorbate, sodium sulfite, tetrasodium ethylenediamineetraacetate (EDTA), ammonium sulfate. The solution is mixed continuously at this temperature for 30 minutes, etoxydiglycol, panthenol, dyes, mica and titanium dioxide are added, argon feed is activated, the solution is heated to 65-70°C and stands for 60 min.

The fatty phase is mixed with the water solution of the colorants at 65-70°C, stands for 30 minutes, then it is cooled to 40°C and silicones, perfume, olive leave propylene glycole extract, keratine hydrolisate, preservative and aminomethyl- propanol are added. The preparation is mixed continuously for 30 minutes, then test samples are taken. In case of positive result of the test for

conformity to applicable standards and specifications, the product is packaged into tubes.

2. Oxidation agent (phase B).

The required amount of water is heated to 45-50°C, ceteareth-20 is introduced and the temperature is raised to 65-70°C, cetearyl alcohol and cetrimonium chloride are introduced and the mass is mixed constantly for 60 min. Then it is cooled to 30°C and sodium stannate is added. EDTA Tetrasodium salt water pre- solution (1 :10), orthophosphoric acid and the remaining water are introduced, followed by hydrogen peroxide. The mass is mixed constantly for 30 min, then test samples are selected and in case of positive test result the product is packaged into special bottles.

Phase A is mixed with phase B immediately prior to use. All hair dye preparations successfully passed toxicological and clinical tests at the Accredited test laboratory of the Federal state funded institution "R.R. Vreden Russian research institute of traumatology and orthopedics under the Ministry of health and social development.

Toxicological tests were evaluated by the cytotoxic action (CTA) based on the morphological parameters of human embryo dermal fibroblast monolayer film integrity and by evaluation of conjunctiva irritation with the aid of chicken embryo choryoallantois membrane.

Clinical tests were conducted on healthy volunteers with no allergic background, in groups of 25 persons from 18 to 45 years old.

Toxicological and clinical tests have proved that the hair dye formulations have no cytotoxic, skin irritation or sensitizing effect.

Thus we have developed an ammonia-free hair dye formulation where the alkaline medium with pH = 10-10.5 is produced with buffer solution of aminomethylpropanol and ammonium sulfate, which ensures deep and intensive hair dyeing without damage and allergic response, itching or tingling and absence of acrid ammonium odor.

References

1. US 7198651 , A 61 K 7/13

2. US 7241318, A 61 K 7/13

3. US 1825883 , A 61 Q 5/06

4. RU 2356590, A 61 Q 5/10

5. US 7427301, A 61 Q 5/10

6. US 7204856, A 61 K 7/13

7. US 1813264, A 61 K 8/81

8. US 7300470, A 61 K 7/13

9. US 7204859, A 61 K 7/13 EP 1813263, A 61 K 8/81

Yoko K., Yoshikatsu Yo. Proposed hair dyeing pattern// J. Cosmet. Sci. 2009. Vol. 31, No. 3. Page 273].

FR 2856292, A 61 K 7/13

UA 70370, A 61 K 7/13

RU 2283643, A 61 K 8/25; A 61 K 8/19; A 61 K 8/23; A 61 Q 5/10

Claims

Patent claim

1. The present hair dye formulation is characterized by its composition of 2 phases which are stored individually from each other and mixed together immediately prior to use, wherin the first phase comprises an oxidation agent in the form of water solution containing hydrogen peroxide, pH = 3,5; and the second phase consists of a mix of aminomethylpropanol and ammonium sulfate constituting a pH=10-10,5 buffer, which are introduced into a creamy emulsion consisting of cetearyl alcohol as thickener, surfactants - glycerol monostearate, ceteareth-30, cocamide MEA or PEG-40 hydrogenated castor oil as emulsifiers; oxidation dyes and/or their inorganic acids and/or direct action dyes as dye components, hexyldecanol, hexyldecyl laurate, propyleneglycol or etoxydiglycol as organic solvents; sodium erythorbate and sodium sulfite as dexodation agents; tetrasodium ethylenediaminetetraacetate as water deionization chelating agent; quaternium-70, hydrolized keratin, avocado oil or dimethicone as conditioners; methylparaben, ethylparaben or propylparaben in phenoxyethanol as preservatives; panthenol and/or olive leave extract as vitamins and provitamins; mica or titanium dioxide as pearling agents, perfume, in the following concentrations mass ratios, % mass: thickener - cetearyl alcohol - 6,0-10,0% emulsifiers: glycerol monostearate, ceteareth-30,

cocamide MEA, PEG-40 hydrogenated

castor oil - 7,5-25,0% organic solvent: hexyldecanol,

hexyld decil laurate, propylene etoxydiglycol

conditioning agent: quaternium -70,

hydrolyzed keratin, avocado oil, dimethicone deoxidant: sodium sulfite, sodium erythorbate perfume preservative: methylparaben, propylparaben, ethylpa

raben in phenoxyethanol chelating agent - tetrasodium ethylene diamine- tetraacetate provitamins and vitamins: panthenol, olive

leaf extract mica, titanium dioxide - 0,5 - 0,8% water up to 100%

2. Hair dye formulation under p. 1 wherein aminomethylpropanol and ammonium sulfate forming a buffer for pH=10-10,5 are introduced into a creamy emulsion in the amount of 0,5-6,0% and 0,5%-l,5% accordingly.

3. Hair dye formulation under p. 1 wherein the dyes contain oxidation dye components are developing agents consisting of aromatic o- and p- phenylenediamines and o- and p-aminophenols (benzine, napthalene, anthraquinone) and nitrogenated hetero cycles (pyrazole, pyrimidine, pyridine etc.), and pigmentation components - m-aminophenols, aromatic and heterocyclic di- and trihydroxy derivatives, their nitro-, chloro-, metoxy- and etoxy derivatives etc.; the pigmentation components may also be selected from direct action dyes (acidic, base (cationic), active, dispersed, vat) constituting nitro, antraquinone, azo, arylmethane, arylamine, phthalocyanine, indigoid and thioindigoid dyes and their heterocyclic counterparts.

4. Hair dye formulation under p. 1 wherein the content of each individual dyeing component introduced into the preparation ranges from 0,0001 to 3,0%.

5. Hair dye formulation under p. 1 wherein the oxidation agent stored in an individual bottle and mixed with the dyeing preparation immediately prior to use contains hydrogen peroxide 1 ,5 - 12,0%, cetearyl alcohol 2,0 - 4,0%, ceteareth-20 1 ,0 - 5,0%, cetrimonium chloride 1,0 - 3,0%, phosphorous acid (cone.) 0,1% - 0,5%, EDTA tetrasodium salt 0,05% - 0,3%, sodium stannate 0,015 - 0,1%.