RU2170571C1 - Agent for hair staining - Google Patents

Abstract

FIELD: cosmetic industry. SUBSTANCE: agent for hair staining has the following components: high- -molecular alcohols, glycerol monostearate, liquid soap, chelating agent, alkalizing agent, staining components, perfume composition and agent has additionally also lanolin, carbamide, boric acid, vegetable oils, ascorbic acid and sodium sulfite as antioxidants and water. Staining agent is safety, it does not show irritating and allergizing effect on head skin and general toxic and sensitizing action. Natural components provide brilliance and silky properties for hair. EFFECT: improved quality and properties of agent. 4 cl, 3 ex

Description

 The invention relates to the cosmetic industry, in particular to the production of hair coloring agents, which are creamy masses of the oil-in-water system with the introduction of oxidative hair coloring components or dyes into them, directly selected by the hair from dyeing compositions.

 The subject of the invention is a hair dye, the composition of the creamy base of which ensures the stability of the creamy consistency of the mass during hair dyeing, optimal conditions and the most gentle dyeing regime, hair care, as well as a method for preparing the product. The colors obtained using these formulations are also distinguished by increased resistance due to more complete penetration of dyes.

Known hair coloring agents whose creamy base may contain high molecular weight alcohols (C ₁₂ -C ₂₀ fractions) [1, 2], glycerol monostearate [1], urea [3], potassium salts of fatty acids (liquid soap, for example, potassium oleate [ 1]). The composition of hair dyes on the market also includes complexones - salts of ethylene diamine-N, N, N ', N'-tetraacetic acid (to reduce water hardness), ascorbic acid and sodium sulfite (antioxidants), ammonia (alkalizing agent) and coloring components.

 As a part of the coloring agent described in the patent [1], cetyl alcohol and glycerol monostearate are used to give the desired consistency, potassium oleate, antioxidant sodium dithionite are used as an emulsifier, ethylenediamine-N, N, N 'tetrasodium salt is used to soften the water hardness. N'-tetraacetic acid, alkalizing agents are ammonia and potassium hydroxide.

The composition of the hair dye
The proposed creamy hair dye product contains high molecular weight alcohols (fractions C ₁₄ -C ₂₀ , mainly cetyl and stearyl alcohol), glycerol monostearate, liquid soap, complexon, alkalizing agent - ammonia, coloring components, perfume composition and water; characterized in that it additionally contains lanolin, urea, boric acid, as a liquid soap contains potassium salts of fatty acids of a hydrolyzate of vegetable oils, as an antioxidant - ascorbic acid and sodium sulfite, as a complexon - disodium salt of ethylene diamine-N, N, N ' , N'-tetraacetic acid, as an alkalizing agent, additionally contains sodium hydroxide in the following ratio of components, wt.%:
High molecular weight alcohols (fractions C ₁₄ -C ₂₀ ) - 8-25
Glycerol Monostearate - 0.1-12
Lanolin - 0.1-12
Liquid soap (in terms of 100% fatty acids) - 0.1-12
Disodium salt of ethylenediamine-N, N, N ', N'-tetraacetic acid - 0.001-1.0
Urea - 0.1-20
Boric acid - 0.01-10
Ascorbic acid - 0.01-5
Sodium sulfite - 0.01-5
Ammonia (in terms of 100%) - 0.01-6
Sodium hydroxide - 0.00-1.50
Coloring components (total content) - 0.0001-10.0
Perfume composition - 0.01-2.0
Water - Up to 100.0
As coloring components, oxidative dyeing compositions can be used containing at least one developer component from para-phenylenediamines, ortho and para-aminophenols and their derivatives, corresponding ortho and para-derivatives of pyridine and pyrimidine, as well as combination components (modifiers colors) from the derivatives of meta-dihydroxybenzene, meta-aminophenol, meta-phenylenediamine, the corresponding meta-derivatives of pyridine, hydroxy-derivatives of the naphthalene series.

 Dyes directly selected by the hair from dyeing compositions, including naphthoquinone derivatives, water-soluble nitro dyes (derivatives of nitro-aminophenols and nitro-phenylenediamines), as well as acidic, direct, active and dispersed dyes from among azo dyes, arylmethane, arylamine, anthraquinone and indigo dyes.

 The content of each individual coloring component when used as part of a hair dye is 0.0001-3.0% by weight.

 Fat components - high molecular weight alcohols, glycerol monostearate and lanolin - are introduced into the paint base as consistency-forming components, giving the base its creamy character. Glycerol monostearate and lanolin are also co-emulsifiers.

 As a liquid soap, the soap base of liquid toilet soap is used, which is a mixture of potassium salts of fatty acids of a hydrolyzate of vegetable oils (primarily sunflower, coconut, palm), which in this system is an emulsifier (surfactant) of an emulsion of fat components in the aqueous phase, and also a solubilizer of coloring components.

 The soap base and lanolin are dispersants when using dispersed dyes in the composition of hair dyes on the proposed basis.

 Ammonia, which is introduced into the composition of the agent as an alkalizing agent, in combination with boric acid, creates a medium (pH ~ 10.0), which is required for the synthesis of the dye and spares the hair and skin, and gives the solution a high buffer capacity.

 Sodium hydroxide is introduced into the composition of the product in an equimolar amount to neutralize mineral acids when using components of oxidative dyeing (aromatic amines) in the form of salts of these acids, as well as when using insoluble or hardly soluble components in water, whose solubility increases significantly in an alkaline medium, for example, compounds containing a carboxyl or hydroxyl group.

 Natural ingredients introduced into the composition give the hair shine and silkiness. Lanolin nourishes the hair, has a beneficial effect on the scalp. Urea moisturizes hair, prevents overdrying and softens them.

 A number of additional components introduced into the composition of the basis of the product in addition to a beneficial effect on the hair helps to optimize the coloring process. The influence exerted by them will be considered proceeding from the mechanism of dye formation from individual components of oxidative dyeing.

) молекулы цветокомпонентов проникают в волос (размер пор сухого волоса ~ 6

при максимальном набухании до 35

[4, 5]), где из них в процессе окисления формируются собственно красители. Последние превосходят по размеру исходные продукты (> 20

) и нерастворимы в воде. За счет этого они "застревают" и удерживаются в волосе. Поэтому, чем глубже цветокомпоненты проникнут в роговой слой до начала конденсации (образования первичного промежуточного продукта конденсации - лейкосоединения красителя), тем прочнее и интенсивнее будет окраска.The basic principle of oxidative dyeing is that it is readily soluble in water and small in size (~ 7-10

) molecules of flower components penetrate into the hair (dry hair pore size ~ 6

at maximum swelling up to 35

[4, 5]), where dyes themselves are formed during the oxidation process. The latter are superior in size to the original products (> 20

) and are insoluble in water. Due to this, they are "stuck" and held in the hair. Therefore, the deeper the flower components penetrate into the stratum corneum before the start of condensation (the formation of the primary intermediate product of condensation, the dye leuko compound), the stronger and more intense the color.

 As you know, the process of dyeing hair is carried out in several stages.

 1. Opening of the cuticle in an alkaline environment, hair swelling.

 2. Sorption of flower components due to diffusion through the opened cuticle scales deep into the stratum corneum.

где X = NH.3. The oxidation of the developer - the para-component (I) under the action of hydrogen peroxide in the presence of ammonia with the formation of a reactive particle - the quinoid derivative of the developer (II) - para-benzoquinoneimine or para-benzoquinondiimine [6], for example
Scheme 1

where X = NH.

где X, Y', Y'' = NH, O;
данная стадия протекает медленно, имеет первый порядок по каждому из компонентов и является лимитирующей, т.е. определяющей скорость всей реакции.4. The electrophilic attack of quinonimine (II), controlled in speed, mainly in the form of an iminium ion (III), on a neutral modifier molecule — the meta component (IV) with the formation of the primary intermediate condensation product — the dye leuko compound (V) [7], for example
Scheme 2

where X, Y ', Y''= NH, O;
this stage proceeds slowly, has a first order for each of the components and is limiting, i.e. determining the speed of the whole reaction.

где X, Y', Y'' = NH, O.5. The formation of indamine dye (VI) by oxidation of the leuko compound (V)
Scheme 3

where X, Y ', Y''= NH, O.

например, обрыв цепи и образование конечной формы красителя.6. Further chain extension (in the presence of unoccupied positions 4 and 6 in the modifier molecule) - condensation of the molecules of the flower components (alternately the developer and the modifier)
Scheme 4

for example, open circuit and the formation of the final form of the dye.

 7. Termination of the staining process - washing off the paint, closing the cuticle flakes by using special acidic rinses.

Based on the presented mechanism, the conditions most favored by the formation of the dye can be formulated:
a) achieving maximum opening of the cuticle and swelling of the hair during dyeing, to ensure the diffusion of flower components into the space between the fibers of the stratum corneum;
b) preventing the condensation of products in the mass of paint: the formation of the primary intermediate reaction product should occur already inside the hair, because of the large size of the leuko-compound of the dye is not capable of diffusion deep into the stratum corneum.

 Alkalizing agents [5], for example, ammonia, are traditionally used to open the cuticle and swell hair. When the hair swells, it can absorb a significant amount of water, and its diameter increases by 18-20% [4]. However, neutral components, such as urea used in the proposed formulation, can also serve this purpose.

 Due to its keratolytic properties and proteolytic activity, urea increases the hair capacity in relation to water and increases the ability of the horny layer of hair (keratin) to swell, which leads to an increase in pore size between protein molecules and facilitates the penetration of coloring components into deeper layers of the hair. The resulting color is more intense, resistant and uniform (less selective).

The introduction of an oxidizing type of urea in the amount of 5% in the paint makes it possible to approximately halve the content of color-forming components, which in addition to the obvious savings has other important advantages:
- the rate of condensation of products in the mass of paint decreases: with a proportional decrease in the concentration of each of the components, the rate of formation of the leuco compound of the dye decreases in proportion to the square of the degree of decrease in the concentration of components, which leads to a more complete selection of components from the mass of paint;
- reduces the possibility of allergic and other undesirable effects of color components during staining due to their lower concentration in the composition.

 Obviously, hair swelling under the action of an aqueous urea solution occurs under much more sparing conditions than with the traditional use of highly alkaline media (usually pH 10.5-11.5). Reducing the alkalinity of the coloring composition to a pH of less than 10.0 allows you to maintain the structure of the hair, and since urea helps to moisturize the hair, it does not dry out, remain soft and easy to comb both during staining and after it even without the use of special rinsing agents that help close the flakes cuticles and hair compression.

 When the urea content is more than 10%, a decrease in the color intensity is observed, which is most likely due to the fact that after equilibrium is reached, the desorption rate begins to exceed the rate of sorption processes. The optimal input of urea to optimize the staining process is from 5 to 10% and can vary for different types of hair and depending on the further composition of the coloring agent.

 The role of the product that prevents the condensation of products in the mass of paint is played by ascorbic acid, which is widely used in the manufacture of hair dyes as an antioxidant and has several advantages over other reagents, such as, for example, thioglycolic acid and sodium sulfite [8].

где X,Y = NH, O.The use of sodium sulfite in the composition of oxidative-type hair dyes as the only antioxidant is impractical because, unlike ascorbic and thioglycolic acids, it does not bind free oxygen, but restores the resulting quinoid compounds (X). Moreover, the reaction mechanism is such that, as a result, the sulfo group is attached to the aromatic core of the developer component molecule with the formation of aromatic sulfonic acid (XII) (Scheme 5)
Scheme 5

where X, Y = NH, O.

 Obviously, in this process, the final product (XII) differs from the original (IX), which leads not only to a change in the staining results, but also to a decrease in the color fastness.

 In contrast to sodium sulfite, ascorbic acid, when introduced into the formulation, is able to prevent the oxidation of the paint, being oxidized by air oxygen diffusing into the paint mass during production and during storage. The recommended input rate for ascorbic acid when used in conjunction with sodium sulfite is 0.3%.

 However, with an increase in the content of ascorbic acid (up to 1.5%), an increase in the intensity of staining is detected. In this case, the mass of paint does not stain when mixed with an oxidizing agent for 2-10 minutes. The hair begins to dye in an intense color, while the mass of the paint remains colorless.

 This is due to the fact that ascorbic acid binds the active oxygen generated during the interaction of ammonia with hydrogen peroxide, preventing the synthesis of the dye even at the initial stage (Scheme 1). This means that flower components can freely penetrate deep into the hair, which, obviously, should lead to an increase in the degree of color stability.

 To improve the staining results, a number of patents suggest the use of a number of weak acids - tartaric [2], citric and lactic [2, 9], phosphoric and glycolic acids [9]. In all cases, patent authors note an increase in color intensity.

 The introduction of boric acid into the composition of the coloring agent leads to a decrease in the oxidizability of the paint in the mass, which, by analogy with the action of ascorbic acid, manifests itself in a decrease in the intensity of the coloring of the coloring composition under the influence of an oxidizing agent.

Так как свободная электронная пара аминогруппы вносит решающий вклад в формирование несвязывающей молекулярной орбитали, являющейся в то же время высшей занятой молекулярной орбиталью (ВЗМО), то в соответствии с теорией молекулярных орбиталей строение комплекса может быть представлено в виде формулы (XIV). Поскольку именно на ВЗМО происходит атака активной частицы в реакции окисления, молекула аминосоединения (I) оказывается защищена на какое-то время от действия окислительных агентов. По мере окисления молекул свободного аминосоединения и выведения его из зоны реакции равновесие смещается в сторону распада комплекса. Таким образом, действие борной кислоты сводится к снижению активной концентрации пара-компоненты (I) в реакционной массе по отношению к реакции окисления. Время замедления реакции должно оказаться достаточным для достижения молекулой поверхности волоса и пенетрации в него, где, в том числе и за счет образования координационных связей с кератиновым волокном, следует разрушение комплекса, и молекула свободного аминосоединения становится доступной действию агента окисления. Дальнейшие процессы происходят уже внутри волоса.The following mechanism of action of boric acid on the process of hair coloring is proposed. Apparently, the observed effect is associated with a slowdown in the initial stage of the reaction — oxidation of the para-component (I) to the quinoid derivative (II) (Scheme 1). Since boric acid is in solution mainly in an undissociated form (pK _a = 9.15), there can be no talk of protonation of the free amino compound (I). At the same time, being a Lewis acid, boric acid could form complexes with aromatic amines (Lewis bases) of the type (XIII) due to coordination (donor-acceptor) bonds, which are in a state of dynamic equilibrium with free amine compounds (Scheme 6). Thus, the free electron pair of the nitrogen atom of the amino group is blocked
Scheme 6

Since the free electron pair of the amino group makes a decisive contribution to the formation of a non-binding molecular orbital, which is at the same time the highest occupied molecular orbital (HOMO), in accordance with the theory of molecular orbitals, the structure of the complex can be represented in the form of formula (XIV). Since it is precisely the HOMO that the active particle attacks in the oxidation reaction, the amino compound molecule (I) is protected for some time from the action of oxidizing agents. As the molecules of the free amino compound are oxidized and removed from the reaction zone, the equilibrium shifts toward the decomposition of the complex. Thus, the effect of boric acid is reduced to a decrease in the active concentration of the para-component (I) in the reaction mass with respect to the oxidation reaction. The reaction slowdown time should be sufficient for the molecule to reach the hair surface and penetrate into it, where, including due to the formation of coordination bonds with the keratin fiber, the complex is destroyed, and the free amino compound molecule becomes accessible to the oxidation agent. Further processes occur already inside the hair.

 The combined use of the considered components - urea, ascorbic acid and boric acid - can significantly reduce the use of expensive and harmful components in terms of their effect on the human body.

 We give the compositions (for coloring components) of hair dyes of oxidative type. Experimental batches of all shades have been developed.

Example 1
Means intended for dyeing hair in light natural (blond, light blond, blond), (medium blond ash, ashen blond) and golden (light blond golden, golden blond, golden ash blond) shades (Table 1) .

Example 2
Means designed for coloring hair in shades of red (copper, mahogany, pomegranate, burgundy, eggplant, black tulip) (table. 2).

Example 3
Means intended for dyeing hair in brown shades (light brown, brown, golden chestnut, chestnut, nut) (table. 3).

 Immediately before use, this product is mixed with a 6% solution of hydrogen peroxide in a ratio of 1: 1, applied to the hair and left for 30 minutes, then rinse thoroughly with water. In conclusion, wash your hair with shampoo and hair balm. The result is hair coloring in accordance with the results.

Method for preparing hair dye
1. Preparation of the melt of the fat phase (phase A).

Fat components - high molecular weight alcohols, glycerol monostearate and lanolin are melted at a temperature of 80-100 ^o C.

 2. Preparation of soap solution (phase B).

The soap base of the liquid toilet soap is introduced into demineralized water (~ 50% of the recipe amount), sodium sulfite, sodium hydroxide and coloring components are added, the dissolution of which is carried out in an alkaline medium, and heated to a temperature of 70-90 ^o C.

 3. Preparation of an acidic solution of dyeing components (phase B).

The remaining components of the dyeing, boric acid, ascorbic acid, urea, disodium salt of ethylenediamine-N, N, N ', N'-tetraacetic acid are dissolved in demineralized water (~ 40% of the formulation amount), heating with stirring to a temperature of 70-90 ^o C .

 The remaining amount of demineralized water (~ 10% of the recipe amount) is used to flush the equipment and bring the mass of the product to the final volume.

 4. Preparation of hair dye.

Hot soapy solution (phase A) is introduced into the melt of fatty components (phase B), cooled with vigorous stirring to 40-50 ^o C.

 An acidic solution of the dyeing components (phase B) is added to the resulting creamy mass and mixed until a homogeneous mass is obtained.

Cool to a temperature of 30-40 ^o C, after which make ammonia water, perfume composition; adjusted with water to 100%.

 The finished mass is analyzed for compliance with regulatory and technical documentation, and then packaged in hermetically sealed tubes.

 Immediately before use, the product is mixed with an aqueous solution of hydrogen peroxide or hydroperite with a content of hydrogen peroxide in terms of 100% in an amount of from 6 to 9%.

 The proposed hair dye products have been tested, prepared for release and will be launched into mass industrial production. Experimental batches have been developed.

 All hair dyeing products have passed toxicological and clinical trials at the Accredited Testing Laboratory Center "Beauty Institute".

 Toxicological tests were performed on laboratory animals. Acute toxicity, irritating (single and repeated) and sensitizing effects were studied.

 As a result of the tests, it was found that hair dye products do not have a general toxic, skin-irritating and sensitizing effect.

 Clinical trials were conducted on 20 clinically healthy individuals, observations were carried out for 30 days.

 Drip and compression tests (absence of hyperemia, swelling of rashes) were performed, the content of total lipids (sebometry) and moisture (moisture measurement) in the skin, the level of pigmentation (pigmentometry) and the skin profile were checked.

 As a result of the tests, it was found that the hair dye is harmless, does not have an irritating and allergic effect, and is intended for hair care.

List of references
1. The patent of Germany DE 4408506, CL A 61 K 7/13 (prototype).

 2. German patent DE 4421031, class A 61 K 7/13.

 3. RF patent RU 2008892, cl. A 61 K 7/13.

 4. I.V. Nosar, V.A. Yushenko, D.A. Gabrielian. On Sat "Tr. All-scientific research institute and design institute of chemical chemistry", 1976, no. 4, 40-49.

 5. I.I. Filonenko, S.N. Grushko. Hair properties and methods of their research. On Sat TSNIITEI PISCHEPROM, 1984, no. 9, 1-16.

 6. J.F. Corbett, J. Soc. Cosmet. Chem., 1969, 20, 253.

 7. J.F. Corbett, J. Soc. Cosmet. Chem., 1973, 24, N 2, 103-134.

 8. H. Wilmsmann, E. Konrad; US Patent 3,337,411.

 9. The patent of Germany DE 19653496, cl. A 61 K 7/13.

Claims (3)

1. A hair dye containing high molecular weight alcohols (fractions C ₁₄ -C ₂₀ , mainly cetyl and stearyl alcohol), glycerol monostearate, liquid soap, complexon, alkalizing agent - ammonia, coloring components, perfume composition, antioxidant and water, characterized in that additionally contains lanolin, urea, boric acid, as a liquid soap contains potassium salts of fatty acids of a hydrolyzate of vegetable oils, as an antioxidant - ascorbic acid and sodium sulfite, as a complexon a - disodium salt of ethylenediamine-N, N, N ', N'-tetraacetic acid, additionally contains sodium hydroxide as an alkalizing agent in the following ratio, wt.%:
High molecular weight alcohols (fractions C ₁₄ -C ₂₀ ) - 8.0 - 25.00
Glycerol monostearate - 0.1 - 12.00
Lanolin - 0.1 - 12.00
Liquid soap (in terms of 100% fatty acids) - 0.1 - 12.00
Disodium salt of ethylenediamine-N, N, N ', N'-tetraacetic acid - 0.001 - 1.00
Urea - 0.1 - 20.00
Boric acid - 0.01 - 10.00
Ascorbic acid - 0.01 - 5.00
Sodium sulfite - 0.01 - 5.00
Ammonia (in terms of 100%) - 0.01 - 6.00
Sodium hydroxide - 0.00 - 1.50
Coloring components (total content) - 0.0001 - 10.00
Perfume composition - 0.01 - 2.00
Water - Up to 100.0
2. Means for dyeing hair according to claim 1, characterized in that the dyeing components are selected from the group of oxidative dyeing compositions containing at least one developer component from para-phenylenediamines, ortho- and para-aminophenols and their derivatives corresponding to ortho- and para-derivatives of pyridine and pyrimidine, as well as combination components (color modifiers) from the derivatives of meta-dihydroxybenzene, meta-phenylenediamine, the corresponding meta-derivatives of pyridine, hydroxy derivatives of the naphthalene series.  3. A means for dyeing hair according to claims 1 and 2, characterized in that the dyeing components are selected from the group of dyes directly selected by the hair from dyeing compositions, including naphthoquinone derivatives, water-soluble nitro dyes (derivatives of nitro-aminophenols and nitro-phenylenediamines), as well as acidic, direct, active and dispersed dyes from azo dyes, arylmethane, arylamine, anthraquinone and indigo dyes.  4. Means for dyeing hair according to claims 1 to 3, characterized in that it contains each individual dye component introduced into the composition by weight of 0.0001 - 3.0%.

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