NO116772B - - Google Patents

Description

Hair dye.

It is known that certain derivatives of anthraquinone can be used, e.g. such as contain amino, hydroxyl, carboxyl or sulfo groups in the nucleus for hair dyeing, especially also human hair.

In the practical use of these known compounds, it is necessary to carry out the dyeing at temperatures between 40 and 60°C. Therefore, heat hoods and similar devices are necessary. Furthermore, the absorbency of these known dyes when incorporated into creams or pastes as they are often used in practice is mostly poor.

It has been found that hair dyes containing the anthraquinone dyes discussed in more detail below surprisingly do not show the above-mentioned disadvantages. The new hair dyes according to the invention are characterized by the content of aminoanthraquinone dyes which in the core are free of acidic groups and which contain a hydrocarbon residue with the formula linked over an oxygen or nitrogen atom to the anthraquinone residue

where n is equal to 1-4" and X means one of the groups -N(CH3)2, -NH(CH2)3NH2, -NH(CH2)2NH2, -NH(CH2)2OH, -NH-C0-NH2 or -NH -CS-NH2, as the dyes are preferably incorporated into a cream containing wetting agent and/or detergent.

The anthraquinone derivatives that are used can be prepared by reacting aminoanthraquinones that contain a reactive halogen atom, an NO,, or OH group, with compounds of the general formula Y(CH2)nX, where X has the same meaning as above and where Y means a group suitable for reaction with the substituted aminoanthraquinone, such as e.g. an OH- or an NH2~ group or a halogen atom.

Consequently, compounds such as e.g. pyridine-2-carbinol, pyridine-2-ethanol, 4-picolylamine, 2-picolyl chloride, dimethylaminoethanol, N-ft-oxetylpropanediamine-(1,3) > ethanol-isopropanol-amine, diethylenetriamine, triethylenetetramine, /5-oxyethylene -urea, t>-oxetylthiourea f, 3-allyloxy-2-oxypropylarin-(1).

The aminoanthraquinone residue must always be free of acidic groups, such as hydroxyl, carboxyl or sulfo groups, but it can, if desired, also contain other substituents, such as e.g. halogen or nitro groups.

The hair dyes can be mixed with Qnskelig moisturizing resp. detergents, especially anionic or non-ionic ones. As moisturizing or detergent, alkylbenzene sulphonates, fatty alcohol sulphates, alkyl sulphonates, fatty acid ethanol amides, addition products of ethylene oxide to fatty acids and fatty alcohols can then be used.

The absorbency of the above-mentioned dyes is also good when mixed with such agents. The hair dyes can thus be produced in the form of shampoos, especially cream-shaped shampoos, which are often desirable in practice.

To the agents according to the invention, thickening agents such as e.g. methyl cellulose, starch, higher fatty alcohols, vaseline, paraffin oil and fatty acids as well as perfume oil or hair care products, such as e.g. pantothenic acid and cholesterol.

The additives are then used in the usual quantities for these purposes. Here, amounts of 0.5 - 30% are particularly taken into account as wetting agent additives and as thickening agent amounts of 0.1 - 25%, calculated for the overall mixture* The concentration of the dyes is, depending on the intended use, up to 5%, preferably however 0.1 - 2%, likewise calculated on the overall mixture.

Similarly, to the new hair dyes, well-known permanent curling agents based on mercapto group-containing compounds such as thioglycolic acid, thiolactic acid, mercaptopropane or mercaptobutanesulfonic acid can be added. The hair dyes can, if desired, be processed from the start with these additives, as the dyes used have the advantage that they are also stable in the presence of these substances.

With the new hair dyes, hair dyeing can be carried out without the aid of heating caps or the like at temperatures below 40°C, preferably room temperature. The hair dyes can be adjusted to a pH range of 7-10. A pH range of 8.5-9.5 is preferably used. The agents can be used to color gray hair or also to recolour hair. The colors are excellently washable and wear-resistant. Likewise, the production of permanent curls with hair that has been treated with the hair dyes according to the invention is possible without a change in the color tone taking place in practice.

Directly absorbing dyes also show a particularly good absorbing ability.

Example 1.

27.2 parts by weight of 1,4-diamino-2-chloroanthraquinone are stirred with 100 parts by weight of pyridine-2-ethanol and 4.4 parts by weight of NaOH powder for 8 hours at a bath temperature of 100°C and 16 hours at 130°C. Excess pyridine-2-ethanol is then distilled off in a vacuum, the crude product is stirred with 100 parts by weight of HgO and suctioned off. The residue is treated with 2500 parts by weight of HgO and 75 parts by weight of concentrated HCl for 10 minutes at 98°C, sucked off at 20°C and dried. You get 23 parts by weight of a blue powder with a melting point of 193-202, which has the following structure:

1 part by weight of the 1,4-diamino-2-(/~2,-pyridiri7-ethoxy)-anthraquinone thus formed is incorporated into a cream with shampooing properties, heating 4.5 parts by weight of cetyl and steryl alcohol, 1.5 parts by weight fatty alcohol mixture (carbon chain length C12 to C^g) and 10 parts by weight of fatty alcohol sulfate (carbon chain length C-^ to C^) at 98°C, add the dye, emulsify with HgO to 95 parts by weight and cool with stirring to room temperature. With ammonia the pH is adjusted to 9.5

and filled with HgO to 100 parts by weight. With this cream, naturally gray hair can be dyed a strong, clear red color with very good washing fastness within 20 minutes at 25°C.

Example 2.

28.4 parts by weight of 1,4-diamino-5-nitroanthraquinone are dissolved in 150 parts by weight of dimethylformamide, mixed with 10.8 parts by weight of 4-picolylamine and 4.4 parts by weight of NaOH powder and stirred for 12 hours at a bath temperature of 100°C. The solvent is distilled off in a vacuum, the residue is stirred into HgO, neutralized with dilute acetic acid and sucked off. After drying, 24.8 parts by weight of a blue dye with a melting point of 185 - 186°C and with formula

1 part by weight of this dye is incorporated into a cream, heating 5 parts by weight of cetyl and 5 parts by weight of stearyl alcohol, 2 parts by weight of wool fat and 12 parts by weight of fatty alcohol sulphate (carbon chain length C^g to C-^) at S& °C, adding the dye, emulsifying with water to 95 parts by weight and cools with stirring to room temperature. After setting the pH value to 7, it is filled with water to 100 parts by weight. With this cream, naturally gray hair is colored within 20 minutes. at 25°C strong blue.

Example 3.

14.2 parts by weight of 1,4-diamino-5-nitroanthraquinone are reacted with 100 parts by weight of N-p-oxetylpropanediamine-(1,3) and 2.2 parts by weight of NaOH powder for 24 hours at 50°C. The reaction mixture is poured with stirring into 1,200 parts by weight of water and sucked off. It is obtained after drying at ^ 0°G

in vacuum 12 parts by weight of a blue powder of the following constitution:

1 part by weight of this dye is incorporated into a detergent cream as indicated in example 2, the pH value being however set to 8 with ammonia. If you treat gray hair with this cream at room temperature, you get a strong blue color with a slightly reddish tone.

Example 4.

In contrast to example 3, 34 parts by weight of 1,4-diamino-5-nitroanthraquinone and 135 parts by weight of N-p-oxetylpropanediamine-(1,3) are reacted without the addition of NaOH for 15 hours at 30°C and left for 48 hours at room temperature. After pouring in 500 parts by weight of ice water, suction and drying, 33 parts by weight of a blue powder with the following formula are obtained: 1 part by weight of this dye is, as described in example 1, incorporated into a detergent cream and natural gray hair is dyed with this cream. You get a blue colouring.

Example 5.

1316 parts by weight of 1,4-diamino-2-chloroanthraquinone are heated with 50 parts by weight of N,N-p-dimethylaminoethanol and 2.2 parts by weight of NaOH powder for 8 hours at 100°C and 16 hours at 130°C bath temperature. Excess dimethylaminoethanol is then distilled off in a vacuum, the residue is stirred

with 200 parts by weight of HgO for 15 minutes, suction off and drying. 10.5 parts by weight of a bluish-red dye with formula are obtained

When treating naturally gray hair with a detergent cream according to example 1, which contains this dye, a clear and strong red coloration is obtained within 20 minutes at 25°C.

It is also already known to dye human hair with anthraquinone dyes which in the core are free of acidic groups and contain at least one heteroatom with the anthraquinone residue connected and with heteroatoms one or more interrupted aliphatic residues. Compared to this known method of working, the agent according to the invention has the advantage that considerably more intense colors are thereby obtained.

Anthraquinone dyes of the type in question are used in practice especially for hair toning and color rinsing. In such treatments, it is practically important that the dyes do not have too high washing fastnesses, so that with repeated toning the addition of the color effects, especially at the ends of the hair in relation to the post-washed first-time toned hair, does not fall too strongly in weight. For this reason, investigations were carried out with regard to the washing fastness of two characteristic compounds on the one hand from the French patent no. and II according to the invention (example 2) II

French Patent No. I.326.406 (I)

In both cases, it is thus 1,4-diaminoanthraquinone dyes which in the five-position have a characteristic group for each case.

For comparison dyes, gray untreated hair was treated for 20 minutes at room temperature with a commercial color cream, which only differed in the used dyes I or II. The strands of hair were rinsed evenly and dried. Then samples I and II were divided (Ia, Ib; Ila, Ilb) and each time one half (Ia, Ila) was washed intensively with a hair shampoo (fatty alcohol ether sulphate solution) under conditions similar to practice and dried. Then, of all four samples, 0.5 g each was treated for one hour with 50 ml of solvent (glacial vinegar) at 80°C, thereby extracting the dye from the hair.

Then the color intensity of the solution of the unwashed sample Ia was compared with the intensity of the washed samples Ib as well as the intensity of the unwashed sample Ila with the intensity of the washed sample Ilb. For this purpose, by diluting the extracts Ia resp. Ila with the solvents samples Ia and Ib as well as samples Ila and Ilb set in the same color. This showed that for setting Ia to the intensity of Ib, a dilution ratio of 1 : 4 was necessary" when setting Ila to Ilb, however, a ratio of approx. 1:7" This result shows a clearly improved leachability of the compound according to the invention.

Claims (1)

Hair dye, characterized by a content of aminoanthraquinone dyes which are essentially acid-free groups and which contain a hydrocarbon residue of the formula -(CH9 ).X connected over an oxygen or nitrogen atom to the anthraquinone residue, and n = 1-4 and X means one of the groups -N(CH3 )2 , -NH(CH2 )2 -NH2 , -NH(CH2 )3 -NH2 , -NH(CH2 )2 0H, -NH-C0-NH2 or -NH-CS-NHg, as the dyes are preferably incorporated into one cream containing wetting agent and/or detergent.