DE1492072A1 - Hair dyes - Google Patents

Description

U92072

.DM D R. J. R I IT bi T Ö T [IR

ING. WOLFRAM HUNlE

t *, ", r /. < : ^ s τ μ a '- ■' ! ■ '· t» N f * ■ ► - ■; ■

PH 92 o72.o company L ¹ OBEAL

Munich, July 2, 1969 M / 7694

Hair dyes

The invention relates to hair dyes based on oxidation dyes which, according to the invention, contain i-phenyl-5-methylpyrazolone- (5) for retarding the oxidation dyes.

Most hair dyes are usually done with Oxydati onsfarbstoffen, which immediately goal an oxidizing agent, preferably hydrogen peroxide, is added to the application to the hair. This oxidizing agent causes the color to develop through

909850/1831 "ad o" ig, _nal

λ'Γ.ΙΙΟ Documents lArt. / § l An *. *. «R. l Sä «j *» change «) *. * 4. i ,. </

oxidative association of the dyes with one another. In addition, the added hydrogen peroxide may also have the task of partially bleaching the hair, so that one at the end of the dyeing process lighter color than the original color is achieved.

It is known that oxidation dyes according to their chemical constitution are extremely sensitive to oxidizing agents, so that it is usually necessary to keep them in the presence of a reducing agent to store and to add substances to solutions of such dyes, which have the task of delaying the oxidation process as much as possible.

In addition, at the beginning of a dyeing process, if the dye solution is mixed with an oxidizing agent, the oxidative union proceed so much delayed that it only occurs after the application of the dye solution the hair takes place and not already in the container, In where the mixture was made.

This condition is of great importance in practice, because the coloring power of the mixture is reduced in the To the extent that the dyes are already oxidized in the vessel used for the preparation of the mixture. It is

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so practically impossible to achieve uniformity, i.e. to achieve the uniform coloring of all locks of hair, if in the period between the application of the color solution on the first and on the last lock of hair the solution in this vessel has been substantially oxidized.

Apart from the fact that with an already partially oxidized Misohung it gets a weaker color the durability of such a weaker coloration is far less than that with a through Mix the dyes with the oxidant fresh prepared staining solution is obtained. On the other hand, the appearance is one obtained by too rapid oxidation Hair coloring unsightly; the resulting rapid darkening makes it impossible to obtain the desired color tone capture.

In order to avoid these disadvantages, it has already been proposed to use the coloring solutions containing an oxidizing agent Add substances such as ammonthioglycolate, sodium sulfite or ascorbic acid, which in one to a certain extent have a retarding effect on the oxidative combination of the dyes.

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Nevertheless, the retarding effect of such additives, which have been used to date, is insufficient, since the dye preparations darken to an extent that cannot be overlooked before all the hair locks have been treated.

The new hair dye preferably contains 1 to 50 moles of the pyrazolone (5) derivative per 100 moles of an oxidation dye.

In addition, the agents used to increase the shelf life can also contain conventional stabilizers such as ammonium thioglycolate, sodium sulfite or ascorbic acid.

In the examples given below, the subject matter of the invention is intended to be explained in more detail without, however, being restricted thereto. In particular, different variants can be made without departing from the scope of the invention.

Example 1 ,

The following mixture is made :

Condensation product of nonylphenol with 4 moles of ethylene oxide 27 ο g

Condensation product of nonylphenol with 9 moles of ethylene oxide 25ο g

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Ethyl alcohol 16o g Ammonia, 22 ⁰ B6 11o cm ³

p-tolylenediamine H g

m-diaminoanisole ο, 5 g

Resorcinol 6 g

m-aminophenol 2.2 g

p-aminophenol 2.3 g

1-phenyl-3-methyl-pyrazolone- (5) 7g

Ethylenediamine tetraacetic acid 2 g Hit water fill up to 1ooo g

t This misappropriation becomes immediately prior to its use with the same volume of hydrogen peroxide (2o vol) ▼ replaced. A red, transparent gel is obtained which is practically unchanged for about 30 minutes bMbt. Will this gel in the usual way up to 9o pounds When white hair is applied, after washing and drying a chestnut brown color is obtained.

Example 2 The following mixture is made:

oleic acid 15o g

Condensation product of a synthetically produced oxo alcohol with 3 moles of ethylene oxide .... 25o g

Butyloellosolre 50 g

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Ethyl alcohol; 15o g

Ammonia, 22 ⁰ Be i. 1oo cnr

p-tolylenediamine 13.5 g

m-diaminoanisole 0.5 g

Resorcinol 5 g

m-aminophenol 2 g

p-aminophenol 2.3 g

1-phenyl-3-methyl-pyrazolone- (5) 7 g

Diethylene-triamine-penta-vinegar- Hatriumaalz

acid .. 2g

Make up to 1,000 g with water

Immediately before applying this mixture to the hair, it is mixed with the same volume of Wajaeratoffsuperoxid (2o vol). The result is a red, transparent gel which remains intact for 30 minutes without undergoing any changes. Are thus treated in the usual way up to 9o i "white hair, so after rinsing and drying, a chestnut hair tint.

In order to show the effect that can be achieved by the method according to the invention, comparative versions were already made with known stabilized dye compositions containing oxidation dyes carried out these experiments

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show the behavior of such compositions in the presence of hydrogen peroxide and without the addition of a Stabilizer, with a known stabilizer and with stabilizers according to the invention.

For this purpose, 6 solutions of the following composition were prepared:
Solution 1

p-toluenediamine base ο, o1 mol

Ethylenediamine tetraacetic acid ο, 1 g

Ammonia 2o # -ig 1o cnr

Fill up with water to 100 g

Solution 2

p-tolylenediamine base o, o1 mol

Ethylenediamine tetraacetic acid o »1 g

Ammonia 2o # -ig 1 ο cm

Ascorbic acid ο.176 g (o, oo1 mole)

Sodium hydroxide 0.08 g (o, oo2 mol)

Make up to 1 oo g with water

Solution 3

p-toluenediamine baae o, o1 mol

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Ethylenediamine tetraacetic acid ο, 1 g

Ammonia 2ο £ -ig loom

Ammonium thioglycolate o, o95 g (o, oo1 mol)

Make up to 100 g with water

Solution 4

p-Toluylenediamine base .. ·. · o, o1 mol

Ethylenediamine tetraacetic acid ο, 1 g

Ammonia 2o% 1 ο or

Sodium sulfite o, 126 g (o, oo1 mole)

Make up to 1 oo g with water

Solution 5

p-toluenediamine base ο, o1 mol

Ethylenediamine tetraacetic acid ο, 1 g

Ammonia 2 ο £ -ig 1 ο om

1-phenyl-3-methylpyrazolon- (5) o, 174 g (οροί mol)

Make up to 1 oo g with water

Solution 6

p-Toluylenediamine baee o, o1 KoI

Xtnylenediamine tetraesaic acid ο, 1 g Ammonia 2o? 6 ig 1 ο '

1-phenyl-3- * ethyl-pyrazolon- (5) _{o.348 g (o r} oo2 mol)

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Fill up with $ aaser to 1 oo g

Each of these solutions was mixed with the same weight of waaeratoffauperoxide (30 vol.) Before each examination, and the change in optical density as a function of time was then determined. A photocolorimeter by Bonet and Maury with a wavelength of $ 52oo was used for the measurements. and using the appropriate green filter.

The mixture of the solutions with the Waaaeratoffauperoxyd were carried out at the time 0. The Srgebniaee of the Investigations aind are compiled in the following table:

solutions
Time 0
1o
2o
3o
4o
6o Absorption (optical density) (Grade Verne)
1oo 2 3 4th 5 6th 1 2.5
8.5
15.5
21.6
27.7
36.7 7.8
11.4
16.4
23.9
27.2
33.5 4.9
1o, 6
14.1
2o, 1
22.1
28.3 2.2
3.3
4.6
8.8
12.7
2o, 3 2.2
2.1
1.5
2.1
2.7
4.4 6th
1o, 7
15.1
22nd
27.4
39.6

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The numerical values listed are also the connected ones Refer to drawing. The time in minutes is plotted on the abscissa and the time on the ordinate optical density of solutions 1 to 6, expressed in degrees Verne.

The numbering of the individual curves corresponds to the individual numbers of the solutions.

It can be seen from this that especially within 30 minutes, that is, that period of time which corresponds to the duration of the treatment in the case of hair coloring, the stabilizing agent according to the invention is sufficient Delays the oxidative union in the staining solutions.

Wae the superiority of the additive according to the invention compared to agents containing ethylenediaminetetraacetic acid not included, this question is answered by comparing the hair coloring effects below the inventive use of phenylmethylpyrazolone versus ethylenediaminetetraacetic acid] !! Sodium, known commercially under the name Trilon B, in an ammonia-containing solution of paratoluylenediamine base.

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For this purpose , the fluctuations in the absorption coefficients of the solutions in question have been investigated using a green filter, the absorption maximum of which is about 5240 £.

Operation!

Each paraffin solution corresponds to a comparison solution which does not contain any paratoluylenediamine base. At the time zero, the dye solution and the comparison solution are mixed with an equal weight of hydrogen peroxide of 30% by volume. The initial transfer is read and measurements are made on the fresh solutions after 5, 1o, 2o, 3o, 4o, 5o and 60 minutes; then after 24 hours with the stabilized solutions.

Comment:

Before every measurement, it is very important to have the ink knife container stir in order to achieve a homogeneous oxidation.

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Oxydationcnor-chwinrlicikelt der LftsunncuR / O 0 Q 7 2

i'carbone solutions solution 1

Solution 2 Solution 3

Paratoluylenedioiaine, - o, ol MeI "l _# 22g o, ol Mol" o # ol llol

baoo 2.301 g Parato- I ₄ 22 g 1 # 22 g

luyloncliaminbaee

Cu 51 ^

Ethylenediamine tetra-
coigescäuro o, l g %
o, lg o _# lg 20% ammonia
(22Ο Bo) Io ecm Xo ecm Io ecm l-phenyl-3-methyl-
5-pyrazolone 0 o _# ool mole
o, 174 g o, oo2 moles
o, 343 g

stand out with water until, loo g

loo g

loo g

Verqleichnlösxmqei} Solution 1 Lung 2 Solution 3 Dye solutions o, l g o # l g OfI g Ethylenediamintotra- Io ecm Io cc » Io ecm 2o% igor Aianoniak
(22 ° Be) O Ojl? 4 g o, 348 g 1-phenyl- 3-mothy 1- D-
pyrasolon loo g loo g
t loo g fill up with water
until

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Two rows of smoking were carried out. Comparisons Curves Al Ai with French legend.

The following can be seen from the parameters, table and curves:

1) Ethylenediaminetetraeaic acid oxidizes the dye solution when mixed with hydrogen peroxide.

2) With 0.174 g of Phenylmethylpyraaolon one obtains a clear solution for 10 minutes. The solution is then oxidized.

3) 0.348 g of phenylmethylpyrasolone delays the oxidation for 3ο minutes.

S ou sults rmipten ι

Ethylenediamine tetraacetic acid plays the role of sequestrant, phenylmethylpyraiolone plays the role of antioxidant or reducing agents a. At least 0.02 moles of phenylmethylpyrasolone are required for 0.01 mole of paratoluylenediamine base.

Increase in the phenylmethylpyrasolone content in the presence of o «1 i» Trilon B.

The following amounts of phenylmethylpyrazolone were examined

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o, g 174 "that is 1o $ the molar amount equivalent to the Paratoluylendiamin

ο »348 g, that bites 2 ο i» the molar amount equivalent to paratoluylenediamine

o _t 522 g, that is to say 3o i> the molar amount equivalent to the oluylenediamine farat

o, g 696, daa heift 4o i> of de "Paratoluylendiamin equivalent molar amount

ο, 87ο g, i.e. 50 % of the molar amount equivalent to the parmtoluenediamine

Remarks:

The dye solutions are naoh to oxidation 24 hour boo clearly more consistent.

Conclusion: Well, 24 hours of booing

0.174 g delay the oxidation for 10 minutes ο, 348 g delay oxidation for 30 minutes ο, 522 g delay the oxidation for 40 minutes 0.696 g delay the oxidation for 50 minutes

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ο, 87o g delay oxidation for 60 minutes

Effect of phenylmethylpyrazolone in the absence of ethylenediaminetetraeaic acid

In this case, too, the solutions are more resistant to oxidation after 24 hours.

With dye solutions of 24 hours « o, 174 g of phenylmethylpyrazolone do not delay the oxidation. The Gemisoh with hydrogen peroxide calls you immediate cloudiness.

give o.348 g of a partially oxidized solution after mixture formation.

0.522 g delay the oxidation for 20 minutes, 0.696 g delay the oxidation for 30 minutes 0.87 g delay the oxidation for 40 minutes.

In summary: With 0.1 # ethylenediaminetetraacetic acid, 0.338 g of phenylmethylpyra.zolon (20% of the molar amount equivalent to the paratoluylenediamine base) has the same effect as o.696 g of phenylmethylpyrazolone alone used (ie 40 % of the equivalent amount of the paratoluylenediamine base equivalent ).

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NB. With 1.74 g of 1-phenyl-3-methyl-5-pyrazolone (i.e. 100 the solutions are cloudy and precipitate.

Effect of ethylenediaminetetraacetic acid alone

These experiments show that ethylenediaminetetraacetic acid only plays the role of sequestering agent; the increase in the content .an Äthylendiamintetraessigeäure about o, 1 i "has almost no influence on the rate of oxidation of the mixture with hydrogen peroxide.

The aforementioned experiments clearly show the advantage of phenylmethylpyrazolone as an antioxidant.

²¹² A-. 909850/1631

Claims (3)

Claims 1. Hair dye containing oxidative dyes, characterized by a content of 1-phenyl-3-methylpyraaolon- (5) · 2. Hair dye according to Claim 1, characterized in that the ratio of the pyrazolone derivative to the oxidation dye is 1 to 50 moles to 100 moles. 3. Agent according to any one of the preceding claims, characterized in that it additionally contains a conventional stabilizer, such as ammonium thioglycolate, sodium sulfite or ascorbic acid. 909850/1631 Blank page