US2944869A

US2944869A - Process for dyeing keratinous material with ortho-diphenols

Info

Publication number: US2944869A
Application number: US709602A
Authority: US
Inventors: Kalopissis Gregoire; Ghilardi Giuliana
Original assignee: LOreal SA
Current assignee: LOreal SA; Monsavon LOreal SA
Priority date: 1957-01-21
Filing date: 1958-01-17
Publication date: 1960-07-12
Anticipated expiration: 1977-07-12
Also published as: DE1106925B; CH345629A; GB831851A; NL224239A

Description

nited Sttes PROCESS FOR DYEI NG KERATINOUS MATERIAL 'WITH ORTHO-DIPHENOLS This invention relates to the dyeing of hair and other keratinous substances.

It is already known to dye hair by means of oxidation dyes, that is to say, compounds which give coloured derivatives only on oxidation. by means of a reactant such as hydrogen peroxide. There may be mentioned among these oxidation dyes aromatic polyamines, aminophenols and certain polyphenols, including triphenols, such as pyrogallol, hydroxyhydroquinone and. its nuclear substitution derivatives. However, it is to be noted that the development of the shade in the dyeing by means of these oxidation dyes isgenerally effected: in alkaline medium and that the shade obtained is: generally not the final shade, but that it changes slowly and reaches this final shade only after 24 hours or evenmore. Moreover, the shades obtained arenot always sufiiciently deep and this disadvantage is overcome by mordanting by means of metallic salts. Unfortunately, such a mordanting treatment makes it substantially impossible to proceed to subsequent treatments such as, for example, permanent waving by means of mercaptans or bleaching by means of hydrogen peroxide or persalts.

The present invention provides a process for dyeing live hair and other keratinous substances by means of solutions of o-diphenols. The process is readily performed, at room temperature, avoids the aforesaid disadvantages and achieves the final desired shade very rapidly, the coloration being fast to light, rubbing and shampooing.

According to the present invention a process of dyeing hair or other keratinous substance comprises applying thereto an aqueous or aqueous alcoholic solution of at least one ortho-diphenol having the following general formula:

in which R represents a hydrogen orhalogen atom or an aldehyde, alkyl, .cycloalkyl, aralkyl, carboxy, carboxyalkyl, alkoxy, nitroalkyl or nitrohydroxyalkyl. group or an amino acid residue, and developing. the shade by means of one or more inorganic oxidizing agents selected from ammonium or alkali metal iodates, periodates and persulphates.

Where the group R is other than hydrogen, the position of the nuclear carbon atom to which the group R is attached may differ in accordance with the isomers which can be actually obtained, but this carbon atom is preferably that in 4-position. v

Ortho-diphenols of the above-defined type include notably, in addition to pyrocatechol (l), the following compounds: homopyrocat'e'chol (2), protocat'ec'huic acid (3),

'protocatechu-al'dehyde 4), 4-bromopyrocatecho1 (5' 4- methoxypyrdcatechol (6'), 3-4-dihydroxy-beta-phenylalanine (7), alpha-(3-4-dihydroxyphenyl) beta nitroethanol (8), but this enumeration cannot be regarded as any limitation of the invention.

The choice of the o-diphenol, or of the respective proportions of the various o-diphenols of the mixture which may be employed, depends principally, though not exclusively, upon the final shade desired. The combined concentration of the o-diphenol or o-diphenols in the aqueous or aqueous alcoholic solution may be comprised Within a fairly wide range depending upon the desired shade. It will preferably be between about 0.01 mole and 1 mole of o-di'pheno'l per litre of solution.

The pH-value of the solutions which may be employed for. carrying out the process according to the invention may vary within a very wide range, e.g. between about 1 and 11. Together with the choice of the particular 0- diphenol or o-dip'henols used, the pH-value permits to control the final shade. Since the invention is not limited to the production of any particular shade, the pH-value at which the process is carried out is not a feature of the invention. Nevertheless it will be understood that, so far as hair-dyeing is concerned. the pH-value should not be such that the solution employed will irritate the scalp or impair the essential properties of the hair, such as its chemical structure, its elasticity and its mechanical strength. In. the case (referred to later herein) where the solution to be applied to hair contains any of the aforesaid oxidizing agents, the optimum choice of the pH-value is also dependent on the nature of this oxidizing agent.

The invention further includes the products of the process of the invention, such as human hair (not on the head) or other forms offhair, felts, furs, feathers and keratinous products generally.

The dyeing process according to the invention may be carried out in various ways. According to a preferred embodiment of the invention, an aqueous or aqueousalcoholic solution of the o-diphenol or o-diphenols is prepared, to which solution the inorganic oxidizing agent or agents specified are added at the time of application to the hair. The pH of this solution may be adjusted to a neutral, acid or alkaline value by the addition of suitable reactants or the solution may be used as such, that is to say, without any component other than the o-diphenols and the oxidizing agents, the pH-value of the solution depending only on the respective proportions of each of these two types of components. Whatever the pI-I-value at which the operation is carried out, the solution is left in contact with the hair e.g. for five to 60 minutes, thoroughly rinsed with water, shampooed, rinsed again and dried.

In this preferred method of carrying out. the process, the inorganic oxidizing agent or agents may be introduced into the o-di'phenol solution, either in the form of powder or in aqueous solution.

According to another embodiment of the invention, the operation is performed in two steps by first applying the solution of the o-diphenol or o-diphenols, free from any oxidizing agent, leaving this solution in contact with the hair e.g. for 5 to 60 minutes, in order to complete the impregnation, gently blotting oh the excess of liquid, optionally after rinsing with water, and then applying to the hair an aqueous solution of the oxidizing agent, and leaving it in contact with the hair for theperiod necessary for the development of the shade, generally from 5 to 20 minutes, the hair then being rinsed, shampooed', rinsed again and dried.

It will be appreciated that the foregoing process, though described in relation to hair, may be applied to alternative keratinous materials. The second embodiment of the invention described above may be modified in various ways; it is possible to use an oxidizing solution, the pH-value of which is neutral, acid or alkaline,

said pH-value being irrespective of that of the o-diphenol solution applied in the first stage. If it is desired to develop the shade in acid medium, the oxidizing solution may be acidified by means of an organic or inorganic acid or by means of any suitable acid buffer. However, if an alkali metal or ammonium iodate or periodate is used, it is preferable not to reduce the pH below 3 and not to use strong inorganic acids for obtaining the lowpH values. Reversely, if it is desired to de'velop the shade in a basic medium, the oxidizing solution may be made alkaline bymeans of any suitable alkaline reagent, for example by means of ammonia, an amine, or an ammonium or alkali metal carbonate or phosphate.

'Whatever the pH-value chosen for the development of the shade and should the process be carried out in one or two stages, the concentration of the oxidizing agent in the solution containing it may be varied between wide limits depending. upon the shade to be obtained and do pending upon the solubility of the oxidizing agents used. Generally speaking, the quantity of oxidizing agent to be employed corresponds to about 0.5 to 10 grams per 100 cc. of the o-diphenol solution employed, whether this solution contains or does not contain the oxidizing agent, the volumes of o-diphenol solution and/ or of oxidizing agent to be employed being determined by the bulk of hair or by the quantity of other keratinous product to be dyed.

Instead of using aqueous or aqueous alcoholic solutions as aforesaid the reactants may be applied in the form of creams, pastes or jellies, the adjustment to the required consistency being effected by any means usual in hair dyeing.

The following examples will serve to illustrate the in vention.

Example I A solution having the following composition is prepared:

Grams Pyrocatechol 2 Acetic acid 0.5

Water to make 100 cc;

time.

Example I] A solution having the following composition is prepared:

Grams Pyrocatechol 3 Acetic a 0.5

Water to make 100 cc.

At the time when this solution is applied to naturally White live hair, there is added thereto 5 grams of potassium periodate. After 20 minutes contact (pH=4), the hair is rinsed with water, shampooed, rinsed again and dried. A beautiful grey-black shade is obtained.

Example Ill The following solution is prepared:

Grams 4-methoxy-pyrocatechol 2 Lactic acid 0.5 Water to make 100 cc.

Immediately before application to live white hair, 1 gram of sodium iodate is added. The solution is left in contact with the hair for 20 minutes, and the hair is thereafter rinsed, shampooed, rinsed again and dried. A

beautiful auburn shade is obtained.

4 Example IV on live white hair.

' Example V A solution having the following composition is prepared:

Grams Beta-(3,4-dihydroxyphenyD-(1) alanine 2 Acetic acid 0.5

Water to make cc.

Immediately before this'solution is applied to live, naturally white hair, 1, gram of sodium iodate is added thereto. The solution is left in contact with the hair for 20 minutes, and the hair isthereafter rinsed, shampooed, rinsed again and dried. I

The hair is dyed a beautiful grey-black.

r Example VI The following solution is prepared:

. Grams Protocatechu-aldehyde 2 Ethyl alcohol 20 Acetic acid 0.5

Water to make 100 cc.

- i Grams 4-bromopyrocatechol 2 Acetic acid 0.5

Water to make 100 cc.

. At the time of use, 5 grams of sodium iodate is added to this solution, which is left in contact with the hair for 15 minutes, whereafter, the hair is rinsed, shampooed, rinsed again and dried. A light brown shade having a red tinge is obtained.

' If the sodium iodate is replacedby an equal weight of potassium periodate, a substantially identical shade is obtained.

Example VIII The following solution is'prepared:

Grams Pyrocatechol 2 20% ammonia so1ution 1.2

Water to make 100 cc.

Shortly before application to the hair, 5 grams of powdered sodium iodate areadded to this solution. The pH-value of the mixture is 9.4. 'After 20 minutes contact with the hair, the latter is rinsed, shampooed, rinsed again and dried. A light brown shade is thereby obtained on naturally white live hair.

Immediately before the hair is impregnated therewith, 5 grams of powdered sodium persulphate is added -to this solution, which is left in contact with the hair for 15 minutes (pH=4.8), whereafter the hair i s rinsed,

shampooed, rinsed again and dried. A dark blond shade is obtained on white or near-white live hair.

Example X 1 gram of sodium iodate is introduced into a solution having the following composition:

Grams 4-methoxy-pyrocatechol 2 20% ammonia solution 1.2 Water to make 100 cc.

After contact for 20 minutes, the hair is rinsed, shampooed, rinsed again. and dried. On greying. hair, a light chestnut having a greenish tinge is thus obtained.

Example Xl The following solution is prepared:

' Grams Protocatechu-aldehyde a- 2 20% ammonia solution 1.2

Water to make 100 cc.

At the time of application to naturally white live hair, Sgrams of sodium iodate is added to this solution. After contact for 20 minutes with the hair, the latter is rinsed, shampooed, rinsed again and dried. A light blond shade is thus obtained.

Example XII A solution having the following composition is prepared:

. Grams 4-bromopyrocatechol .t... 2 20% ammonia 1 ,1.2

Water to make 100 cc.

Before this solution is applied to the hair, 5 grams of sodium iodate is added thereto. It is. left in contact with the-hair for 15 minutes, whereafter the hairis rinsed, shampooed, rinsed again and dried. A light chestnut colour is thereby obtained.

Example XIII A. solution having the following composition is prepared:

Gram

Pyrocatechol 1 Water to make 100 cc.

Live grey hair is impregnated with this solution. After contact for minutes, the. excess of liquid is blotted off, for example by means of a towel, and a 4% by weight aqueous sodium iodate solution (pH=5) is then applied. This solution is left in contact with the hair for minutes, and the hair is then rinsed, shampooed, rinsed again and dried. The hair is dyed a light blond verging on mahogany.

Example XIV A solution having the following composition is applied to nearly white live hair:

Grams Pyrocatechol 4 Acetic acid 0.5'

Water to make 100 cc.

After contact for 10 minutes and gentle blotting, a 4% by weight aqueous sodium iodate solution is applied to the hair. This solution is left in. contact with the hair for 1 0 minutes, Whereafter the hair is rinsed, shampooed, rinsed again and dried. A light mahogany shade is obtained. 7 1 Example X V The following solution is prepared:

Grams 4-brornopyrocatechol 2 Acetic acid 0.5

Water to make 100 cc.

Example X VI Naturally white live hair is impregnated with the following solution:

Grams Pyrocatechol l 20% ammonia solution 1.2

Water to make cc.

The solutionis left in contact with the hair for 10 minutes and the hair is then gently blotted. The following composition is then applied:

Grams Sodium io 4 20% ammonia solution 1.2 Water to make 100 cc.

After a period of 10 minutes, the hair is rinsed, shampooed, rinsed again and dried; A blond shade with a slight violet tinge is obtained.

Example VII A solution having the following composition is prepared:

Grams Pyrocatechol 3 Sodium tartrate 7 Tartaric acid 5.2

Water to make 100 cc.v

The pH-value of this solution is 3.1. 7.2 grams of sodium persulphate'are added to this solution, which is immediately applied to naturally white live hair. After 5 minutes, the pH-value of the solution close to the cortex of the hair is 2.8. After a total impregnation time of 25 minutes, the hair is briefly rinsed, shampooed,

rinsed again and dried. 'The shade obtained is a very light blond.

Example XVIII The following'solution is prepared:

Grams Pyrocatechol 3 Acetic acid 1 Water to make 100 cc.

The pH-value of the solution. is 2.8. At the time of the application of the solution to live, naturally white hair, 2 grams of sodium iodate are added. The solution is left in contact with the hair for 15 minutes, during which it is observed that the pH-value of the part of the solution close to the hair does not vary. The hair is then briefly rinsed, shampooed, rinsed again and dried. The shade thus obtained is ash-chestnut.

Example XIX The following composition is prepared:

Grams Pyrocateehol 6 Sulphonated higher fatty alcohol 3 Water to make 100 cc.

The pH-value of this mixture is 4. 4 grams of sodium iodate are added to this composition which is immediately applied to naturally white live hair. After contact for 15 minutes, during which it is observed that the pH of the solution close to the hair does not vary, the hair is rinsed with tapwater and dried. An ash-chestnut shade is obtained.

If, in this example, the sodium iodate is replaced by '1. A process for dyeing hair and other keratinous ma terials which comprises applying thereto an aqueous solution consisting of at least one orthodiphenol of the general formula:

wherein R is selected from the class consisting of the hydrogen atom, the halogen atom, aldehyde, alkyl, carboxy, alkoxy, nitro-hydroxyalkyl and alpha amino propanoic groups, and an oxidizing agent selected from the class consisting of ammonium and alkali metal iodates, periodates and persulphates.

2. A process for dyeing hair and other keratinous materials which comprises applying thereto an aqueous solution consisting, in the global proportion of 0.1 to 1.0 mole per litre, of at least one orthodiphenol of the general formula:

wherein R is selected from the class consisting of the hydrogen atom, the halogen atom, aldehyde, alkyl, carboxy, alkoxy, nitro-hydroxyalkyl and alpha amino propanoic groups, said solution also containing a freshly added oxidizing agent selected from the class consisting of ammonium and alkali metal iodates, periodates and persulphates, the quantity of oxidizing agent being 0.5 to grams per litre of said orthodiphenol solution.

3. A process for dyeing hair'- and other keratinous materials which comprises applying thereto an aqueous solution consisting, in the global proportion of 0.1 to 1.0 mole per litre, of at least one orthodiphenol of the general formula:

wherein R is selected from the class consisting of the hydrogen atom, the halogen atom, aldehyde, alkyl, carboxy, alkoxy, nitro-hydroxyalkyl and alpha amino propanoic groups and thereafter applying thereto an oxidizing agent selected from the class consisting of ammonium and alkali metal iodates, periodates and persulphates, the quantity of oxidizing agent being 0.5 to 10 grams per litre of said orthodiphenol solution.

4. A process for dyeing hair and other keratinous materials which comprises applying thereto an aqueous solution consisting, in the global proportion of 0.1 to 1.0

mole per litre, of at least eral formula:

wherein R is selected from the class consisting of the hydrogen atom, the halogen atom, aldehyde, alkyl, carboxy, alkoxy, nitro-hydroxyalkyl and alpha amino propanoic groupsand thereafter applying thereto a solution of an oxidizing agent selected from the class consisting of ammonium and alkali metal iodates, periodates and persulphates, the quantity of oxidizing agent being 0.5 to 10 grams per litre of said orthodiphenol solution, and allowing said oxidizing solution to remain in contact with the hair for 5.20 minutes. i

5. A process for dyeing hair and other keratinous materials which comprises applying thereto an aqueous solution of pH 3 to 11 consisting, in the global proportion of 0.1 to 1.0 mole per litre, of at least one orthodiphenol of the general formula:

wherein R is selected from the class consisting of the hydrogen atom, the halogen atom, aldehyde, alkyl, carboxy, alkoxy, nitro-hydroxyalkyl and alpha amino propanoic groups, said solution also containing a freshly added oxidizing agent selected from the class consisting of ammonium and alkali metal iodates, periodates and persulphates, the quantity of oxidizing agent being 0.5 to 10 grams per litre of said orthodiphenol solution.

6. A process for dyeing hair and other keratinous materials which comprises aplying thereto an aqueous solution of pH 3 to 11 consisting, in the global proportion of 0.1 to 1.0 mole per litre, of at least one orthodiphenol of the general formula:

wherein R is selected from the class consisting of the hydrogen atom, the halogen atom, aldehyde, alkyl, carboxy, alkoxy, nitro-hydroxyalkyl and alpha amino propanoic groups and thereafter applying thereto an aqueous References Cited in the file of this patent UNITED STATES PATENTS 2,539,202 Peck Ian. 23, 1951 FOREIGN PATENTS 745,144 Great Britain Feb. 22, 1956 OTHER REFERENCES Kass: Am. Perf. and Aromatics, August 1956, pp. 34-37.

Kass: Am. Perf. and Aromatics, September 1956, pp. 47-50.

one orthodiphenol of the gen-

Claims

1. A PROCESS FOR DYEING HAIR AND OTHER KERATINOUS MATERIALS WHICH COMPRISES APPLYING THERETO AN AQUEOUS SOLUTION CONSISTING OF AT LEAST ONE ORTHODIPHENOL OF THE GENERAL FORMULA: