US2719104A

US2719104A - Dyeing composition and process for keratinaceous material

Info

Publication number: US2719104A
Application number: US236275A
Authority: US
Inventors: Carl G Westerberg
Original assignee: Individual
Current assignee: Individual
Priority date: 1951-07-11
Filing date: 1951-07-11
Publication date: 1955-09-27
Anticipated expiration: 1972-09-27

Description

United States Patent DYEING COMPOSITION AND PROCESS FOR KERATINACEOUS MATERIAL Carl G. Westerberg, Sierra Madre, Calif.

No Drawing. Application July 11, 1951,

Serial No. 236,275

19 Claims. (Cl. 16788) The present invention relates to a novel dyeing composition for keratinaceous material, such as hair, wool, fur, feathers and the like. The dye compositions of the present invention are capable of producing a variety of colors and a variety of shades in the various colors, depending upon variations in time, concentration and pH of the dye composition employed. The dyed materials are permanently dyed the desired color and are particularly desirable for hair dyeing, inasmuch as they are harmless when used as herein described.

It is therefore an object of the present invention to provide novel hair dyeing compositions capable of producing a variety of colors and a variety of shades in the various colors.

It is another object of the present invention to provide a novel hair-dyeing composition which is completely harmless, and which is capable of simple and easy use by the inexperienced user to produce evenly dyed hair which permanently retains the desired color.

The compositions of the present invention are composed of a plurality of components. The essential components are three, (1) a water soluble thiol compound, such as a water soluble thiol salt or an ester, (2) a soluble heavy metal salt and (3) an alkali. In addition, the compositions may contain a plurality of additional optional ingredients. A desirable ingredient is a wetting agent of the non-soapy type. Typical of these wetting agents are alkylaryl sulphonates, sulphated lauryl alcohol and sulphonated oils. The composition may be thickened with a water soluble gum as an additional optional ingredient. The particular forms of the compositions will be described in more detail hereinafter.

Considerable variation is possible in each of the essential ingredients. Thus, with reference to the thiol compound, it has been found that thioglycolic acid employed in the form of its salts such as sodium and ammonium salts, is particularly desirable and readily available for this purpose. However, other thiol compounds which are water soluble may be used. These include the glycerol ester of thioglycolic acid, as Well as other esters of thioglycolic acid. Similarly, 2 -mercaptyl. ethanol (SHCI-IzCHzOH) may be used. In place of these specific materials any Water soluble compound having a thiol group may be employed.

As to the heavy metal salts that may be employed, these include a considerable number, of which cobalt, nickel, iron, manganese and bismuth are particularly desirable. A variety of colors may be obtained from these metals, varying from a bright yellow with bismuth to a very dark brown, almost black color when using nickel. Cobalt and manganese give a variety of brown colors, Whereas iron produces a reddish brown color. The heavy metal may be employed in any of a variety of water soluble salts. Of these the sulphates, chlorides, acetates, lactates, nitrates, some carbonates and subcarbonates may be employed. It will be appreciated that the salt which is selected for any particular metal should be a water soluble salt.

Fee

Almost any water soluble alkaline material may be employed. Preferably this alkali is an organic alkali and preferably volatile; such as ammonia, amines and the like. Suitable amines include methyl, ethyl, propyl, isopropyl amines or diamines, monoethanolamine, morpholine and numerous other similar compounds. Inorganic alkaline materials, such as sodium and potassium hydroxides, carbonates, phopshates and the like, which do not interfere with the heavy metal salts may be employed.

The dyeing compositions in condition for actual use are in aqueous solution. Under these circumstances a complex is formed of the alkali, the thiol compound and the metal salt. These complexes are colored and are water soluble. They have an apparent afiinity for any material containing keratin and can be used for dyeing keratinaceous materials by the simple application of the aqueous solution thereto. For the purpose of obtaining a uniform dyeing, it is preferred to have the composition contain a non-soapy wetting agent, which serves to bring the aqueous solution into uniform contact with all of the filaments. The complex appears to form a further complex with the thiol groups contained in the keratinaceous material.

For the purpose of marketing these dyeing compositions they may be packaged in a variety of ways. Some of the finished dyeing compositions are unstable when kept for extended periods of time, and accordingly it is preferred that they be mixed shortly prior to the time of use. Thus iron and manganese tend to oxidize the thiol group in the thiol compound and accordingly cause the mixture to lose its dyeing power when stored over extended periods of time. Accordingly, with such compositions it is preferred to maintain the iron and manganese salts separate from the thiol compounds until immediately prior to use. Antioxidants such as propylgallate may be used to delay the oxidation of such mixed dyeing compositions.

In contrast to the instability of these iron and man ganese compositions, solutions containing soluble nickel salts have been kept for several months in admixture with the thiol compound without any apparent deterioration of the dyeing power of the material. It is often desirable to package these compositions in the form of two aqueous solutions, one containing the soluble metal salt and the other containing the alkali and the thiol compound. One of these solutions can then also contain the wetting agent and a water soluble gum as a thickening agent. As an alternative the respective solutions may be formulated in the form of a cream with an emulsified oil base or mixed with a sulphonated oil. In addition the materials may be supplied in the form of the dry ingredients which can be mixed by the user. Any of this variety of ways of preparing the composition may be employed.

The dyeing operation may also be effected by first treating the material to be dyed with the thiol compound and then treating the material, either with or without prior rinsing with the heavy metal salt solution. In this manner, the color develops first right in the material being dyed rather than as a color complex which is added as such to the material. It should be pointed out that where the thiol compound and the metal salt are used separately as described immediately above, the thiol solution alone need be alkaline for reaction with the keratinaceous material. The heavy metal salt solution may be acid, neutral or alkaline as desired, and the dyeing action is still obtainable.

The pH of the dyeing composition may be varied widely to produce different effects. Some of the metals employed in the present dying compositions will transmit the dye to white wool yarn under a Wide range of pH, ranging from slightly acid to strongly alkaline. A pref- 3 erable pH is from 8 to 10.5. The depth of the color varies directly with the pH, the deepest color being achieved at the highest pH. For example, by varying the pH of nickel-containing dyeing compositions, it is possible to vary the color from light brown to a very dark brown or almost black.

Variations in color may also be obtained by varying the amounts of the metal present and the concentration of the complex used. It is preferred to employ the alkali, the thiol compound and the metal compound in substantially equivalent amounts. It will be apparent that an excess of any of the components of the composition will not adversely affect the action of the combination but will be essentially a waste of that particular component. Colors may also be varied by the use of combinations of metals rather than a single metal. As illustrated in the following examples the metal compound should preferably be present in an amount at least about 3.3 per cent by weight of the total dyeing solution and preferably from about to per cent. While it is preferred to employ the alkali, the thiol compound and the metal compound in substantially equivalent amounts they may be varied considerably as shown in the examples.

In employing the composition it is merely necessary to apply the composition to the material to be dyed and usually from 5 to 10 minutes is sufficient time to effect a satisfactory dyeing operation. Usually beyond this time period no further dyeing action is obtained. Variation in the color may be obtained by shortening the dyeing period below the 5 to 10 minutes which effects the full action of the dye.

The following examples will serve to illustrate the invention:

Example 1 Thioglycolic acid 70% cc 7.0 NHiOH 28% cc 30.0 Sulphonated oil cc 1.0 NiCl2.6H2O gr 10.0

H2O to make 100.0 cc.

Example 2 Thioglycolic acid 70% cc 7.0 NHQOH 28% cc 20.0 Sulphonated oil cc 1.0 NiCl2.6H2O "grams" 10.0

H2O to make 100.0 cc.

White wool yarn was dyed for periods of 5, 10 and minutes. Again the dyeing reaction was substantially complete in the first five minutes and there was little variation in color between the samples. These samples were approximately the same color as the dyed wool samples of Example 1.

Example 3 Thioglycolic acid 70% cc 7.0 NH4OH 28% 10.0 Sulphonated il cc 1.0 NiCl2.6H2O grams 10.0

H2O to make 100.0 cc.

White wool yarn was dyed with this solution for periods of 5, 10 and 15 minutes. In this instance the dyeing reaction did not appear to be complete within five minutes but had been approximately completed in ten minutes. All of these samples were somewhat lighter than the samples dyed in Examples 1 and 2.

4 Example 4 The dyeing solution in Example 3 Was diluted with an equal volume of water. White wool yarn was dyed with this diluted solution for periods of 5, l0 and 15 minutes. The sample treated for five minutes was a light cream to tan color, the ten minute sample was a tan color, and the fifteen minute sample was a fairly dark tan color.

Example 5 The solution of Example 3 was diluted with twice its volume of water and white wool yarn was again dyed for periods of 5, 10 and 15 minutes. The solution was effective to tint the yarn, the depth of the tint increasing with the length of time. The fifteen minute sample was slightly lighter in color than the ten minute sample of Example 4.

Example 6 Glyceryl thioglycolate 50% (Evans Chemetics Thiovanol) cc 10.0 NHQOH 28% cc 10.0 NiCl2.6H2O grams 10.0 Sulphonated oil cc 1.0

H20 to make 100.0 cc.

White wool yarn was dyed with this solution for periods of 5, 10 and 15 minutes. The five-minute sample was a distinct tan color, whereas the 10 and 15 minutes samples were progressively darker.

Example 7 Glyceryl thioglycolate 50% cc 10.0 NH4OH 28% cc 30.0 NiCl2.6H2O grams 10.0 Sulphonated oil cc 1.0

H20 to make 100.0 cc.

Example 8 Mercaptoethanol cc 6.0 NH4OH 28% cc 20.0 Sulphonated oil cc 1.0 NiCl2.6H2O rams" 10.0

H2O to make 100.0 cc.

White wool yarn was dyed for five minutes with this solution and took on a very dark brown color.

Cotton yarn and wool yarn were treated simultaneously with the dyeing solution. The wool yarn immediately picked up the dye color, whereas the cotton remained its original white color.

Example 9 Solution A:

Thioglycolic acid 70% cc 7.0 NH4OH 28% cc 20.0 Sulphonated oil cc 1.0 H20 to make 100.0 cc.

Solution B:

NiCl2.6H2O grams 10.0 Sulphonated oil cc 1.0

H20 to make 100.0 cc.

Solution A was a water white solution and was applied to hair and was rinsed out completely. The hair, while still damp was then treated with solution B which was only slightly colored, and the hair immediately took on a deep brown color.

Mix A and B prior to use.

These solutions were made up and were then mixed immediately prior to use. The results obtained with this are the same as those obtained with Example 2. This example demonstrates the possibility of preparing separate solutions which may be sold as such and which may be mixed immediately prior to use.

Example 11 Grams Thioglycolic acid 6.0 Cobalt a tat 10.0

Morpholine and water suflicient to make 100.0 cc. and

a pH of 9.5.

White wool yarn dyed with this solution took on a deep brown color.

Example 12 Grams Glyceryl thioglycolate 50% (Evans Chemetics Thiovanol) 12.0 Bismuth nitrat 10.0 Isopropylamine and water sufficient to make 100.0 cc.

and a pH of 10.

White wool yarn was dyed with this solution and took on a brilliant yellow color.

Example 13 Grams Glyceryl thioglycolate 12.0 Ferric sulphat 10.0

Ammonia and water sufiicient to make 100.0 cc. and

a pH of 10.5.

White wool yarn was dyed with this solution and the yarn immediately took on a reddish brown typically iron color.

Example 14 Grams Mercaptoethanol 6.0 Manganous chloride 10.0

Water and ammonia sufiicient to make 100.0 cc. and a pH of 8.

White wool yarn was dyed with this solution and took on a very dark brown color.

The above examples are also useful for the dyeing of human hair. For example, one of the nickel dyeing solutions was employed to dye blond hair. At a pH of 8.5 the hair took on a light brown color, at a pH of 9.5 the hair took on a quite deep brown color, whereas at a pH of 10.5 the hair became almost black.

In addition, various samples of white wool yarn were dyed with mixtures of bismuth and nickel. By this means it was able to control the depth of the brown color so that any minute variation between the bright yellow color obtained with the bismuth and the deep brown obtained with nickel was obtainable.

As many apparently Widely different embodiments of this invention may be made Without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments herein.

What I claim is:

1. A dyeing composition for keratinaceous material comprising an aqueous solution of a water soluble thiol 6 compound, a water soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition and a water soluble alkaline material, the solution having a pH Within the approximate range of 8-105.

2. A dyeing composition for keratinaceous material comprising an aqueous solution of a water soluble salt of thioglycolic acid, a water soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition and a volatile alkali, the solution having a pH Within the approximate range of 8-105.

3. A dyeing composition for keratinaceous material comprising an aqueous solution of sodium thioglycolate, a water soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by Weight of the total composition and ammonia, the solution having a pH within the approximate range of 8-105.

4. A dyeing composition for keratinaceous material comprising an aqueous solution of sodium thioglycolate, a water soluble cobalt salt in an amountequal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 8-105.

5. A dyeing composition for keratinaceous material comprising an aqueous solution of sodium thioglycolate, a water soluble nickel salt in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 8-105.

6. A dyeing composition for keratinaceous material comprising an aqueous solution of sodium thioglycolate, a water soluble iron salt in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 8-105.

7. A dyeing composition for keratinaceous material comprising an aqueous solution of sodium thioglycolate, a water soluble manganese salt in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH Within the approximate range of 8-105.

8. A dyeing composition for keratinaceous material comprising an aqueous solution of sodium thioglycolate, a water soluble bismuth salt in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 8-105.

9. A dyeing composition for keratinaceous material comprising an aqueous solution of a water soluble ester of thioglycolic acid, a Water salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition, and a volatile alkali, the solution having a pH within the approximate range of 8-105.

10. A dyeing composition for keratinaceous material comprising an aqueous solution of glyceryl thioglycolate, a water soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 8-105.

11. A dyeing composition for keratinaceous material comprising an aqueous solution of 2-mercaptoethanol, a water soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 8-105.

12. A process of dyeing keratinaceous material which comprises applying thereto an aqueous solution of a water soluble thiol compound, a water soluble salt of a heavy metal in an amount equal to at least about 3.3 per cent by weight of the total composition and a water soluble alkaline material, the solution having a pH within the approximate range of 8-10.5.

13. The process of dyeing keratinaceous material which comprises applying thereto an aqueous solution of a soluble salt .of thioglycolic acid, a soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition, and a water soluble alkaline material, the solution having a pH within the approximate range of 810.5.

14. The process of dyeing keratinaceous material which comprises applying thereto an aqueous solution of a soluble salt of thioglycolic acid, a soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by Weight of the total composition, and a volatile alkali, the solution having a pH within the approximate range of 8-10.5.

15. The process of dyeing keratinaceous material which comprises applying thereto an aqueous solution of a soluble salt of thioglycolic acid, a soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition, and and ammonia, the solution having a pH within the approximate range of 8-10.5.

16. The process of dyeing keratinaceous material which comprises applying thereto an aqueous solution of ammonium thioglycolate, a water soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the Solution having a pH within the approximate range of 810.5.

17. The process of dyeing keratinaceous material which comprises applying thereto an aqueous solution of sodium thioglycolate, a water soluble salt of a metal selected from 8 the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 53-105.

18. The process of dyeing keratinaceous material which comprises applying thereto an aqueous solution of glyceryl thioglycolate, a water soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 8-10.5.

19. The process of dyeing keratinaceous material which comprises applying thereto an aqueous solution of 2- mercaptoethanol, a water soluble salt of a metal selected from the group consisting of cobalt, nickel, iron, manganese and bismuth in an amount equal to at least about 3.3 per cent by weight of the total composition and ammonia, the solution having a pH within the approximate range of 810.5.

References Cited in the fileof this patent UNITED STATES PATENTS 1,937,365 Stoddard Nov. 28, 1933 2,261,094 Speakman Oct. 28, 1941 2,540,980 Den Beste Feb. 6, 1951 FOREIGN PATENTS 117,071 Australia June 3, 1943 318,045 France Oct. 4, 1902 OTHER REFERENCES Hall: Textile Colorist, February 1942, pp. 63-65.

Winter: Hair Dyes of Today, Soap Perfumery and Cosmetics, December 1938, pp. 1080-1084 and 1088; pp. 1081, 1082 and 1084 particularly pertinent.

Allen: Review of Hair Dyes, Soap Perfumery and Cosmetics, September 1938, pp. 815-817, and 819; p. 819 particularly pertinent.

Claims

1. A DYEING COMPOSITION FOR KERATINACEOUS MATERIAL COMPRISING AN AQUEOUS SOLUTION OF A WATER SOLUBLE THIOL COMPOUND, A WATER SOLUBLE SALT OF A METAL SELECTED FROM THE GROUP CONSISTING OF COBALT, NICKEL, IRON, MANGANESE AND BISMUTH IN AN AMOUNT EQUAL TO AT LEAST ABOUT 3.3 PER CENT BY WEIGHT OF THE TOTAL COMPOSITION AND A WATER SOLUBLE ALKALINE MATERIAL, THE SOLUTION HAVING A PH WITHIN THE APPROXIMATE RANGE OF 8-10.5.