GB1576165A

GB1576165A - Hair structure composition and method using same

Info

Publication number: GB1576165A
Application number: GB5215677A
Authority: GB
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1976-12-20
Filing date: 1977-12-15
Publication date: 1980-10-01
Also published as: FR2374027A1; NL7713156A; FR2374027B1; DE2657613A1; ATA902477A; BE861990A; IT1091577B; AT353978B

Description

(54) HAIR STRUCTURE IMPROVING COMPOSITION AND METHOD USING SAME (71) We, HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN, a German company of 67 Henkelstrasse, 4000 Dusseldorf-Holthausen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a composition comprising carboxylic acid alkoxy methyl esters for improving the structure of hair damaged by hairdressing operations such as waving, blonding or dyeing processes.

It is common knowledge that cosmetic treatment of human hair for reasons of fashion leads, in many cases, to damage to the hair structure. Treatment which can cause damage to a greater or lesser extent constitutes, for example, permanent waving, repeated cold waving, blonding and brightening processes and the dyeing process with oxidation dyes, particularly with simultaneous brightening. Damage to the hair is manifested by a loss of its natural lustre, an unattractive dull appearance and, in the case of greater damage, by the splitting of the ends of the hair, the breaking-off of the hair or by the appearance of small knots in the hair.

Attempts have already been made to improve the structure of hair, damaged in this manner, by treatment with various agents, although a satisfactory solution has not yet been found. Thus, in accordance with German Auslegesschrift (Published Specification) 1,148,039, low molecular formaldehyde preliminary condensation products of urea or thiourea are applied to the hair and, by further condensation on the surface of the hair and, if required, also in the capillary spaces, lead to the formation of a film and the strengthening of the hair. However, this only imparts a greater hold to the damaged hair by means of a synthetic resin structure and does not improve the structure of the damaged hair. Furthermore, attempts have been made to improve the properties by cosmetic treatment of damaged hair by treating the hair with agents which contained multiple aldehydes such as glycol dialdehyde, glycerol aldehydes, glutaric dialdehyde and other aliphatic or aromatic polyaldehydes. The chief disadvantage of agents of this type is that they can cause serious irritation to the scalps of sensitive persons.

It has now been found that carboxylic acid alkoxy methyl esters of the following general formula can be used to advantage for the purpose of improving the structure of damaged hair:

in which Rl and R2 represent, independently of one another, hydrogen, an hydroxyl group, an alkyl radical having 1 to 4 carbon atoms, the radical -OR4 in which R4 represents an alkyl radical having 1 to 4 carbon atoms, the radical -COOR5 in which R5 represents an alkyl radical having 1 to 4 carbon atoms or the group -CH2-O-R3, with the proviso that R1 and R2 cannot simultaneously represent an hydroxyl group, the radical -OR4 or the radical -COOR5, and R3 represents an alkyl radical or hydroxy alkyl radical having 1 to 18 carbon atoms.

The carboxylic acid alkoxy methyl ester to be used in accordance with the present invention can be produced, in accordance with methods known from the literature, from the corresponding carboxylic acids by reaction with the chloromethyl alkyl ethers in the presence of a base in an inert solvent in accordance with the following reaction pattern:

In these structural formulae, the radicals R1, R2 and R3 have the meaning given above.

By way of example, the following compound may be mentioned as the carboxylic acid alkoxy methyl esters to be used in accordance with the present invention: acetic acid methoxy methyl ester, acetic acid ethoxy methyl ester, acetic acid butoxy methyl ester, propionic acid methoxy methyl ester, propionic acid butoxy methyl ester, valeric acid methoxy methyl ester, isobutyric acid ethoxy methyl ester, caproic acid methoxy methyl ester, caproic acid ethoxy methyl ester, caproic acid propoxy methyl ester, glycolic acid methoxy methyl ester, glycolic acid ethoxy methyl ester, glycolic acid butoxy methyl ester, lactic acid methoxy methyl ester, lactic acid ethoxy methyl ester, lactic acid propoxy methyl ester, ethoxy acetic acid methoxy methyl ester, malonic acid (ethyl) methoxy methyl ester, malonic acid-di-ethoxy methyl ester, malonic acid-di-propoxy methyl ester, malonic acid-di-butyoxy methyl ester. Owing to their action, the greatest importance is attached to the malonic acid-di-alkoxy methyl esters in turn including malonic acid-di-ethoxy methyl ester and -di-methoxy methyl ester.

Advantageously, in accordance with the present invention, the carboxylic acid alkoxy methyl esters are used in the form of an acid aqueous-alcoholic solution which is applied to the hair after the permanent waving, cold-waving, the blonding or the dyeing process and before further treatment of the hair. In so far as they are stable in an acid environment, strengthening and brightening substances which, for example, improve the combability, can also be introduced into this acid treatment solution. The pH value of the acid treatment solution, containing the carboxylic acid alkoxy methyl esters to be used in accordance with the present invention, varies between the values 2.5 to 6.5, preferably 2.5 to 4.0. The content of the carboxylic acid alkoxy methyl esters in the treatment solution is 1 to 10 percent by weight, preferably 2 to 7 percent by weight, relative to the total solution.

The treatment solution may be adjusted to the desired pH value by means of physiologically harmless acids such as lactic acid, tartic acid, and citric acid. Ethanol and isopropanol act as the alcoholic components of the aqueous-alcoholic solution.

The structure-improving agents are made up in the form of a two-component pack, one of the components generally constituting the acid aqueous-alcoholic solution including any strengthening and brightening additives, and the second component being the carboxylic acid alkoxy methyl ester. The two compnents are combined before use, thus producing the treatment solution ready for use. The damaged hair is impregnated with the solution and is subsequently dried by means of a hair-dryer, the application of the structure-improving treatment solution in many cases being the last treatment before the hair is dressed.

The following Examples are intended to further explain the present invention, but without limiting the invention to these Examples.

EXAMPLES Some of the carboxylic acid alkoxy methyl esters, to be used in accordance with the present invention, will be further described in the first instance.

A) Producing the malonic acid-di-ethoxymethyl ester.

C2H5O - CH2-OOC-CH2 -COO -CH2 -OC2H5 52 g (0.5 mol) of malonic acid were dissolved in a mixture of 200 ml of acetic acid and 50 ml of tetrahydrofuran, and 94.5 g (1 mol) of chloromethyl ether were added drop-by-drop under cooling. After 30 minutes, 101 g (1 mol) of triethylamine were added drop-by-drop under agitation. The mixture was subsequently heated to boiling for a further 2 hours. The mixture was filtered after cooling, the solvent was distilled off, and the residue was fractionally distilled under reduced pressure. 62 g of malonic acid-di-ethoxy methyl ester were obtained, corresponding to a yield of 56%of theory, having the following characteristic data: b.p. 99"C / 0.06 mm, nD = 1.4260.

The following products were produced in an analogous manner.

B) Malonic acid-di-methoxy methyl ester CH30 - CH2- OOC -CH2 - COO - CH2 -OC2H5 20 b.p. 95"C / 0.04 mm, nD = 1.4270 Yield 58% of theory.

C) Malonic (ethyl)methoxy methyl ester C2H5OOC - CH2 - COO - CH2 - OCH3 b.p. 39"C / 0.03 mm, nD = 1.4132 Yield 43% of theory.

D) Glycolic acid methoxy methyl ester HO - CH2 COO - CH2 - OCH3 20 b.p. 85"C / 0.01 mm, nD = 1.4251 Yield 32% of theory.

E) Glycolic acid butoxy methyl ester HO - CH2 COO - CH2 -OC4H9 20 b.p. 98"C / 0.03 mm, nD = 1.4385 Yield 67% of theory.

F) Caproic acid ethoxy methyl ester C5HltCOO - CH2 - OC2H5 b.p. 42"C / 0.03 mm, a020 = 1.4162 Yield 81% of theory.

A so-called panel test was carried out in order to show the structure-improving action. A group of 15 trained persons examined and evaluated the appearance, feel and combability of treated strands of hair. The evaluation scale extended from 0 to 10, low numbers indicating poor assessments and high numbers indicating satisfactory assessments. In detail, the following properties were tested and were evaluated as described hereinafter. The point values 1 to 9 lay between the two extremes Number of points Number of points 0 dull, lustreless to 10 high gloss, smooth 0 hard, bristly feel to 10 soft, silky, pleasant feel 0 badly combable, many to 10 satisfactorily combable, hairs breaking off no hairs being destroyed The strands of hair to be tested were damaged by blonding and waving. The degree of damage was reduced by intermediate treatments with a solution of the structure-improving compound. The criteria used were an untreated strand of brown, natural hair to which the assessment mark 10 had been allocated, and a strand of the same starting hair which had been damaged by blonding and cold-waving it four times without treatment with a structureimproving agent and which had received the assessment mark 0. In detail, the treatment was effected in the following manner: The strand of hair was blonded for 45 minutes at room temperature, subsequently rinsed thoroughly with water heated to 400C, and then rubbed with a towel and dried by means of a hair-dryer.

Blonding was effected with a mixture of the following composition: A cream -of the following constituents was first produced: Cetyl-stearyl alcohol 11.0 parts by weight Lauryl sulphate 12.0 parts by weight Ammonium sulphate 1.0 parts by weight Ammonia, conc. 14.0 parts by weight Water 62.0 parts by weight In order to produce the blonding mixture, 50 g of the cream were mixed with 50 g of a 6% hydrogen peroxide solution and 14 g of ammonium peroxide disulphate.

The dry strand of hair was impregnated with the acid solution of the carboxylic acid alkoxy methyl ester whose action was to be tested, surplus liquid was rubbed from the hair by means of a towel, and the hair was subsequently dired by means of a hair-dryer.

The hair was treated with a solution of 5 g of the corresponding carboxylic acid alkoxy methyl ester in a mixture which comprised 30 g of isopropanol and 65 g of water, the solution having been adjusted to a pH value of 2.5 with lactic acid.

The blonded strand of hair treated with the solution of the structure-improving compound was intensively wetted for 30 minutes with a waving fluid and was subsequently treated for 10 minutes with a fixing mixture containing bromate. The hair was dried with a hair-dryer after having been thoroughly rinsed out.

The waving fluid was a 6 % thioglycolic acid solution which had been adjusted to a pH value of 9.3 with ammonia.

The fixing mixture had the following composition: Potassium bromate 3.5 parts by weight Tartaric acid 0.4 parts by weight Water 96.1 parts by weight The hair was subsequently treated again with the solution of the structure-improving compound in the manner described above. The operations were repeated in the described sequence until the hair had been blonded four times, waved four times and treated eight times with the solution of the structure-improving compound. The comparison strand was subjected to the same bleaching and waving processes, although without intermediate treatment with the solution of the structure-improving compound. The strands of hair were assessed after all these treatments had been completed.

The evaluation resulted in the assessment marks, given in the following Table 1, which constitute in each case the average value of the 15 individual assessments of the three properties tested and thus give an overall picture of the structure-improving action of the individual compound.

Table 1 Compound Assessment mark Untreated, natural hair 10 Malonic acid-di-ethoxy methyl ester 9 Malonic acid-di-methoxy methyl ester 9 Malonic acid (ethyl)methoxy methyl ester 4 Glycolic acid methoxy methyl ester 6 Glycolic acid butoxymethyl ester 7 Caproic acid ethoxy methyl ester 6 Hair which had been bleached and waved 4 times wthout intermediate treatment with the solution of the structure-improving compound 0 The above Table shows that considerable structure-improving properties are to be ascribed to the compounds to be used in accordance with the present invention, since the value 10 would mean that the hair damaged by repeated blonding and waving behaves like the untreated starting hair owing to the intermediate treatment with the solution of the structure-improving compound.

Compositions of two-component treatment solutions for improving the structure of damaged hair are given hereinafter: Structure-improving composition 25.0 g Component I: Isopropanol 25.0 g Perfume oil Lactic acid 1.0 g Water 95.0 g Component II: Malonic acid-di-ethoxy 5.0 g Methyl ester The components are thoroughly mixed before use. The treatment solution has a pH value of 2.5.

Tartaric acid, citric acid and other physiologically harmless acids may be used instead of lactic acid for the purpose of adjusting the acid pH value. Malonic acid-di-methoxytmethyl ester, malonic acid(ethyl)methoxy methyl ester, glycolic acid methoxy methyl ester, glycolic acid butoxy methyl ester, caproic acid ethoxy methyl ester and other carboxylic acid alkoxy methyl esters covered by the above-mentioned general formula can also be used as structure improving substances.

Structure-improving composition at the same time having a strengthening and brightening action Component I: Ethanol 30.0 g Perfume oil 0.3 g Polyvinylpyrrolidone 4.0 g Pentaethoxy ethyl stearyl-ammonium chloride 0.4 g Water 58.3 g 93.0 g Component II: Glycolic acid methoxy methyl ester 7.0 g The components are throughly mixed before use. The pH value of the finished treatment solution was 2.25.

All the other carboxylic acid alkoxy methyl esters mentioned above may be used instead of the glycolic acid methoxy methyl ester.

WHAT WE CLAIM IS: 1. A hair-structure improving composition comprising an acid aqueous-alcoholic solution of at least one carboxylic acid alkoxy methyl ester of the general formula Rl - CH - COO - CH2 - O - R3 R2 in which R, and R2 represent, independently of one another, hydrogen, an hydroxyl group, an alkyl radical having 1 to 4 carbon atoms, the radical -OR4 in which R4 represents an alkyl radical having 1 to 4 carbon atoms, the radical -COOR5 in which R5 represents an alkyl radical having 1 to 4 carbon atoms or the group -CH2-O-R3, with the proviso that Rl and R2

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Table 1 Compound Assessment mark Untreated, natural hair 10 Malonic acid-di-ethoxy methyl ester 9 Malonic acid-di-methoxy methyl ester 9 Malonic acid (ethyl)methoxy methyl ester 4 Glycolic acid methoxy methyl ester 6 Glycolic acid butoxymethyl ester 7 Caproic acid ethoxy methyl ester 6 Hair which had been bleached and waved 4 times wthout intermediate treatment with the solution of the structure-improving compound 0 The above Table shows that considerable structure-improving properties are to be ascribed to the compounds to be used in accordance with the present invention, since the value 10 would mean that the hair damaged by repeated blonding and waving behaves like the untreated starting hair owing to the intermediate treatment with the solution of the structure-improving compound. Compositions of two-component treatment solutions for improving the structure of damaged hair are given hereinafter: Structure-improving composition 25.0 g Component I: Isopropanol 25.0 g Perfume oil Lactic acid 1.0 g Water 95.0 g Component II: Malonic acid-di-ethoxy 5.0 g Methyl ester The components are thoroughly mixed before use. The treatment solution has a pH value of 2.5. Tartaric acid, citric acid and other physiologically harmless acids may be used instead of lactic acid for the purpose of adjusting the acid pH value. Malonic acid-di-methoxytmethyl ester, malonic acid(ethyl)methoxy methyl ester, glycolic acid methoxy methyl ester, glycolic acid butoxy methyl ester, caproic acid ethoxy methyl ester and other carboxylic acid alkoxy methyl esters covered by the above-mentioned general formula can also be used as structure improving substances. Structure-improving composition at the same time having a strengthening and brightening action Component I: Ethanol 30.0 g Perfume oil 0.3 g Polyvinylpyrrolidone 4.0 g Pentaethoxy ethyl stearyl-ammonium chloride 0.4 g Water 58.3 g 93.0 g Component II: Glycolic acid methoxy methyl ester 7.0 g The components are throughly mixed before use. The pH value of the finished treatment solution was 2.25. All the other carboxylic acid alkoxy methyl esters mentioned above may be used instead of the glycolic acid methoxy methyl ester. WHAT WE CLAIM IS:

1. A hair-structure improving composition comprising an acid aqueous-alcoholic solution of at least one carboxylic acid alkoxy methyl ester of the general formula Rl - CH - COO - CH2 - O - R3 R2 in which R, and R2 represent, independently of one another, hydrogen, an hydroxyl group, an alkyl radical having 1 to 4 carbon atoms, the radical -OR4 in which R4 represents an alkyl radical having 1 to 4 carbon atoms, the radical -COOR5 in which R5 represents an alkyl radical having 1 to 4 carbon atoms or the group -CH2-O-R3, with the proviso that Rl and R2

cannot simultaneously represent an hydroxyl group, the radical -OR4 or the radical -COOR5, and R3 represents an alkyl radical or hydroxy alkyl radical having 1 to 18 carbon atoms.

2. A composition as claimed in claim 1 in which the carboxylic acid alkoxy methyl ester is a malonic acid-di-alkoxy methyl ester.

3. A composition as claimed in claim 2 in which the malonic acid--ethoxy methyl ester is malonic acid-di-ethoxy methyl ester.

4. A composition as claimed in claim 2 in which the malonic acid-di-alkoxy methyl ester is malonic acid-di-methoxy methyl ester.

5. A composition as claimed in any of claims 1 to 4 in which the composition has a pH value of from 2.5 to 6.5.

6. A composition as claimed in claim 5 in which the pH value is from 2.5 to 4.0.

7. A composition as claimed in any of claims 1 to 6 in which the carboxylic acid alkoxy methyl ester is present in an amount of from 1 to 10 percent by weight based on the total weight of the composition.

8. A composition as claimed in claim 7 in which the said ester is present in an amount of from 2 to 7 per cent by weight based on the total weight of the composition.

9. A composition as claimed in any of the preceding claims in which the aqueous alcoholic solution is an aqueous ethanslic or aqueous isopropanolic solution.

10. A composition as claimed in any of the preceding claims which contains one or more of lactic acid, tartaric acid or citric acid as pH adjusting agent.

11. A composition as claimed in any of the preceding claims which also comprises hair strengtheners and/or brightening agents.

12. A method of reducing damage caused to hair by hair-dressing operations involving the use of chemical treating agents which comprises contacting the hair after the hairdressing operation with a composition as claimed in any of claims 1 to 11.

13. A method as claimed in claim 12 in which the contacting of the hair with the said composition as claimed in any of claims 1 to 11 is effected before the hair is subjected to a further hairdressing operation.

14. A method as claimed in claim 12 or 13 in which after contact with the said composition hair is dried.

15. A composition as claimed in claim 1 substantially as hereinbefore described in any one of the Examples.

16. A method as claimed in claim 12 substantially as hereinbefore described in any one of the Examples.