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Publication numberUS3760819 A
Publication typeGrant
Publication dateSep 25, 1973
Filing dateSep 9, 1970
Priority dateSep 9, 1970
Publication numberUS 3760819 A, US 3760819A, US-A-3760819, US3760819 A, US3760819A
InventorsG Vogt
Original AssigneeOreal
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Permanent waving of hair with quaternary ammonium alkylating agents and ammonium thioglycolate
US 3760819 A
Abstract
A method of permanently waving keratin substrates, such as hair, by applying thereto keratin softening agents and a quaternary ammonium halide salt keratin alkylating agent. Quaternary ammonium halide salts that make suitable keratin alkylating agents are mono, bis and tri quaternary reaction products or mixtures thereof selected from the group consisting of the reaction products of (1) hexamethylaminetetramine and cyanuric chloride; (2) hexamethylaminetetramine and 1,4-dichlorobutene; (3) hexamethylaminetetramine and p-bis-chloromethylbenzene; and (4) triethanolamine and cyanuric chloride.
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United States Patent [191 Vogt [451 Sept. 25, 1973 PERMANENT WAVING OF HAIR WITH QUATERNARY AMMONIUM ALKYLATING AGENTS AND AMMONIUM THIOGLYCOLATE [75] Inventor: Giinther Vogt,Schifferstadt/Pflaz,

Germany [73] Assignee: LOreal, Paris, France [22] Filed: Sept. 9, 1970 [211 Appl. No.: 70,919

Related U.S. Application Data [63] Continuation of Ser. No. 598,959, Dec. 5, 1966, abandoned, which is a continuation-in-part of Ser. No. 212,158, July 24, 1962, abandoned.

[52] US. Cl 132/7, 8/127.51,260/248.5, 260/2495, 260/2496, 260/249], 424/71, 424/72 [51] Int. Cl A45d 7/06 [58] Field of Search 424/71, 72; 8/127.5l; 132/7 [56] References Cited UNITED STATES PATENTS 2,749,342 6/1956 Auchincloss 260/2485 3,142,623 7/1964 Zviak et al 424/72 3,228,829 1/1966 Wolf et a1. 424/249 3,244,710 4/1966 Larsen 260/248.5

FQREIGN PATENTS OR APPLICATIONS 1,150,943 7/1963 Germany 424/72 Primary Examiner-Albert T. Meyers Assistant ExaminerVera C. Clarke Att0rneyCushman, Darby and Cushman and H01- combe, Wetheril1 & Brisebois [57] ABSTRACT 5 Claims, N0 Drawings PERMANENT WAVING OF HAIR WITH QUATERNARY AMMONIUM ALKYLATING AGENTS AND AMMONIUM THIOGLYCOLATE This application is a continuation of U.S. Pat. application Ser. No. 598,959, filed Dec. 5, 1966; which is a continuation-in-part of U.S. Pat. application Ser. No. 212,158, filed July 24, 1962; both now abandoned.

The present invention relates to the permanent shap ing of keratin substrates, and more particularly to improvements in the permanent waving of living hair.

Conventional permanent waves involve two steps. In the first step, a reducing agent, such as ammonium thioglycolate, is applied to the keratin substrate to split the disulfide links in the keratin into free thiol groups to make shaping, such as waving, of the substrate possible. In the second step, the shape is permanently fixed by reconstituting the disulfide links through the application of an oxidizing agent. In an alternate procedure, the shape is fixed by blocking the thiol groups by the application of a monoor bifunctional alkylating agent. This procedure involves two steps. In the treatment of wool, for instance, it has been proposed to use monoand bifunctional organic halides in organic solvents as alkylating agents, but this system cannot be used for living hair. Other methods of this type utilize aqueous solutions of quaternary ammonium salts which may be decomposed to produce an alkyl group resulting in an S-alkylation. The decomposition of the quaternary ammonium salt on the substrate and the resultant alkylation depend on the constitution of the compound which must be able to undergo the reaction mechanisms examined by Ingold et al. (Journal of the Chemical Society of London 1928, 3,125; 1929, 2,375; 1933, 66; and 1933 526) and by Snyder and Speck, Journal of the American Chemical Society 61, 668, 1939.

l have now found that novel, water-soluble, readily decomposable and non-toxic monoand polyquaternary ammonium compounds for this purpose may be obtained from tertiary aliphatic or alicyclic dior polyamines or alkanolamines and acyclic or cyclic monoor polyhalogen compounds containing a conjugate double bond. The preferred halogen compound is 2,4,6-trichloro-l,3,5-triazine (cyanuric chloride). The invention covers a method of permanently waving keratin substrates, such as hair, by applying thereto keratin softening agents and a quaternary ammonium halide salt keratin alkylating agent. Quaternary ammonium halide salts that make suitable keratin alkylating agents are mono, his and tri quaternary reaction products or mixtures thereof selected from the group consisting of the reaction products of (1) hexamethylaminetetramine and cyanuric chloride; (2) hexamethylaminetetramine and 1,4-dichlorobutene; (3) hexamethylaminetetramine and p-bis-chloromethylbenzene; and (4) triethanolamine and cyanuric chloride.

More specifically the new compounds of this invention are (1) mono, di and tri hexamethylenetetramine cyanuryl chloride; (2) mono, di and tri triethanolamine cyanuryl chloride; (3) mono and di hexamethylenetetramine butene chloride; and (4) mono and di hexamethylenetetramine para-.bis-methylbenzene chloride.

The alkylating agents of the invention are produced by reacting a solution containing stoichiometric amounts of the components in anhydrous polar solvents or suspensions thereof. The reaction product is recovered as a solid. Typical methods of forming the reaction products of this invention are illustrated by examples 1 to 4 below.

Examples 1 to 12 relate to preferred di or bisquaternary ammonium salts, but it should be noted that the mono and tri quaternary ammonium salts may also be used to alkylate keratin substrates. Furthermore the mono, bis and tri quaternary salts may be used individually or in various mixtures to alkylate the keratin substrate. Austrian Pat. No. 174,377 also illustrates other methods of producing the mono, bis and tri quaternary ammonium salts of this invention.

The quaternary ammonium alkylating compounds of the present invention may be used in a one-step process of permanently shaping keratin substrates, such as the permanent waving of living hair, since said component will effect S-alkylation on the hair keratin only at an elevated temperature by decomposition of said compound in the aqueous alkaline solution conventionally used in the permanent waving of hair without causing premature alkylation of the thioglycolate reducing agent. In view of the stability of the quaternary ammonium compounds of this invention in thioglycolate solutions, these alkylating agents may be put into the permanent wave solution and stored at ambient temperatures for extended periods of time. This is an additional advantage in using these compounds since it simplifies handling and application.

The optimum pH range of the permanent wave solution is 8 to 10 and the preferred molar ratio concentration of the keratin softening agent, for instance ammonium thioglycolate, to the quaternary ammonium compound is 0.5-1 1.

While in no way limited thereto, the method of pre paring some of the quaternary ammonium salts of this invention will be illustrated by examples 1 to 4.

EXAMPLE 1 Preparation of the bis-quaternary ammonia salt obtained by reacting hexamethylenetetramine and cyanuric chloride, having the formula:

The hexamethylenetetramine was dried in an oven for 5 hours at C. Then 28 grams of hexamethylenetetramine was dispersed in 60 cc. of dioxane.

A solution containing 20 g. of cyanuric chloride in 40 cc. of dioxane was prepared. This solution was added to the hexamethylenetetramine suspension while cooling to room temperature. The resulting mixture was stirred until the odor of cyanuric chloride disappeared completely. After drying the reaction mixture, a yellow powder was obtained. The yield was 40 percent and the product had a fusion point of 189 C.

EXAMPLE 2 Preparation of the bis-quaternary ammonia salt obtained by reacting triethanolamine and cyanuric chloride having the formula:

1H. \IL

EXAMPLE 3 Preparation of the bis-quaternary ammonia salt obtained by reacting hexamethylenetetramine and 1,4- dichloro-2-butene, having the formula:

HOCHzCH;

The hexamethylenetetramine was pulverized and dried in an oven for 5 hours at 1 C. A suspension of 28 g of the dry substance is prepared in 50 ml. of dioxane, and g. of l,4-dichloro-2-butene are added to the suspension.

The mixture was left for 8 days in a closed bottle. At the end of this time, a thick, yellowish mass was formed. The dioxane was dried and the residue was washed several times with methyl ethyl acetone to eliminate the excess dichlorobutene.

A 60 percent yield of a yellow powder was obtained which had a fusion point of 157 C.

EXAMPLE 4 Preparation of the bis-quaternary ammonia salt ob- The hexamethylene tetramine was pulverized and dried in an oven for 5 hours at 1 10 C. A suspension of 28 g. of dried hexamethylenetetramine was prepared in 50 ml. of methylethyl acetone. Next g. of para-bischloromethylbenzene was dissolved in just the necessary amount of dioxane and this solution was added to the preceding suspension. The mixture was kept in a tightly closed bottle for 3 days. The residue was then dried and washed with methylethyl acetone and ether.

Sixty-five percent of the desired compound was obtained in the form of a white powder, having a fusion point of 212 C.

Examples 5 to 12 illustrate how the quaternary ammonium salts of this invention may be used to alkylate or permanently wave keratin substrates.

EXAMPLE 5 ml ofa 10 percent ammonium thioglycolate solution was adjusted with ammonia to a pH of 9. 1.5 of urea and 6.5 of the bis-quaternary ammonium salt of hexamethylenetetramine and cyanuric chloride of Example l were dissolved in the solution. Untreated strains of hair were impregnated with the solution, wound on curlers and subjected to the effects of the solution for 15 minutes at ambient temperature. The temperature was thereupon raised for 5 minutes to 55 C. The hair was then carefully rinsed and dried.

EXAMPLE 6 100 ml ofa 10 percent ammonium thioglycolate solution was adjusted with ammonia to a pH of 9.5 and 1.5 of urea and 7.5 g of the bis-quaternary ammonium salt of triethanolamine and cyanuric chloride of Example 2 were dissolved in the solution. The hair was treated with this solution as in Example 5.

EXAMPLE 7 Untreated strains of hair were impregnated with the thioglycolate solution of Example 5, wound on curlers and subjected to the effects of the solution of 15 minutes at ambient temperature. The bis-quaternary ammonium salt of Example 5 was then added to the solution on the hair and the temperature was raised for five minutes to 55 C. The hair was then carefully rinsed and dried.

EXAMPLE 8 The procedure was the same as in Example 7 but the ammonium salt of Example 6 was used.

EXAMPLE 9 Example 6 was repeated but the ammonium salt was substituted by the bis-quaternary ammonium salt of hexamethylenetetramine and 1,4-dichloro-2-butene of Example 3. The hair was treated as in Example 5.

EXAMPLE 10 Example 9 was repeated but the ammonium salt was added only shortly before the temperature was raised.

EXAMPLE 1 1 Example 6 was repeated but the ammonium salt was substituted by the bis-quaternary ammonium slat of hexamethylenetetramine and p-bis-chloromethyl benzene of Example 4. The hair was treated as in Example 5.

EXAMPLE 12 Example 1 1 was repeated but the ammonium salt was added only shortly before the temperature was raised.

in all examples, the hair received a good permanent wave of soft hand.

Using the standards of alkali solubility of Am. Dyestuffs Rep. 25, 542 (1936), the following values were obtained:

Untreated Hair Treated According to Example Conventional Hair 5,6,7,8,9,l0,l1 ,12 5 5.7, 5.8, 7.0, 6.0, 4.3, 8.4, 4.9, 8.8 10.2

What is claimed is:

l. A composition for facilitating the permanent shaping of keratin substrates comprising an aqueous ammoniacal solution, having a pH of 8 to 10, of a keratin reducing amount of ammonium thioglycolate and a kera- 5 tin alkylating amount of a quaternary ammonium comhaving a fusion point of 157 C; and

4. bis-quaternary ammonium salt of hexamethylenetetramine and para-bis-chloromethylbenzene of the formula pound alkylating agent selected from the group consist- C111 ing of N N 1. bis-quaternary ammonium salt of hexamethylene- 2 CI'I;N\ /N tetramine and cyanuric chloride of the formula 10 3 I 01- N N (:1- HOCHQCH; N CHZCH1OH I l j CH2 CH1 CH2 CH; 01 1{OcH,cH,;N-|c c N-cI-ncH,0I-I 01- l oucrncm N N cincmon 1 having a fusion point of 189 C;

2. bis-quaternary ammonium salt of triethanolamine having a fusion point of 152 C;

3. bis-quaternary ammonium salt of hexamethylenetetramine and 1,4-dichloro 2-butene of the formula cm CH5 having a fusion point of 212 C, the ratio of the molar concentration of ammonium thioglycolate to the quaternary ammonium compound alkylating agent being 0.5:1 to 1:1.

2. The composition of claim 1 having a pH of 9.

3. The composition of claim 2 which also contains urea.

4. A method of permanently shaping living hair comprising the steps of applying to the hair in amounts effective to facilitate the shaping of said hair the composition of claim 1, shaping the hair, keeping said composition on the hair for about 15 minutes at ambient temperature, then raising the temperature to about 55 C, keeping said composition on the hair for about 5 minutes at 55 C, rinsing and then drying the hair.

'5. The composition of claim 3 wherein said ammonium thioglycolate is present in amounts of about 10 weight percent, said urea is present in amounts of about 1.5 g and said quaternary ammonium compound alkylating agent is present in amounts of about 6.5 to 7.5 g

per m1 of said composition.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2749342 *Jan 21, 1955Jun 5, 1956Auchincloss ReginaldHeterocyclic nu-adducts
US3142623 *Nov 22, 1961Jul 28, 1964OrealPermanent waving of hair and analogous processes
US3228829 *Nov 4, 1963Jan 11, 1966Dow Chemical CoPreservation of aqueous dispersions
US3244710 *Dec 23, 1963Apr 5, 1966Dow Chemical CoIodine complexes of hexamethylene-tetramine quaternary salts
DE1150943B *Jan 31, 1961Jul 4, 1963Guenther Vogt Dipl Chem DrVerfahren zur dauernden Verformung von Keratinfasern, insbesondere lebendem Haar
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4391286 *Feb 19, 1981Jul 5, 1983Helene Curtis IndustriesHair conditioning and composition therefor
US4507280 *Feb 12, 1982Mar 26, 1985Clairol IncorporatedHair conditioning composition and method for use
US4572220 *Jun 30, 1983Feb 25, 1986Helene Curtis Industries, Inc.Composition for altering the configuration of hair
US4588760 *Aug 9, 1985May 13, 1986Clairol IncorporatedHair treatment composition
US4663158 *Feb 22, 1985May 5, 1987Clairol IncorporatedHair conditioning composition containing cationic polymer and amphoteric surfactant and method for use
USRE29883 *May 25, 1977Jan 16, 1979Cosan Chemical CorporationAntibacterial product
DE2447547A1 *Oct 4, 1974Jun 19, 1975Cosan Chem CorpAmmoniumaddukt und seine verwendung als antimikrobiotisches mittel
Classifications
U.S. Classification132/206, 544/185, 544/190, 8/127.51, 544/209, 544/204, 424/70.2
International ClassificationA01N43/64, C07D487/18, A61K8/49, A61Q5/04, A61K8/46
Cooperative ClassificationC07D487/18, A61Q5/04, A61K8/4966, A61K8/46
European ClassificationA61K8/46, A61K8/49F4, A61Q5/04, C07D487/18