Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3206362 A
Publication typeGrant
Publication dateSep 14, 1965
Filing dateJul 3, 1963
Priority dateJul 4, 1962
Also published asDE1467818A1, DE1467818B2, DE1467818C3
Publication numberUS 3206362 A, US 3206362A, US-A-3206362, US3206362 A, US3206362A
InventorsArthur Maeder, Burkhart Lange, Jean Hollub
Original AssigneeCiba Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Setting lotion for hair
US 3206362 A
Abstract  available in
Images(4)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,206,362 SETTING LOTEON FOR HAIR Jean Hollub, Geneva, Eurkliart Lange, Basel, and Arthur Maeder, Therwil, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Filed July 3, 1963, Ser. No. 292,756 Claims priority, application Switzerland, July 4, 1962, 8,02 8/ 62 12 Claims. (Cl. 167-811) It is known to use hairdressing preparations in order to maintain the hair in a desired shape. For this purpose there may be applied to the dry, combed hair a film-forming substance which has a setting effect on the hair. These preparations, also called hair lacquers, are primarily applied to the hair in the form of aerosol sprays. In this manner, depending on the amount of spray used, there is produced, especially on the outside, a coating of laquer of varying thickness which by virtue of its inner strength has a setting and stiffening effect on the individual hairs. There are also known preparations which are applied to the damp hair in aqueous form. In this case the hair is advantageously rolled into the desired shape and then dried. In this method the damp hair is impregnated with the setting lotion and after drying all hairs are completely covered with a very thin film; the hair treated in this manner does not feel stiff as it usually does when sprays are applied to it, it has a soft feel and has been set in the desired style.

From German Auslegeschrift 1,084,440 it is known to to use hairdressing preparations containing a basic polymer capable of forming salts, for example the chloride of the homopolymer of 2-vinyl 5-methylpyridine and of the acrylic acid diethylaminoethyl ester. However, after drying these salts form film that are soluble in water at room temperature. While their use in setting lotions does produce a setting coating on the hair, this coating is, because of its solubility in water, not resistant to moisture so that when the hair so treated is once more curled it can no longer be set in the original style. In a moist atmosphere any hair dressing preparation producing a non-moisture resistant film Will migrate along the hairs and collect at the tips.

It has now been found that certain Water-soluble salts of basic copolymers obtained by linear addition are rendered, by simple drying at temperatures ranging from 18 to 60 C. resistant to or soluble in water. Hair treated with such salts has the advantage that neither rain nor damp air will dissolve the coating. When hair treated with the setting lotion of the invention is exposed to moisture, then again laid in the desired style and dried, the resulting hairstyle is again stable as to shape. With known setting lotions based on dextrins, tragacanth,

' requirements, namely it must be capable of forming salts that are soluble in water, and it must form a water-insoluble film when its aqueous solution is dried at 18 to 60 C.

The present invention provides a moisture-resistant setting lotion in the form of an aqueous or aqueous-alcoholic solution for setting hair that has been laid in the damp state, the said solution containing an amount of 0.5 to 5% of a salt, which is at least soluble in an aqueous-alcoholic solution, of a weak inorganic or organic acid and a basic copolymer capable of forming films; the copolymer contains at least an amount of a basic mono meric compound containing a tertiary nitrogen atom sufficient to ensure that after the hair has been dried at a temperature ranging from 18 to C. a water-insoluble film is left on it. Furthermore, the present invention provides a method of making water waves of enhanced durability, more specially in a damp atmosphere, wherein damp hair is impregnated with an aqueous or aqueous alcoholic solution containing 0.5 to 5% of a salt, which is at least soluble in an aqueous-alcoholic solution, of a Weak inorganic or organic acid and a basic copolymer capable of forming films, the said copolymer containing a basic monomer with a tertiary nitrogen atom in an amount sufficient to ensure that after having been dried the hair is covered with a water-insoluble film, whereupon the impregnated hair is laid in the desired shape and dried at a temperature ranging from 20 to 60 C., preferably from 30 to 50C.

The solubility of the salts in water must be such that they are soluble at 15 to 25 C. and at a concentration of up to 20% by weight in water or in an aqueous-alcoholic mixture of 2 parts by weight of ethanol and at least 8 parts of water. If the share of the salt-forming, basic component is too large, drying does not convert the films into the water-insoluble state; if it is too small, no watersoluble salts are formed. The expert will be able to ascertain by simple tests the maximum and minimum amounts of basic component required to ensure the desired solubility of the salts in water and their capability of forming a water-insoluble film.

The solubility of the salts in water and their capability of forming water-insoluble films depend also on the kind and amount of the non-basic comonomers. When, for example, acrylamide or its N-substituted alkylacrylamides are used the share of the basic component maybe smaller than when esters of acrylic or methacrylic acid are used. Since the manufacture of copolymers having the desired properties depends on a number of factors that affect one another, it is not possible to lay down a rule applicable to all cases. If the basic component used is an NzN- dialkylaminoalkyl acrylamide, it should as a rule be used in an amount not exceeding 30% by weight and not less than 5%. When an NzN-dialkylaminoalkyl methacrylic acid ester is used, the less pronounced solubilizing properties require 50% by weight or even more to be used.

As acids capable of forming salts there come into consideration weak inorganic or organic acids, that is to say acids whose dissociation constant is below 10- There may be mentioned: Boric, carbonic, formic, acetic, propionic and lactic acid. It is of special advantage to use a readily volatile acid, such as carbonic, formic or acetic acid.

To test the salts for their capability of forming waterinsoluble films an aqueous solution of the salts is poured over a plate of glass and allowed to evaporate at 18 to 25 C. The film (film thickness about 201.1.) is then dried for 1 hour at 45 C. The film is then kept covered with water for 1 hour at 18 to 25 C., and its dissolution or stability respectively is ascertained.

As a rule, the setting lotions contain the salts described above in a concentration of 0.5 to 5%, preferably 0.75 to 2% by weight. The solvent used may be water or, more advantageously, it is a mixture of alcohol and water because the alcohol promotes the evaporation and drying. The aqueous preparation used as setting lotion may contain, apart from the solvent or solvents and the salt of the basic copolymer, the conventional additives such as perfume, softening agents, evaporation accelerators and the like. As relevant examples there may be mentioned higher monohydric alcohols with 6 to 18 carbon atoms, polyhydric alcohols such as ethyleneglycol and polyethyleneglycols, condensation products of ethyl- 'contains at least one tertiary nitrogen atom, there are particularly suitable the compound-s of the following types:

(a) Basic amides or esters of aliphatic a:,B-ethylenically unsaturated monocarboxylic or dicarboxylic acids with 3 to carbon atoms;

(b) Basic vinyl ethers.

The copolymers are particularly advantageous to manufacture from the compounds of type (a), especially from the basic acides of polymerizable aliphatic otIB-UHSEIUI- rated monocarboxylic acids whose molecule contains a tertiary nitrogen atom in the amide constituent. The

basic amides and esters are derived from an one-unsaturated acid of the acrylic acid series, that is to say from homologues of acrylic acid, such as methacrylic or cro tonic acid, or from the corresponding dicarboxylic acids, such as fumaric, itaconic or citraconic acid.

The basic amides and esters of monocarboxylic acids correspond preferably to the general formula where X represents ahydrogen atom or the methyl group, n and s each is 1 or 2, and R and R each stands for an a-lkyl radical with 1 to 4 carbon atoms. R and R may also be linked together to form a heterocycle. When rr=1, the formula represents an amide of a copolymeriza- 'ble acid; when n=2 it stands for a corresponding ester. As examples of basic amides of the Formula 1 there may be mentioned:

Acylic acid-'y-diethylaminopropylamide, Methacrylic acid-'y-dimethylaminopropylamide, Methacrylic acid-,8-diethylaminoethylamide, Acrylic acid-fl-dimethylaminoethylamide, Acrylic acid-,B-N-morpholinoethylamide, and Acrylic acid-,B-pyrrolidinoethylamide.

As examples of basic esters of the Formula 1 there may be mentioned:

Acrylic acid-.B-diethylaminoethyl ester,

Acrylic acid-fi-dimethylaminoethyl ester, Methacrylic acid-'y-diethylaminopropyl ester, and Acrylic acid-'y-di-n-butylaminopropyl ester.

Compounds of the type (a) may also be basic amides or esters of aliphatic azB-unsaturated dicarboxylic acids, such as maleic acid-' -dimethylaminopropylamide, fumaric acid-di-[y-dimethylaminopropyl]-amide and fumaric aciddifl-diethylaminoethyl] -ester.

As examples of the basic vinyl ethers mentioned under (b) there may be used vinyl ethers containing a tertiary nitrogen atom andup to 12 carbon atoms, specifically the following: ,B-diethylaminoethyl vinyl ether, fl-di-n-butylaminoethyl vinyl ether, fi-morpholinoethyl vinyl ether and 4-dimethylaminophenyl-(1)-methylvinyl ether.

The manufacture of the basic monomers to be used according to this invention is known and does not form an object of the invention.

The polymerization may be conducted in solution or in emulsion, using the measure conventionally employed in the polymerization technique. Preferably, the polymerization is performed in solution. The basic copolymers may be manufactured by the processes described in the Brtish patent application No. 871,295, granted October 18, 1961, by A. Maeder, and British patent application No.

876,674, granted December 27, 1961, by A. Maeder. To convert the basic polymer into the salt, the polymer solution is concentrated by evaporating the solvent, whereupon advantageously the calculated amount of acid is added and the whole is diluted with water. When the salt to be manufactured is the carbonate, the solution is freed from the solvent and diluted with water and carbon dioxide is injected into it while cooling with ice.

As monomers with which the basic monomers are to be copolymerized there are suitable non-basic compounds which likewise contain a carbon-to-carbon double bond, more especially an H C:C group, in particular vinyl esters of organic acids, for example vinyl acetate, formate, butyrate or benzoate, or vinylaryl compounds such as styrene or substituted styrenes, compounds of the acrylic acid series such as esters of acrylic acid and alcohols or phenols that contain 1 to 12 carbon atoms and no tertiary amino group, for example ethyl acrylate, butyl acrylate and dodecyl acrylate, acrylonitrile or acrylamide and its derivatives substituted on the amide nitrogen, such as, NzN-diethyl acrylamide, NzN-dihyroxyethyl acrylamide, N-n-propyl acrylamide, N-tertiary butyl acrylamide, NzN- di-n-butyl-acrylamide and hexamethylolmelamine triacrylamide; furthermore, analogous derivatives of methacrylic, ot-chloracrylic, crontonic, maleic or fumaric acid. There may also be used polymerizable vinyl ethers such as vinylethyl ether. Preferred use is made of derivatives of acrylic and methacrylic acid (said derivatives being .free from basic nitrogen atoms) and among them above all the esters with aliphatic alcohols, or the N-monosubstituted amides in which an aliphatic substituent is linked to the amide nitrogen atom through a secondary or tertiary carbon atom. Particularly suitable are ternary copolymers that contain as the film-forming component 30 to 50% of an ester of acrylic or methacrylic acid and an alkanol with 1 to 4 carbon atoms; as setting and sheenforming component 30 to 50% of an N-monoalkyl-substituted or N:N-dialkyl-substituted acrylamide whose substituents contain 2 to 4 carbon atoms each, and as saltforming component 5 to 20% of an N:Ndi-(C C alkylamino- (C -C alkylacrylamide.

Percentages in the following examples are by weight.

Example 1 160 parts of ethyl acrylate, 200 parts of N-tertiary butyl acrylamide and 40 parts of NzN-diethylaminopropyl acrylamide are dissolved at room temperature in 320 parts of absolute ethanol in a 2-filter flask equipped with stirrer, reflux condenser and thermometer. The flask is then scavenged with nitrogen and the batch is heated to the boiling point of ethanol. 0.4 part of azo diisobutyronitrile is then added, and this addition is repeated four times at intervals of 1 hour each. The polymerization is slightly exothermic. 1 hour after the last addition of catalyst the mixture iscooled to room temperature.

Yield: 710 parts of a low viscous, colorless and clear resin solution having a solids content of 56%, which corresponds to a polymer yield of almost The resin solution is mixed with 14.5 parts of acetic acid (100% and 1265 parts of deionized water are slowly run in. The resulting thinly viscous, opalescent solution is filtered through a clarifying filter.

Yield: about 2000 parts, solids content 20.5%, pH::5.5.

When the solution is poured over a glass plate and allowed to dry in air, it forms a transparent, colorless film which, after having been stored for 72 hours at 18 C., still remains completely insoluble on immersion for 60 minutes in water at 18 C.

Example 2 Setting lotions are prepared with the use of the undermentioned salts, having the following composition:

1.25% of a salt of a copolymer Nos. 1 to 14, 0.4% of hexanol, 0.1% of urea,

0.6% of a condensation product from 1 mol ofstearyl alcohol and 25 mols of ethylene oxide,

% of alcohol,

made up to 100% with water.

The salts concerned are the following products:

( 1) Formate salt of the copolymer from 40% of ethyl acrylate, 55% of N-teritary butyl acrylamide and 5% of N:N-diethylaminomethacrylate.

(2) Acetate salt of the copolymer from 90% of ethyl acrylate and 10% of N:N-diethylaminopropyl acrylamide.

(3) Acetate salt of the copolymer from 50% of ethyl acrylate, 40% of N-teritary butyl acrylamide and 10% of NzN-diethylaminopropyl acrylamide.

(4) Acetate salt of the copolymer from 80% of ethyl acrylate, 10% of N-teritary butyl acrylamide and 10% of NzN-diethylaminopropyl acrylamide.

(5) Propionate salt of the copolymer from 80% of ethyl acrylate and 20% of NzN-diethylaminopropyl acrylamide.

(6) Acetate salt of the copolymer from 40% of ethyl acrylate, 50% of NzN-di-n-butyl acrylamide and 10% of N:N-diethylaminopropyl acrylamide.

(7) Carbonate salt of the copolymer from 85% of nbutyl acrylate and of NzN-dimethylaminoethyl acrylamide.

(8) Borate salt of the copolymer from 70% of methyl acrylate and 30% of NzN-diethylaminopropyl acrylamide.

(9) Lactate salt of the copolymer from 30% of ethyl acrylate, 10% of lauryl acrylate, 40% of NzN-diethyl acrylamide and of N:N-diethylaminoethyl acrylamide.

(10) Acetate salt of the copolymer from 40% of methyl methacrylate, 40% of n-butyl acrylate and 20% of NzN-diethylaminopropyl methacrylamide.

(11) Propionate salt of the copolymer from 50% of methyl acrylate, 15% of vinyl acetate and 35% of diethylaminopropyl vinyl ether.

(12) Acetate salt of the copolymer from 40% of ethyl acrylate, 30% of N-tertiary butyl acrylamide and 30% of N:N-diethylaminoethyl vinyl ether.

(13) Formate salt of the copolymer from 30% of ethyl acrylate, 20% of N-teritary butyl acrylamide and 5 0% of N:N-diethylaminoethyl methacrylate.

(14) Acetate salt of the copolymer from 75% of ethyl acrylate and of di-(N:N-dimethylaminopropyD- fumaric acid amide.

The hair is thoroughly washed and then dried with a towel only so much as to leave it damp. 10 to ml. of setting lotion are then applied so as to leave the hair thoroughly damp. The hair is then given the desired style (preferably by curling) and dried in air heated up to C. In all 14 cases there are obtained water waves which display a coating that is resistant to moist air. The hair can be styled again in the damp state and without additional treatment, and the resulting hairstyle is permanent.

What is claimed is:

1. A composition for setting hair that has been shaped in the damp state, comprising a solvent selected from the class consisting of water and a mixture of water and alcohol, and, in an amount of 0.5 to 5 percent, calculated on the total of the solution, a salt which is soluble in said solvent, of a weak acid selected from the group consisting of boric acid, carbonic acid, formic acid, acetic acid, propionic acid and lactic acid and a basic, filmforming copolymer, said copolymer consisting of (1) 30 to percent by weight of units of an alkyl ester of an acid selected from the group consisting of acrylic and methacrylic acid, wherein the alkyl has 1 to 4 carbon atoms, (2) 30 to 50 percent by weight of units of a substituted acrylamide selected from the group consisting of N-mono-alkyl-substituted and NzN-dialkyl-substituted acrylamide, the substituents containing 2 to 4 carbon atoms each, and (3) 5 to 20 percent by weight of units of an N:N-dialkyl-amino-alkylacrylamide, wherein the alkyl radicals contain at least 2 and at most 3 carbon atoms.

2. A composition for setting hair that has been shaped in the damp state, comprising a solvent selected from the class consisting of water and a mixture of water and alcohol, and, in an amount of 0.5 to 5 percent, calculated on the total of the solution, a salt Which is soluble in said solvent, of acetic acid and a basic, film-forming copolymer, said copolymer consisting of 30 to 50 percent by weight of units of ethyl-acrylate, 30 to 50 percent by weight of units of N-tertiary butyl-acrylamide, and 5 to 20 percent by weight of units of NzN-diethylaminopropyl-acrylamide.

3. A composition for setting hair that has been shaped in the damp state, comprising a solvent selected from the class consisting of water and a mixture of water and alcohol, and, in an amount of 0.5 to 5 percent, calculated on the total of the solution, a salt which is soluble in said solvent, of acetic acid and a basic, film-forming copolymer, said copolymer consisting of 40% of ethyl acrylate, 30% of N-tertiary butyl acrylamide and 30% of NzN-diethylaminoethyl vinyl ether.

4. A composition for setting hair that has been shaped in the damp state, comprising a solvent selected from the class consisting of water and a mixture of water and alcohol, and, in an amount of 0.5 to 5 percent, calculated on the total of the solution, a salt which is soluble in said solvent, of acetic acid and a basic, filmforming copolymer, said copolymer consisting of 30% of ethyl acrylate, 20% of N-tertiary butyl acrylamide and 50% of NzN-diethylaminoethyl methacrylate.

5. A composition for setting hair that has been shaped in the damp state, comprising a solvent selected from the class consisting of water and a mixture of water and alcohol, and, in an amount of 0.5 to 5 percent, calculated on the total of the solution, a salt which is soluble in said solvent, of acetic acid and a basic, film-forming copolymer, said copolymer consisting of 75% of ethyl acrylate and 25% of di-(N:N-dimethylaminopropyl)- fumaric acid amide.

6. A method for making water waves of enhanced durability in a damp atmosphere, wherein the damp hair is impregnated with a composition as claimed in claim 1, the impregnated hair is laid in the desired shape and dried at. a temperature ranging from 20 to 60 C.

'7. A method for making water waves of enhanced durability in a damp atmosphere, wherein the damp hair is impregnated with a composition as claimed in claim 2, the impregnated hair is laid in the desired shape and dried at a temperature ranging from 20 to 60 C.

8. A method for making water waves of enhanced durability in a damp atmosphere, wherein the damp hair is impregnated with a composition as claimed in claim 3, the impregnated hair is laid in the desired shape and dreed at a temperature ranging from 20 to 60 C.

9. A method for making water waves of enhanced durability in a damp atmosphere, wherein the damp hair is impregnated with a composition as claimed in claim 4, the impregnated hair is laid in the desired shape and dried at a temperature ranging from 20 to 60 C.

10. A method for making water waves of enhanced durability in a damp atmosphere, wherein the damp hair is impregnated with a composition as claimed in claim 5, the impregnated hair is laid in the desired shape and dried at a temperature ranging from 20 to 60 C.

11. A composition for setting hair that has been shaped in the damp state, comprising a solvent selected from the class consisting of water and a mixture of water and alcohol and, in an amount of 0.5 to 5 percent, calculated on the total of the solution, a salt which is soluble in said solvent, of lactic acid and a basic, film-forming copolymer, said copolymer consisting of 30 to 50 percent 7 by Weight of units of ethyl-acrylate, 30 to 50 percent by Weight of units of N-tertiary butyl-acrylarnide, and 5 to 20 percent by Weight of units of NzN-diethylaminopropyl-acrylamide.

12. A composition for setting hair that has been shaped in the damp state, comprising a solvent selected from the class consisting of Water and a mixture of water and alcohol and, in an amount of 0.5 to 5 percent, calculated on the total of the solution, a salt which is soluble in said solvent, of formic acid and a basic, film-forming copolymer, said copolymer consisting of 30 to 50 percent by weight of units of ethyl-acrylate, 30 to 50 percent by weight of units of N-tertiary butyl-acrylarnide, and 5 to 20 percent by weight of units of NzN-diethylaminopropyl-acrylamide.

References Cited by the Examiner UNITED STATES PATENTS 2,808,388 10/57 Hellman 260--29.6 1 3,069,390 12/62 Kline et al 16787.2

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2808388 *Jul 29, 1955Oct 1, 1957Eastman Kodak CoHydrosols of acrylic esters and hydrophobic monomers polymerized with cationic or ampholytic hydrophilic copolymers and process for making same
US3069390 *Jul 17, 1959Dec 18, 1962Borden CoPolymeric amides from polymeric acrylic acid esters and n-aminoalkyl alkanol amines and reaction products therefrom
US3078185 *Mar 22, 1954Feb 19, 1963Rohm & HaasStabilization of protein-containing textiles with nitrogen containing polymers
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3530215 *Jul 28, 1966Sep 22, 1970RevlonConditioning hair with quaternized homopolymers
US3726288 *Aug 4, 1971Apr 10, 1973Nat Starch Chem CorpProcess for setting hair using a preparation comprising a single fixative-thickener
US3954113 *Dec 14, 1973May 4, 1976Colgate-Palmolive CompanyMethod of and means for cleaning hair between shampoos and methods for preparing such means
US4149551 *Mar 28, 1977Apr 17, 1979The Procter & Gamble CompanyMethod of conditioning hair using a flexible substrate
Classifications
U.S. Classification132/206, 424/70.16, 424/70.17, 8/127.51, 524/555
International ClassificationA61B, A61K, A61Q5/06, A61K8/81, A61K8/72
Cooperative ClassificationA61K8/8158, A61Q5/06
European ClassificationA61K8/81K6, A61Q5/06