US3188275A

US3188275A - Vinyl acetate polyethylene glycol copolymer hair setting composition

Info

Publication number: US3188275A
Application number: US204038A
Authority: US
Inventors: Erlemann Gustav
Original assignee: F Hoffmann La Roche AG
Current assignee: F Hoffmann La Roche AG; Hoffmann La Roche Inc
Priority date: 1961-06-26
Filing date: 1962-06-21
Publication date: 1965-06-08
Anticipated expiration: 1982-06-08
Also published as: FI42985C; BE619352A; ES278639A1; NL278987A; FI42985B; OA00928A; IT943002B; GB944834A; DE1467925A1; SE303826B; CH408288A

Description

United States Patent The use of hair setting preparations, particularly after the hair has been Washed, is known. On drying, these preparations should form an invisible film on the surface of the hair to impart thereto superior mechanical strength. Furthermore, these preparations should make possible a light form of coitfure which holds in place over a long period of time. These preparations are known in the art as hair sets. Depending upon the solubility of the high polymer component in general contained therein, these preparations are in the form of aqueous, alcohol or aqueous-alcoholic solutions.

As the high polymer component of certain hair set preparations of the prior art, there have been used, for example, water-soluble substances, such as polyvinylpyrrolidone, vegetable gums, alginates, as well as cellulose derivatives. Preparations which contain such watersoluble, high polymer materials are disadvantageous, however, in that they are hygroscopic. The hair loses its resiliency after a short time and the hairdo collapses, for the high molecular weight compound produces only extra weight. Such preparations are unsatisfactory for use by persons having slightly oily hair since hair of this type becomes stringy very quickly.

High molecular weight, alcohol-soluble, film-forming compounds, such as polyvinyl acetate, maleic ethers, etc., form a deposit when applied to damp or hand toweldried hair. Preparations containing these compounds do not, therefore, form an unbroken film. After combing, a residue is left behind, and, as a result, hair which is treated with such products appears dull and lifeless and it proceeds to lose its resiliency.

It has now been found, unexpectedly, that the disadvantages referred to heretofore can be avoided and that hair having outsanding resiliency can be obtained when there is used, as the film-forming agent in hair set preparations, a mixture comprising (1) a copolymer of vinyl acetate and polyglycols, e.g., polyethylene glycol, copolymerized in a ratio of from about 1 to about 3 parts by weight of polyglycol for each part by weight of vinyl acetate and (2) panthenol or a panthenol ether. These mixtures are neither soluble in water nor soluble in absolute alcohol. They are, however, slightly soluble in mixtures of water and alcohol, for example, in aqueous alcohol solutions containing from about 30% to about 70% by weight of alcohol. Aqeuous alcohol solutions of this nature, preferably those containing ethyl alcohol and isopropyl alcohol as the alcohol compo nent, are used in producing the compositions of this invention.

The quantity of copolymer which is used in preparing the compositions of this invention may vary. Generally, the copolymer will comprise from about 1% to about of the total weight of products. Similarly, varying amounts of the panthenol component can be used. Broadly, however, panthenol, or a panthenol ether, will comprise from about 0.1% to about 3.0% of the weight of the product.

It has been found to be advantageous to use d-panthenol, or an ether derived from d-panthenol, in carrying out the present invention. As to the ethers used herein, panthenol methyl ether, panthenol ethyl ether,

panthenol allyl ether, panthenol n-decyl ether, panthen ol cetyl ether, panthenol diethylaminoethyl ether, panthenol phytyl ether, panthenol geranyl ether, pantenol tetrahydrofurfuryl ether, panthenol guaicol ether and panthenol ethyl mercapto ether, are of particular importance. These ethers are new compounds which can be obtained by the reaction of a,'y-dihydroxy-fifl-dimethylbutyrolactone with a suitable ether of 3-hydroxypropylamine.

Moreover, the compositions of this invention can addantageously contain triols, such as 1,2,3-trihydroxy- 3,7-dimethyloctane, l,2,3-trihydroxy-3,7, 1 l-trimethyldodecane, or, preferably, 1,2,3-trihydroxy-3,7,11,15-tetramethylhexadecane. These triols can advantageously comprise up to about 1.0% of the weight of the present compositions. These triols are also new compounds. They can be obtained by reacting dihydrolinalool (3,7-dimethyl-3-hydroxyoctaene-l), tetrahydronerolidol (3,7,1=l-trimethyl-3-hydroxydodecaene-l), or isophytol with an organic peracid, for example, performic acid, and by saponifying the reaction product, thus obtained, with an alkali, for example, with sodium hydroxide.

The preferred products of the invention are obtained using the following-name ingredients, in the quantities indicated:

Percent by weight Vinyl acetate-polyethyleneglycol copolymer 2.0 to 5.0 Panthenol or panthenol ether 0.3 to 1.0 3,7,1l,l5-tetramethyl-1,2,3-

trihydroxyhexadecane 0.2 to 0.5

Water-alcohol (40:60 to 60:40 parts by weight) as needed to make Hair, which is treated with the hair treating compositions of this invention, shows not only the desired strength but also an unexpected resiliency. All other properties such as gloss, combabih'ty, durability and firmness of the witfure are outstanding.

The preparations can be applied either to hand towel.- dried hair or damp hair without affecting the uniform formation of the film. After drying, the resulting film is hydrophobic and the coiffure is resistant to the humidity of the atmosphere.

Another unexpected efiect is that slightly oily hair remains soft and resilient for a longer period of time. Additionally, the use of these products provides a lasting set for hair of this nature.

For a fuller understanding of the nature and objects of this invention, reference may be had to the following examples which are given merely as further illustrations of the invention and are not to be construed in a limiting sense.

Example 1 A hair set was prepared by mixing the following-named ingredients in the proportions hereinafter indicated. All parts given are parts by weight, unless otherwise indicated.

Perfume and color, as needed.

Such product was found to be highly suited for use as a hair setting composition for normal hair.

For the sake of completeness, the method for producing the 3,7,11,IS-tetramethyl-l,2,3-trihydroxyhexadecane employed in this example is set forth hereinafter. It should 3 be fully understood, however, that, in and of itself, neither the compound, nor the process for its production, constitutes a part of the present invention.

200 grams of isophytol and 570 ml. of formic acid were mixed in a reaction vessel fitted with a stirrer, thermon eter and dropping funnel and the homogeneous mixture was stirred for two hours at a temperature of 40 C. Thereafter, the reaction mixture was cooled to a tempera ture of about C. and to it there was added, over a period of about 15 minutes, a solution of 83 grams of hydrogen peroxide (30% by weight) and 11 ml. of water. The temperature of the reaction mixture rose slowly and it was held at 40 C. with the aid of an ice bath. When, after nearly an hour, the temperature fell below 40 C. without cooling, the reaction mixture was maintained, for an additional two-hour period, at a temperature of about 40 C. by means of a water bath. Thereafter, the reaction mixture was poured into a mixture of 1 liter of ice water and 500 ml. of ether. The water layer was removed and the ether solution which remained was washed two times, using about 150 ml. of water each time. The ether layer was evaporated and the residue was mixed with 300 ml. of concentrated ammonia. This mixture was shaken thoroughly and then allowed to stand 15 minutes at room temperature. Subsequently, the water and ammonia were removed in a rolling evaporator at a temperature of about 50 C. by the use of a water pump and the viscous residue was taken up in 1500 ml. of ether. The ether solution was washed three times, using 200 ml. of watereach time, dried over sodium sulfate, filtered and the ether evaporated off. There was obtained 220 grams of 3,7,11,15 tetramethyl 1,2,3 trihydroxyhexadecane (dihydro-dihydroxyphytol) in the form of a bright, yellow colored, viscous oil. The product was recovered at 130 C./0.0l mm. by subsequent molecular distillation.

Example 2 In this example, a hair setting composition, particularly well suited for use on slightly oily hair, was prepared.

The composition was obtained by mixing the followingnamed ingredients in the quantities hereinafter indicated. All quantities set forth are parts by weight, unless otherwise stated.

Parts Vinyl acetate-polyethyleneglycol (1:1) COPOlYIXIGIp. 4.0 Panthenol ethyl ether 1.0 3,7,1l,1S-tetramethyl-l,2,3-trihydroxyhexadecane 0.2 Ethyl alcohol 45.0 Water 49.8

Perfume and color, as needed.

Example 3 In this example, a hair setting composition was prepared which is especially suitable for use on dry hair.

This composition was prepared by mixing the following-named ingredients in the quantities indicated. Unless otherwise stated, all parts given are parts by weight.

Parts Vinyl acetate-polyethyleneglycol (1:2) copolymer 3.0 Panthenol phytyl ether 1.0 3,7,11,15-tetramethyl1,2,S-trihydroxyhexadecane 0.5 Ethyl alcohol 50.0 Water 45.5

Perfume and color, as needed.

Example 4 In and of themselves, neither the panthenol ethers used in the preceding examples, nor the process by which they are produced, are part of the present invention. However, for the sake of completeness, a process for the production of the panthenol ethers used in Examples 2 and 3 hereof, as well as for the production of other ethers suitable for use in the present invention, is included herein.

Thus, 89.0 grams of 3-methoxy propylamine were added, all at once, to 130.0 grams or" D()-u-hydroxypfi-dimethyl y-butyrolactone. The reaction commenced immediately and the temperature of the reaction mixture rose to about 50 C. without the application of external heating. As the temperature thereof commenced to drop elow 50 C., heat was applied to the reaction mixture to maintain it at about 50 C. for two hours.

There was obtained, in a quantitative yield, panthenol methyl ether, that is, D(+)-(aw-dihydroxy-fi,fi-dimethylbutyryl)-(3-methoxy-propylamine), in the form of a colorless light fluid which was soluble in water and in conventional organic solvents, for example, alcohols, ketones and diethyl ether; [a] :28.0 (c.=3.0075 in water). During high vacuum distillation of this product, partial racemization occurred.

The 3-methoxy-propylamine (boiling point 114- 116 C./760 mm.), used in this example, was prepared by the catalytic hydrogenation of 3-methoxy-propionitrile in methanol in the presence of ammonia.

In a similar manner, there was obtained:

From 3-ethoxy-propylamine (boiling point 132C./ 760 mm.): panthenol ethyl ether, [a] +27.8

(c.=2.8935 in water);

From 3 (n-decyloxy) propylarnine (boiling point 14-5147 C./11 mm.): panthenol-n-decyl ether, [u] =+28.75 (c.=3.1l25 in methanol);

From 3-tetrahydrofurfuryloxy-propylamine (boiling point 100-102 C./ 10 mm.): panthenol tetrahydrofurfuryl ether, '[a] =+20.01 (c.=3.135 in water);

From 3-geranyloxy-propylamine (boiling point 138- 140 C./ 10 mm.): panthenol geranyl ether, [a] =+27.5 (c.=3.086 in methanol);

From 3-phytyloxy-propylamine (boiling point 168- 170 C./ 0.04 mm.): panthenol phytyl ether,

[ct] =+i3.37 (c -3.035 in methanol).

1 claim:

1. A composition comprising (a) a copolymer of vinyl acetate and polyethylene glycol, (b) a compound selected from the'group consisting of panthenol, panthenol methyl ether, panthenol ethyl ether, panthenol allyl ether, panthenol n-decyl ether, panthenol cetyl ether, panthenol diethylaminoethyl ether, panthenol phytyl ether, panthenol geranyl ether, panthenol tetrahydrofurfuryl ether, panthenol guaicol ether and panthenol ethyl mercapto ether, and (c) a member selected from the group consisting of aqueous ethyl alcohol and aqueous isopropyl alcohol, there being present in said component (a) from about 1 to about 3 parts by weight of polyethylene glycol for each part by weight of vinyl acetate therein and there being present in said component (c) from about 30% to about 70% by weight of said alcohol, said component (a) comprising from about 1% to about 10% and said component (b) comprising from about 0.1% to about 3% of the total weight of the composition.

2. The composition of claim 1 which contains also up to about 1% by weight of a member selected from the group consisting of 1,2,3-trihydroxy-3,7-dimethyloctane, 1,2,3-trihydroxy-3,7,ll-trimethyldodecane and 1,2,3-trihydroxy-3 ,7,11 ,1S-tetramethylhexadecane.

3. The composition of claim 1 wherein panthenol is employed.

4. The composition of claim 1 wherein the ethyl ether of panthenol is employed.

5. The composition of claim 1 wherein the phytyl ether of panthenol is employed.

6. A composition comprising (a) from about 2% to 5% by weight of a copolymer of vinyl acetate and polyethylene glycol, (b) from about 0.3% to about 1% by weight of a compound selected from the group consisting of panthenol, panthenol methyl ether, panthenol ethyl ether, panthenol allyl ether, panthenol n-decyl ether, panthenol cetyl ether, panthenol diethylaminoethyl ether, panthenol phytyl ether, panthenol geranyl ether, panthenol tetrahydrofurfuryl ether, panthenol guaicol ether and panthenol ethyl mercapto ether, and (c) a member selected from the group consisting of aqueous ethyl alcohol and aqueous isopropyl alcohol, and being present in said component (a) from about 1 to about 3 parts of weight of polyethylene glycol for each part by weight of vinyl acetate and there being present in said component (0) from about 30% to about 70%by Weight of the said alcohol.

7. The composition of claim 6 which contains also up to about 1% by weight of a member selected from the group consisting of 1,2,3-trihydroxy-3,7-dimethyloctane, 1,2,3-tril1ydroXy-3,7,1l-trimethyldodecane and 1,2,3-trihydroxy-3,7,1 1,1S-tetramethylhexadecane.

8. The composition of claim 6 which contains also from about 0.2% to about 0.5% by weight of 1,2,3-trihydroxy- 3,7,1 1,1S-tetramethylhexadecane.

9. The composition of claim 8 wherein panthenol is employed.

It). The composition of claim 6 wherein the ethyl ether of panthenol is employed.

11. The composition of claim 6 wherein the phytyl ether of panthenol is employed.

References Qited by the Examiner UNITED STATES PATENTS OTHER REFERENCES Harry, Modern Cosmeticology, volume 1, Leonard Hill Limited, London (1955), pages 4764753 and 734-747. 7 Sagarin, Cosmetics, Science and Technology, Interscience Publishers, Inc New York (1957), pages 534-536.

Sein'mmel Briefs, No. 303, June 1960, 1 page.

JULiAN S. LEVTTT, Primary Examiner.

LEWIS GOTTS, FRANK CACCIAPAGLIA, JR.,

. Examiners.

Claims

1. A COMPOUND COMPRISING (A) A COPOLYMER OF VINYL ACETATE AND POLYETHYLENE GLYCOL, (B) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF PANTHENOL, PANTHENOL METHYL ETHER, PANTHENOL ETHYL ETHER, PANTHENOL ALLYL ETHER, PANTHENOL N-DECYL ETHER, PANTHENOL CETYL ETHER, PANTHENOL DIETHYLAMINOETHYL ETHER, PANTHENOL PHYTYL ETHER, PANTHENOL GERANYL ETHER, PANTHENOL TETRAHYDROFURFURYL ETHER, PANTHENOL GUAICOL ETHER AND PANTHENOL ETHYL MERCAPTO ETHER, AND (C) A MEMBER SELECTED FROM THE GROUP CONSISTING OF AQUEOUS ETHYL ALCOHOL AND AQUEOUS ISOPROPYL ALCOHOL, THERE BEING PRESENT IN SAID COMPONENT (A) FROM ABOUT 1 TO ABOUT 3 PARTS BY WEIGHT OF POLYETHYLENE GLYCOL FOR EACH PART BY WEIGHT OF VINYL ACETATE THEREIN AND THERE BEING PRESENT IN SAID COMPONENT (C) FROM ABOUT 30% TO ABOUT 70% BY WEIGHT OF SAID ALCOHOL, SAID COMPONENT (A) COMPRISING FROM ABOUT 1% TO ABOUT 10% AND SAID COMPONENT (B) COMPRISING FROM ABOUT 0.1% TO ABOUT 3% OF THE TOTAL WEIGHT OF THE COMPOSITION.