US3156664A - Sprayable film-forming composition containing a partial amine saltpartial ester - Google Patents

Description

United States Patent SPRAYABLE FILM-FORMING COMPOSITION CONTAINING A PARTIAL AMINE SALT- PARTIAL ESTER Michael A. Manganelli, Springfield, Mass., assignor to Monsanto Company, a corporation of Delaware No Drawing. Filed Nov. 2, 1959, Ser. No. 850,081

8 Claims. (Cl. 26033.4)

This invention relates to sprayable film-forming compositions. More particularly, the invention relates to sprayable film-forming compositions which are adapted for use as hair sprays and are non-corrosive to metal.

Copending application S.N. 664,498, filed June 10, 1957, in the name of Charles L. Mills, Jr. now Pat. No. 2,957,838, discloses sprayable compositions comprising a halogenated alkane propellant, an anhydrous alcohol, and an alkyl half ester of an olefin-maleic anhydride copolymer. These compositions are particularly well adapted for use as hair sprays because of their ability to form thin, transparent, non-hygroscopic, non-tacky films which hold hair waves in place without imparting a lacquered appearance, do not flake when the hair is combed, and are readily soluble in mild alkali. However, these compositions present a serious storage problem because of their tendency to corrode metal. Difiiculty is encountered in modifying the compositions to reduce or eliminate this undesirable tendency, because it is necessary that this modification of the compositionbe accomplished without an accompanying loss of one or more of the properties which make the compositions useful as hair sprays and, preferably, without imparting an objectionable odor or tendency toward discoloration on aging.

One object of this invention is to provide new sprayable film-forming compositions.

Another object is to providenewsprayable film-forming compositions which are adapted for use as hair sprays.

A further object is to provide such compositions which are non-corrosiveto metal.

These and other objects are attained by dissolving an olefin-maleic anhydride copolymer or an alkyl partial ester thereof in an, anhydrous alkanol to form an alcoholic solution of a partially esterified polymer, adding a tertiary amine to aminate the free carboXyl groups of the partially e'sterified polymer, and pressurizing the solution of aminated polymer with an aerosol propellant.

The followingexamples are givento illustrate the invention. Parts mentioned are parts by weight.

EXAMPLE I Six parts of an ethyl half ester of ethylene-maleicv anhydride copolymer having an average molecular Weight .tairisthe configuration, e.g., wave, imparted tothe hair 3,156,664 Patented Nov. 10, 1964 ICC before spraying. The film is non-hygroscopic and nontacky, does not impart a lacquered appearance to the hair, does not flake even after the hair has been combed several times, and is easily and completely removed from the hair by Washing with warm water and soap or conventional shampoo preparations.

Substantially the same results are obtained when hair spray compositions are prepared by the process of Example I from the following formulations:

Formulation A Parts Ethyl half ester of propylene-maleic anhydride co- The sprayable film-forming compositions of the invention are prepared by dissolving an olefin-maleic anhydride copolymer or an alkyl partial ester thereof in an anhydrous alkanol to form an alcoholic solution of a partially esterified polymer, adding a tertiary amine to aminate the free carboxyl groups of the partially esterified polymer, and pressurizing the solution of aminated polymer with an aerosol propellant. V

The olefin-maleic anhydride copolymers are copolymers of 40-60 molar proportions of maleic anhydride with 60-40 molar proportions of an olefin containing 2-4 carbon atoms, i.e., ethylene, propylene, butylene, or isobutylone. Usually the components of the copolymer are combined in equimolar proportions. Any such copolymer may be used in preparing the compositions of the invention it it has an average molecular weight in the range of l0,000-70,000, if it is soluble in an anhydrous alkanol containing l-4 carbon atoms after having been esterified to the extent of 50-70% with an alkanol containing 1-4 carbon atoms, and if is still-solublein the anhydrous alkanol after the free carbonyl groups of the esterified copolymer have'been aminated with a tertiary amine.

The alkyl partial esters of olefin-maleic anhydride copolymers are the 'alkanol-soluble materia'lsiobtained by este'rifying the aforementioned anhydride copolymers to the extent of 50-70% with an alkanol containing 1-4 carbon atoms, Formation of the half esters is a substantially spontaneouss eaetion, beingaccomplished by merely esterifying alkanol. For example, when parts by Weight of an ethylene-maleic anhydride copolymer having an average molecular weight of about 10,000 are dissolved in 5 parts by Weight of ethanol at room temperature under anhydrous conditions, about 1.8 parts by weight of ethanol spontaneously react with the copolymer to form the ethyl half ester. \Vhen further esterification is desired, the reaction is conducted thermally in the presence of an acid catalyst. The catalyst and water of esterification must be removed before utilizing these further esterified copolymers in the preparation of the compositions of the invention.

The olefin-maleic anhydride copolymer or alkyl partial ester thereof should be used in such amount that the aminated resin formed therefrom constitutes 0.5-5% by weight of the final composition. Usually, in making 100 parts by weight of composition, this amount is in the range of about 0.1-3 parts by weight when an unesterified anhydride copolymer is the starting material and in the range of about 0.2-4 parts by weight when an alkyl partial ester is the starting material.

In making the compositions of the invention, the anhydride copolymer or alkyl partial ester thereof is dissolved in an hydrous alkanol containing 1-4 carbon atoms, i.e., methanol, ethanol, propanol, isopropanol, or a butanol. The alkanol should comprise 25-50% by weight of the final composition. When an unesterified anhydride copolymer is used as a starting material, a sufficient excess of alkanol should be employed to accomplish 50% eaterification of the copolymer in situ.

The tertiary amine which is added to the alcoholic solution of partially esterified copolymer can be any tertiary amine which reacts with the copolymer to form an aminated material soluble in the anhydrous alkanols of the invention, e.g., trimethylarnine, triethylamine, tri- 5 propylamine, tributylamine, tripentylamine, N,N dimethylanline, etc. Because of their commercial availability and the especially desirable properties of the salts which they form with the partially esterified copolymers, triethylamine, tripropylamine, and tributylamine are particularly suitable aminating agents. The amount of tertiary amine employed depends on the properties desired for the aminated material, a balance of corrosion inhibition and other properties, e.g., water sensitivity and alkali solubility, being obtained by varying the degree of amination of the free carboxyl groups of the partially esterified copolymer. When the greatest degree of corrosion inhibition is desired, the tertiary amine should be employed in the amount required to aminate all of these free earboxyl groups. According to a preferred embodiment of the invention, the extent of amination should be such that not more than of the potentially free carboxyl groups of the anhydride copolymer exist as free carboxyl groups in the aminated, esterified copolymer. Usually about 0.06-3 parts by weight of tertiary amine are used in making 100 parts by weight of composition.

The aerosol propellant used to pressurize the alcoholic solution of aminated polymer is a liquefied gas capable of exerting a total pressure of -50 p.s.i. at room temperature. It may be one or a mixture of halogenated hydrocarbons chosen to give the desired vapor pressure and is preferably a halogenated alkane containing l-5 carbon atmos, e.g., trichlorofluoromethane, dichlorodifiuoromethane, 1,2-dichloro-l,1,2,2-tetrafluoroethane, etc., or mixtures thereof. A :50 mixture of trichlorofluoromethane and dichlorodifiuoromethane is particularly suitable. The amount of propellant employed varies with the amounts of the other ingredient of the composition; usually the propellant comprises about 45-75% by weight of the final composition.

The properties of the compositions of the invention can be varied by the incorporation of minor amounts of optional ingredients such as plasticizers, lanolin, non-drying oils, waxes, dyes, pigments, perfumes,, etc. For example,

a hair spray composition which is effective for a wide range of hair conditions is obtained by adding 1.5 parts of butyl phthalyl butyl glycolate and 2 parts of lanolin to the composition of Example I.

When a plasticizer for the resin is included in the compositions, it can be used in amounts ranging up to 25% by weight, based on the weight of aminated resin. Suitable plasticizers are odorless esters which are soluble in the anhydrous alkanols of the invention, e.g., dialkyl phthalates such as diethyl phthalate, dioctyl phthalates. etc.; alkyl phthalyl alkyl glycolates such as butyl phthalyl butyl glycolate, etc.; adipates, sebacates, etc, and mixtures thereof.

The products of the invention are sprayable filmforming compositions which are substantially non-corrosive to metal. They are particularly useful as hair sprays because of their ability to form thin, transparent, non-hygroscopic, non-tacky films which hold hair waves in place without imparting a lacquered appearance, do not flake when the hair is combed, and are readily soluble in mild alkali.

It is obvious that many variations may be made in the products and processes set forth above without departing from the spirit and scope of this invention.

What is claimed is:

l. A liquified sprayable film-forming composition comprising about 45-75% by weight of a halogenated C -C alkane propellant capable of exerting a total pressure of 25-50 p.s.i. at room temperature, about 25-50% by weight of anhydrous alkanol containing 1-4 carbon atoms, and about 0.5-5 by weight of an alkanol-soluble partial amine salt, partial ester of a C -C olefin-maleic anhydride copolymer wherein, of the potentially free carboxyl groups, up to 20% exist as free carboxyl groups, 57-70% exist as esters with an alkanol containing 1-4 carbon atoms, and the remaining 10-50% exist as salts with a tertiary amine selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine and N,N-dimethylaniline, said copolymer before esterification and amination having an average molecular weight of l0,00070,000.

2. A composition as in claim 1 wherein 50-70% of the potentially free carboxyl groups exist as alkyl ester groups and, correspondingly, 5030% of the potentially free carboxyl groups exist as tertiary amine salt groups.

3. A composition as in claim 1 wherein the tertiary amine is triethylamine.

4. A composition as in claim 1 which contains up to 25% by weight, based on the weight of aminated, esteritied copolymer, of an ester-type plasticizer which is soluble in an anhydrous alkanol containing l-4 carbon atoms.

5. A composition as in claim 1 wherein the propellant is a 50:50 mixture of trichlorofluoromethane and dichlorodifluoromethane, the anhydrous alkanol is anhydrous ethanol, the olefin is ethylene, the esterifying alkanol is ethanol, and the tertiary amine is triethylamine.

6. A composition as in claim 1 wherein the propellant is a 50:50 mixture of trichlorofluoromethane and dichlorodifluoromethane, the anhydrous alkanol is anhydrous propanol, the olefin is propylene, the esterifying alkanol is ethanol, and the tertiary amine is triethylamine.

7. A sprayable film-forming composition comprising about parts by weight of anhydrous ethanol, about 444 parts by weight of a 50:50 mixture of trichlorofluoromethane and dichlorodifluoromethane, about 1.5 parts by weight of butyl phthalyl butyl glycolate, about 2 parts by weight of lanolin, and about 9.5 parts by weight of a partial amine salt, partial ester of an ethylene-maleic anhydride copolymer in which 50% of the potential free carboxyl groups are esterified with ethanol and the remaining 50% are aminated with triethylaminc, said copolymer before esterification and amination having an average molecular weight of about 25,000.

8. A. process for preparing a liquified film-forming composition which comprises dissolving about 0.1-4 parts by weight of a polymer in about 25-50 parts by weight of 5 an anhydrous alkanol containing 1-4 carbon atoms, adding to this alcoholic solution about 0.06-3 parts by weight of a tertiary amine selected from the group consisting of trimethyl-amine, triethylamine, tripropylamine, tributylamine, tripentyl'amine and N,N-dimethy1aniline, and pressurizing the resultant solution to a total pressure of 25- 50 p.s.i., determined at room temperature, with about 45- 75 parts by weight of a halogenated C -C alkane propellant, said polymer being a member of the group consisting of the C -C olefin-maleic anhydride copolymers having average molecular weights in the range of 10,000-

6 70,000 and the partial esters thereof which are esterified to the extent of 50-70% with an alkanol containing 1-4 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS 2,881,155 Hankins Apr. 7, 1959 2,897,172 M=aeder July 28, 1959 2,913,437 Johnson Nov. 17, 1959 2,957,838 Mills Oct. 25, 1960 2,977,334 Zopf et al. Mar. 28, 1961

Claims (1)

1. A LIQUIFIED SPRAYABLE FILM-FORMING COMPOSITION COMPRISING ABOUT 45-75% BY WEIGHT OF A HALOGENATED C1-C5 ALKANE PROPELLANT CAPABLE OF EXERTING A TOTAL PRESSURE OF 25-50 P.S.I. AT ROOM TEMPERATURE, ABOUT 25-50% BY WEIGHT OF ANHYDROUS ALKANOL CONTAINING 1-4 CARBON ATOMS, AND ABOUT 0.5-5% BY WEIGHT OF AN ALKANOL-SOLUBLE PARTIAL AMINE SALT, PARTIAL ESTER OF A C2-C4 OLEFIN-MALEIC ANHYDRIDE COPOLYMER WHEREIN, OF THE POTENTIALLY FREE CARBOXYL GROUPS, UP TO 20% EXIST AS FREE CARBOXYL GROUPS, 57-70% EXIST AS ESTERS WITH AN ALKANOL CONTAINING 1-4 CARBON ATOMS, AND THE REMAINING 10-50% EXIST AS SALTS WITH A TERTIARY AMINE SELECTED FROM THE GROUP CONSISTING OF TRIMETHYLAMINE, TRIETHYLAMINE, TRIPROPYLAMINE, TRIBUTYLAMINE, TRIPENTYLAMINE AND N,N-DIMETHYLANILINE, SAID COPOLYMER BEFORE ESTERIFICATION AN AMINATION HAVING AN AVERAGE MOLECULAR WEIGHT OF 10,000-70,000.