US 3141825 A
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United States Patent O 3,141,825 COLD WAVE LOTION PACKAGE Robert L. Goldemberg, Haworth, N .J and Harold Akrongold, Laurelton, N.Y., assignors to Shulton, Inc., Clifton, N.J., a corporation of New Jersey No Drawing. Filed May 17, 1962, Ser. No. 195,427 2 Claims. (Cl. 16787.1)
This invention relates to a cold wave lotion package, i.e., an applicator container haying therein a cold hair waving lotion, also known as a permanent waving lotion.
In this specification all percentages and parts are given on a weight basis unless otherwise indicated.
Cold wave lotions made by mixing thioglycolic acid, water and ammonium hydroxide or methylamine or ethylamine are known. In such lotions the thioglycolic acid reacts with the base and is present as the thioglycolate. It is the practice, however, in this art to refer to such lotions in terms of the original constituents mixed to produce the lotion, e.g., a water solution of ammonium hydroxide and thioglycolic acid, and this practice will be followed for the most part in this specification.
The hair waving industry has increasingly sought to package thioglycolic acid-ammonium hydroxide hair waving lotions in applicator bottles such as the well known plastic, including polyethylene, squeeze bottles. However, this has not been possible prior to the present invention because thioglycolic acid-ammonium hydroxide preparations heretofore known deteriorate excessiyely when stored in flexible plastic containers including the known polyethylene squeeze bottles.
To ,enable the facile application of the lotion to the human hair, in accordance with known waving techniques, including the so-called permanent hair waving techniques, a number of concerns bottle the lotions in glass containers and include in the package an empty applicator bottle, usually a polyethylene sgneeze bottle. Th s, of course, has the objection of requiring the consumer to fill the applicatorbottle for application of the lotion. Furthermore, the applicator bottle once filled must be used reasonably promptly. Storage of the 10- .tion in the applicator bottle for any considerable length of time results in deterioration of the thioglycolic acidammonium hydroxide lotion. Storage of ammonium thioglycolate lotions at 45 C. in the polyethylene squeeze bottle lined with a cured epoxy resin, as disclosed in United States Patent 2,836,319,granted May 27, 1958, for six months showed a loss ofabout 8% of the thioglycolic acid and 14.5% ofthe ammonium hydroxide. A loss of this order results in a commercially unsatisfactor-y product. Use of an unlined polyethylene squeeze bottle results in a markedly greater deterioration of the ammonium thioglycolate lotion.
It is a principal object of the present invention to proyide a polyethylene squeeze bottle applicator package .containing hair waving lotion of the thioglycolic acid-ammonium hydroxide type, which package can be stored for considerable periods, six months and longer at normal temperatures encountered, including summer temperatures in hot climates, without excessive deterioration of the lotion taking place within the applicator bottle so .that the lotion retains its hair waving properties.
Other objects .and advantages .of .this invention will be apparent from the following .detailed description thereof.
In accordance with vthis invention, a hair .waving lotion made by mixing from 4% to 7%, preferably 5 to 6%, thioglycolic acid; from 1% to 6.51%, preferably 2% to 4%, monoethanolamine; and from 0.1% to 2.6%, preferably 1% to 2%, ammonium hydroxide, but not more than one mol of ammonium hydroxide per ;mol of thioglycolic acid, the rest being chiefly water, is packaged in a Poly hyl n qu e t le ne and 9 coa d with a i ed e oxy e n, h amounts of ammon um hyd X d a monq h nolam ne wi hi th afa said ran e a hose t produ a loti n av n a PH W h n th rang of from t 4- s ot n an' ls 9 ain ar additive in th conve t o a sm ll mo nts, Such a hai o ditione s, We ng agents fo a din p ict iq of h lot on in o he ha op ifying, ic e i c lor n p rta ni and ab li i g ag nts.
The polyethylene squeeze bottle used is of the type dis osed in Unit d States Paten ,836,319., a ted M y 2 58- t s made by lining a poly hyl ne b 1.6 w th li in cons i ut d of a c red mix re of:
(1) An epoxy resin composition containing by weight from about to about 10% of the reaction product of epichlorohydrin, p,p'-dihydroxy-:d.iphenyldimethyl methane epihydric alcohol and from about 10% to about 90%"of the reaction product of epichlorhydrin and dimethyl, p-hydroxyphenyl, p-hydroxy-m-(phydroxybenzyDpheriyl methane, and
(2) The reaction product of epi'chlohydrin and p,p'-dihydroxy-diphenylmethyl methane,
said (1) and (2) being admixed in a ratio of between about 1:1 and about 50:1. Preferably a ratio of (l) to (2) between 5:1 and 15:1 is employed.
Any .of the conventional hardeners can be employed to cure the epoxy resin composition. Epoxy resins can be readily hardened or cured to an insoluble, infusible state by reaction of theep'oxy' and hydroxyl groups with crosslinking agents including diamines or polyamines,such as metaphenylene diamine, diethylene triamine and the polyethylene polyamines; diisocyanates, such as methylene bis-(4-phenyl') isocyanate; dialdehydes, such as glyoxal'; dimercaptans; and amides and polyamides, such as those disclosed in United States Patent 2,705,223. Preferably the epoxy'resin mixture is cured by a hardener admixed therewith .in a ratio between about 1:1 and about 10:1 by weight. Particularly desirable curable mixtures contain epoxide and ha rdener in a ratio of between about 4:1 and about 6:1 by weight.
The epoxy resin is applied to the polyethylene surface to be lined ,or coated in an uncured state, dissolved in a suitable solvent such as toluene, methylethyl ketone, and the like. Preferably, sufficient solvent is employed to produce a solids content between about 35% and about 75%. The coating may be applied by conventional techniques, such as by spraying, or manually by at least partially filling the bottle followed by suitable manipulative and draining steps to insure the application of an even lining to the interior surface. If the coating is applied to the exterior surface of the bottle, it need simply be immersed in a bath of the coating material and allowed to drain." Exterior coatings also' may be applied by spraying techniques. Where the coatings are applied by spray techniques, it is desirable to chemically pretreat the substrate and thus insure enhanced'continuity hesion ,of the coating.
llhe cured coating or lining is produced in situ by subjecting the coated article to a curing temperature for a period of time necessary to produce the desired chemical reaction. Desirably, the coating is cured at a temperature or -220 F. for a period of at least a half hour. Shorter periods of time may obviously be employed with higher curing temperatures. The curing time and tempera-tures can also be varied by the amount .andlype of catalyst or hardening agent employed. i
The thioglycolic acid is first mixed with the monoethanolamine. The amount of monqethanolamine, within the range above given, and the additionof the ammonium hydroxide in the amounts indicated bring the pH of the resultant lotion to within the range of 9.0 to 9.4 which is the pH range for most eifective hair waving.
Surprisingly and unexpectedly, the hair waving lotion made by mixing as its essential constituents thioglycolic acid, monoethanolamine and ammonium hydroxide in the proportions herein disclosed, which, as noted, involves not more than one mol of ammonium hydroxide per mol of thioglycolic acid, can be stored in the cured epoxy lined or coated, or both lined and coated, polyethylene squeeze bottles without excessive deterioration of the waving lotion taking place. In a comparative test involving the same cured epoxy lined polyethylene squeeze bottle and the storage therein at 45 C. for six months, on the one hand, of (a) a standard ammoniumthioglycolate lotion (containing no monoethanolamine) and, on the other hand, (15) a lotion formulated in accordance with this invention containing the same amount of the thioa glycolic acid, monoethanolamine (about 3.6%) and ammonium hydroxide (about 1.5%), (b) showed a loss of 37% less thioglycolic acid and 77% less ammonium hydroxide as compared with (a).
(a reaction product of epichlorohydrin, p,p'-dihydroxy diphenyl dimethyl methane and epihydric alcohol) with 315% of (a reaction product of epichlorhydrin and p,p-dihydroxy diphenyl dimethyl methane).
Four parts of the resultant mixture were mixed with This diiference is the one part of hardener difference between a commercially satisfactory lotion and one that is unsatisfatcory, i.e., the difference between success and failure.
Why the cured epoxy lined polyethylene squeeze bottle containing a lotion made by mixing thioglycolic acid, monoethanolamine and ammonium hydroxide in the proportions above disclosed shows such remarkably better keeping qualities, and does not deteriorate excessively on storage at normal temperatures, say below 45 C., for reasonably long periods of time, of the order of six months or longer, is not fully understood. While this invention is not to be limited to this explanation, which is advanced to facilitate'a better understanding of the invention, experimental evidence indicates that the presence of the relatively large amounts of ammonium hydroxide required in the ammonium hydroxide-thioglycolic acid lotions to maintain the lotion at a pH of about 9 to 9.4, at which the lotion is most effective, results in excessive deterioration of the lotion when stored in polyethylene squeeze bottles, including such bottles lined or coated, or both lined and coated, with cured epoxy resins as disclosed in United States Patent 2,836,319. In the package of this invention containing not more than one mol of ammonium hydroxide per mol of thioglycolic acid and containing monoethanolamine having a pH of between 9 and 9.4, the hair waving benefits of the ammonium hydroxide are obtained notwithstanding that the amount of ammonium hydroxide present is markedly less than the amounts employed in heretofore known thioglycolic acid-ammonium hydroxide hair waving lotions, and, surprisingly and unexpectedly, these benefits are obtained without excessive deterioration of the lotion taking place upon storage in the polyethylene bottle lined or coated with the epoxy resin for relatively long periods of time, of the order of six months and longer.
The following examples are given to illustrate this invention. It will be appreciated this invention is not limited to these examples.
Example I The polyethylene bottle was lined with a cured epoxy resin made by mixing 65% of and the resultant mixture diluted with methylethyl ketone to a solids content of 60%. The interior surface of a polyethylene squeeze bottle was lined by the known pourin pour-out technique and the liner cured at F. for two hours.
The lined bottle was filled with the following composition:
Thioglycolic acid percent 5.4
Monoethanolamine do 3.6
Ammonium hydroxide do 1.4
Water do 89.6
Example 11 In this example the same type of polyethylene squeeze bottle having the cured epoxy lining was used. This lined bottle was filled with the following composition:
Thioglycolic acid percent 5.3 Monoethanolamine do 1.5 Ammonium hydroxide do 2.0 Water do 91.2 pH 9.2
In this example, the amount of ammonium hydroxide is approximately one mol per mol of thioglycolic acid, which represents the maximum relative amounts of ammonium hydroxide and thioglycolic acid.
Example III This example involved the use of the same type of polyethylene squeeze bottle lined with a cured epoxy resin as in the other two examples. The lined bottle was filled with the following composition:
Thioglycolic acid percent 5.2 Monoethanolamine do 3.4 Ammonium hydroxide do 1.3 Water do 90.1 pH 9.25
It will be understood the present invention is not to be limited to the above description thereof, given for purposes of exemplification, except as indicated by the appended claims.
' What is claimed is:
1. A hair waving lotion package consisting of a polyethylene squeeze bottle having a cured epoxy resin coating consisting essentially of (1) an epoxy resin composition containing by Weight from about 90% to about 10% of the reaction product of epichlorhydrin, p,p-dihydroxydiphenyldimethyl methane and epihydric alcohol, and from about 10% to about 90% of the reaction prodnot of epichlorhydrin and dimethyl, p-hydroxyphenyl, phydroXy-o-(p-hydroxybenzyl) phenyl methane; (2) the reaction product of epichlorhydrin and p,p'-dihydroxy-diphenyldimethylmethane; said (1) and (2) being admixed in a ratio of between about 5:1 and 45:1, and a hardener, on at least one surface thereof completely covering said surface, said bottle containing a hair Wave lotion consisting essentially of from 4% to 7% by weight of thioglycolic acid, from 1% to 6.5% monoethanolamine, from 0.1% to 2.6% ammonium hydroxide, and the rest being 15 substantially entirely water, said mixture containing not more than one mol of ammonium hydroxide per mol of thioglycolic acid and having a pH within the range of 9 to 9.4.
2. A package as defined in claim 1, in which the lotion consists essentially of from 5% to 6% thioglycolic acid, from 2% to 4% monoethanolarnine, from 1% to 2% ammonium hydroxide and not more than one mol of ammonium hydroxide per mol of: thioglycolic acid, has a pH Within the range of from 9.0 to 9.4, and the said cured epoxy resin coating is a lining for the interior of the 10 polyethylene squeeze bottle.
References Cited in the file of this patent UNITED STATES PATENTS 2,836,319 Pinsky et al May 17, 1958 2,847,351 Brown et al Aug. 12, 1958 2,876,781 Martin Mar. 10, 1959