US 3895104 A
Sunscreening compositions and methods of using the same to protect human skin from erythema-causing radiation by applying to the skin compositions containing a cosmetic carrier, at least one ultraviolet absorbing material which has a maximum absorption peak between 280 millimicrons to about 320 millimicrons and a polyamide resinous material which is capable of forming a film and is alcohol-soluble. Sunscreening compositions containing the polyamide resinous materials, when applied to the skin, form a long lasting protective film which resists removal by water and perspiration.
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Description (OCR text may contain errors)
United States Patent [191 Karg [ SUNSCREENING METHOD AND COMPOSITION CONTAINING FILM FORMING POLYAMIDE MATERIAL  Inventor: Gerhart Karg, Pompton Lakes, NJ.
 Assignee: Avon Products, Inc., New York,
 Filed: June 13, 1972 21 Appl. No.: 262,375
 U.S. Cl. 424/59; 424/47; 424/60; 424/78; 424/81; 424/170  Int. Cl A61] 23/00  Field of Search 424/59, 60, 78 A; 260/78 A  References Cited UNITED STATES PATENTS 3,529,055 9/1970 Skoultchi et a1 424/59 X 3,622,545 11/1971 FOldi et al 260/78 A I 3,666,732 5/1972 Skoultchi et al 260/78 A FOREIGN PATENTS OR APPLICATIONS 862,718 2/1971 Canada 424/59 [451 July 15,1975
9/1948 France 424/60 OTI-IER PUBLICATIONS Steinhauer et al., Chem. Abs. 1970, Vol. 73, pp. 1l2871x.
 ABSTRACT Sunscreening compositions and methods of using the same to protect human skin from erythema-causing radiation by applying to the skin compositions containing a cosmetic carrier, at least one ultraviolet absorbing material which has a maximum absorption peak between 280 millimicrons to about 320 millimi crons and a polyamide resinous material which is capable of forming a film and is alcohol-soluble. Sunscreening compositions containing the polyamide resinous materials, when applied to the skin, form a long lasting protective film which resists removal by water and perspiration.
8 Claims, No Drawings SUNSCREENING METHOD AND COMPOSITION CONTAINING FILM FORMING POLYAMIDE MATERIAL BACKGROUND OF THE INVENTION It is believed desirable in our society to secure tanning of the skin for purposes of appearance. It is well known that ultraviolet radiation produced by the sun or by sun lamps and other tanning means between the wave lengths of about 280 millimicrons to about 320 millimicrons are responsible for distressing burning which is suffered by overexposure to such tanning means while the ultraviolet radiation of longer wavelengths of up to about 420 millimicrons causes the aesthetically desirable tanning coloration of the skin. In order to prevent or substantially reduce sunburn while promoting the development of a tanning appearance various so called sunscreening formulations have been produced and are commercially available. These are adapted to be applied over the body areas which are to be exposed and their formulations generally contain a compound which can absorb ultraviolet radiation in the range of from about 280 to 320 millimicrons and thus alleviate the problems of erythema.
In addition to the above noted primary sunscreening function, a commercially suitable agent should be essentially resistant to removal by fresh or salt water or through the perspiration of the user while, at the same time, be completely removable from the skin upon washing with ordinary soap and water. It should be, moreover, fully compatible with organic solvents as well as with the various ingredients which may be present in suntan preparations such as, for example, oils, perfumes, pigments, and aerosol propellants. Finally, the sunscreen agent should be fully resistant to any breakdown resulting from the exposure to the ultraviolet radiation and, most certainly, it should be entirely harmless to the user.
In the past various chemical compounds have been utilized as sunscreening agents for suntan formulations. Compounds, such as aminobenzoic acid, its derivatives and esters as well as substituted benzophenones and other well known compounds which absorb in the range of from 280 millimicrons to 320 millimicrons have been commonly used in commercially available suntan preparations. These preparations, however, are not substantive to the skin and, therefore, do not yield a long lasting protective screen.
Suntanning preparations are generally used in hot weather and at beaches where people enjoy bathing. Therefore, compositions containing crystallizable ultraviolet absorbers which are generally used lack the ability to be long lasting. When the volatile vehicle, in which these compounds are formulated, evaporates from the skin the sunscreening compound rapidly crystallizes or forms globular material on the skin which is easily removable by the action of water or perspiration. Furthermore, the continuity of the protective material is thus broken and the desired protection is destroyed. To overcome these various deficiencies attempts have been made to incorporate ultraviolet absorbing groups in compounds which would be more resistant to the action of water or would be insoluble in water. Higher esters of aminobenzoates are known to form an oily film which are more resistant to removal by water. These materials, although overcoming one problem, are limited in scope due to their melting and boiling points,
their reactivity with other materials as well as their tendency to break down under ultraviolet radiation.
SUMMARY OF THE INVENTION It has now been found that sunscreening compositions which are useful in absorbing the erythemaproducing radiation can be made comprising an ultraviolet absorbing material and a polyamide resinous material having the properties of being soluble in alcohol and capable of forming a film material. The polyamide material can be encompassed into the various cosmetic carrier materials known to be useful by the practitioner. The resultant formulations, when topically applied to the skin, will form a film material which will resist removal by the action of fresh or salt water or through perspiration of the user.
DETAILED DESCRIPTION OF THE INVENTION Sunscreening formulations containing polyamide resinous material are capable of screening harmful ultraviolet radiation while permitting transmission of the beneficial rays. In this manner the individual may subject himself to sunlight or sun lamps to cause the aesthetically desirable tanning of the skin while substantially alleviating the problems of sunburn and its accompanying discomfort and pain.
The compositions of the present invention are applied to the skin in any fugitive dermatologically acceptable carrier. The carrier material shall contain at least one compound which has a characteristic maximum ultraviolet absorption peak between about 280 millimicrons and about 320 millimicrons. In addition, the carrier material shall also contain a polyamide film forming material as herein described. The compositions may be in the form of a homogenous solution or dispersion. The fugitive carrier material contained therein may be alcohols, water-alcohol mixtures and the like. The carrier may also be chosen from oil-inwater emulsions wherein the amount of oil present is not sufficient to permit formation of an over-plasticized polymeric film. The specific type of carrier material or carrier system which is to be utilized will depend upon the type of application, the degree of application and the desirability of particular bases to different users.
The polyamide materials which have been found most useful in forming long lasting sunscreen compositions are those which are insoluble in water, are compatible with the carrier material and which, upon evaporation of said carrier material, form a substantive film material.
Polymeric material useful herein includes homopolymers and copolymers of acrylamide. The pendant amide moiety may have substituted groups attached to the nitrogen atoms wherein said substituted groups may be selected from the groups consisting of hydrogen, alkyl, substituted alkyl, alkenyl, aryl, substituted aryl and alkaryl groups. The groups on each nitrogen atom present in the polyacrylamide may have the same or dissimilar substitution. As to the alkyl groups they are preferably C, to C such as methyl, ethyl, n-propyl, butyl, amyl, hexyl, heptyl, nonyl groups and the like; the alkenyl groups can be allyl, methallyl, crotyl and the like; and the substituted alkyls are exemplified by the cyano, hydroxy, alkoxy or halo C -C radicals with examples being cyanoethyl, cyano-n-propyl, cyano-n-butyl, hydroxyethyl, hydroxyisopropyl, hydroxyhexyl, methoxymethyl, methoxypropyl, propoxypropyl, butyoxyethyl, chloropropyl, chloroethyl, chlorodecyl and the like. With respect to the aryl radicals these can be phenyl, tolyl, xylyl, diphenyl and the like; the substituted aryl radicals are illustrated by anisyl, hydroxyethyl phenyl, meta-chlorotolyl and the like; and the alkyaryl groups can be benzyl, phenethyl, phenol n-propyl, 2,4- dimethylbenzyl and the like. The polymeric material contemplated herein does not of necessity have to have all substituted groups the same. Therefore, the polymer contemplated may contain nitrogen atoms of the pendant amide groups which are unsubstituted, monosubstituted or disubstituted and are all the same or, alternatively, pendant groups which differ one from'another such as where some pendant groups are unsubstituted amide groups and some are substituted amides. The resulting polymeric material must be insoluble in water, be capable of forming a substantive film and be soluble in alcohols.
Polymeric materials useful herein include homopolymers and copolymers of acrylamide such as polyacrylamide, N,N-dimethylacrylamide, N,N- diethylacrylamide, N,N-dibutylacrylamide, N,N-di(,8- hydroxyethyl)acrylamide, N,N-dimethoxymethylacrylamide, N-methylacrylamide, N-ethyl acrylamide, N-methoxymethyl acrylamide, N-ethyl-N-cyanoethyl acrylamide, N-phenyl acrylamide, (N,N-dimethyl) (NN'-diethyl)acrylamide, (N,N-dimethyl) (N-ethyl) acrylamide, (N,N-diphenyl) (N'-methyl)acrylamide and the like.
Polyacrylamides useful in this invention may be made in any of the known methods such as by free radicalpolymerization of the desired monomeric constituents.
Polyamides useful in forming the long lasting sunscreen composition of this invention may be polymers formed from the reaction of polyamines with a polybasic acid. Methods of preparing these polyamides by condensation of polyamines and polycarboxylic acids or anhydrides are well known in the art and need not be described here. The polyamides may be derived from such polyamines as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, 1,4-diaminobutane, 1,3- diaminobutane, hexamethylenediamine, 3 ,3
iminobispropylamine and the like. Typical polycarboxylic acids which may be condensed with the polyamines to form the desired polyamide are oxalic, malonic, succinic, glutaric, adipic, palmitic, suberic, azelaic, sebacic, malic, phthalic, cyclohexandicarboxylic, and the like as well as their isomers, homologs and andydrides. Alternately, or in addition to the above polycarboxylic acids, the polyamide may be formed from unsaturated polycarboxylic acids or anhydrides such as maleic, fumaric, citraconic and itaconic acids and the like. It is understood that the polyamide formed shall be water insoluble, compatible with the carrier material used and having the property of forming a film material upon evaporation of the carrier material.
The amount of polymeric material which is incorporated into the sunscreening compositions may range from about 0.1 to about 50 weight percent based on the total weight of the composition with a preferred range of from about 5 to about 25 percent. While in some instances greater or lesser amounts of the polymeric material may be used, it has been found, in general, that the foregoing range of polymeric material incorporated into the sunscreening compositions is most suitable in yielding a film-forming composition which is resistant to removalby' fresh or salt water or through perspiration.
The long-lasting sunscreening compositions, as herein described, contain one or more additional ultraviolet absorbing materials which have a maximum absorption peak in the range of from 280 millimicrons to 320 millimicrons. Examples of such compounds are the aminobenzoic acids or esters of these materials, substituted benzophenones, compounds having a benzanilide nucleus, organosilicon esters and other compounds which are wellknown to those skilled in the art. These selective ultraviolet absorbing compounds may be used in the composition of this invention in quantities ranging from 0.1% to about 10% based on the total weight of the sunscreening composition. Normally effective amounts of these materials range from 0.1% to about 6% depending upon the activity of the chromophoric absorbing group.
The cosmetic carrier material may be a C C lower alcohol or mixtures of two or more different alcohols. The alcohols may be any dermatologically acceptable material which will evaporate from the skin after application such as methanol, ethanol, propanol, isopropanol and the like. Such alcohols may be used alone or with other polyols such as ethylene glycol, 1,2- propanediol, 1,3-propanediol, 1,3-butanediol, 1,4- butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, glycerol, trimethylol ethane pentaerythritol, sorbitol and the like.
The cosmetic carrier material may be a mixture of the above alcohols with water. Normally the amount of water present is less than the majority of the total carrier material. The maximum amount of water which may be present in dependent upon the compatibility of the specific polyamide used with the alcohol-water mixture. In addition, an oil may be present. The oil material, such as a mineral, vegetable or animal oil, to be limited to such quantity so as to not plasticize the polyamide resultant film to the degree that a tacky material results.
The sunscreening compositions, as described hereinabove, are applied to the skin in any convenient manner such as by hand rubbing small amounts onto the exposed skin which is to be subjected to the suntan causing radiation. Alternately, the composition may be sprayed by an aerosol container onto the exposed skin. The applied composition will form a film on the treated skin which is resistant to removal by the abrasive action of fresh or salt water or through perspiration of the user. Instead it remains as a continuous sheet material which is substantive to the skin surface. This sheet material contains entrapped therein the ultraviolet absorbing compound or compounds which effectively protect the skin from erythema-causing rays.
In addition, other of the usual components such as perfumes, fillers, dyes, colorants, emulsifiers and the like may be added to the long lasting sunscreen compositions described hereinabove. The type and amount of such additional components will depend on the factors EXAMPLE 1 Compositions are prepared by forming aqueousalcoholic solutions having the following composition:
Ethyl alcohol 78 parts Propylene glycol l parts Water 5 parts Poly N.N-dimethyl acrylamide 7 parts Colorant and Perfume to suit The solutions are each mixed with 4% of one of the following UV absorbing compounds:
(a) Ethyl-1,2-diphenylethylene-l-carboxylic acid (b) Diethyl p-dimethylamino-benzalmalonate (c) Di-isobutyl p-dimethoxymethylamino benzalmalonate (d) Ethyl p-dimethyl aminocinnamate (e) lsobutyl p-dihydroxymethylamino cinnamate (f) Amyl p-dimethylamino benzoate (g) Ethyl p-dimethylamino benzoate (h) N,N-dimethyl benzocaine (i) p-dimethylamino benzamide Samples are applied to the skin and the treated areas exposed to ultraviolet rays (Xenon-arc Solar Simulator) for time periods equivalent to from 2 to 6 times the previously established minimum erythema] dose for each volunteer. Substantially no erythema was observed at the treated sites over a twenty-four hour period.
To determine the substantivity of the compositionsthe volunteers had areas of their forearms treated with each of the test samples, exposing the treated area to the UV source for a time greater than the established minimum erythemal dose (MED) and then subjecting the areas to water (8090F.) immersion throughs for periods ranging from 5 to 15 minutes and re-exposing the treated areas. Observation of the treated areas after 24 hours showed substantially no reddening.
EXAMPLE II Alcoholic substantive sunscreen compositions are prepared by mixing 70 parts ethanol, 10 parts glycerol, parts of a polyamide resin made from ethylene diamine and an unsaturated dimer acid (18 carbons/carboxyl group) and 5 parts of each of the UV absorving compounds listed in Example I.
The compositions are tested in the same manner as the compositions of Example I. The compositions showed protection to erythema causing rays and substantive properties after exposure to water.
EXAMPLE II] An alcoholic substantive sunscreen composition is prepared by mixing the following:
Ethanol 70 parts Polyamide resin (as described in Example ll) 15 parts -Continued Oleyl alcohol-propylene oxide adduct 12 pans Amyl-para-dimethyl aminobenzoate 3 parts The composition is tested in the same manner as the compositions of Example I. The composition showed protection .to erythema causing rays and substantive properties after exposure to water. The MED increase for the tested volunteers was 3.6 before exposure to water and remained at 3.6 after exposure to water.
EXAMPLE IV A composition is prepared by mixing the following:
Ethanol parts Polyamide resin (1,3 propylene diamineunsaturated dimer acid) 15 parts Oleyl alcohol/propylene oxide adduct 9 parts Dimethyl procaine decyl bromide 6 parts The composition was tested in the manner described in Example I. The treated areas of the skin showed good protection qualities and when tested for substantive properties showed a MED increase of 2.7 prior to water treatment and 2.7 after such treatment. The treated area, therefore, has equal protection before and after subjection to water.
EXAMPLE V A comparison test was made in which an erythema UV absorbing compound is mixed with a carrier material which does not contain a polyamide resin. The composition comprises:
Ethanol 82 parts Polyoxyethylene 10 parts Dimethyl procaine octadecyl bromide 8 parts The sample is tested as described in Example I. The sample showed a high degree of protection but the substantive test gave a MED value of 6 prior to water treatment and 0.0 after such treatment.
It will be understood that it is intended to cover all changes and modifications of the examples of the invention herein chosen for the purpose of illustration which do not constitute departures from the spirit and scope of the invention.
What is claimed is:
1. A method of protecting human skin from erythema-causing radiation comprising applying to the skin a sunscreening composition containing from about 0.1 to about 10 percent of the composition of at least one ultraviolet absorbing material having a maximum absorption peak between about 280 millimicrons and 320 millimicrons and from about 0.1 to about 50 percent of the composition of a water-insoluble, alcoholsoluble, film-forming polyamide material, said materials being incorporated in from about 40 percent to 99.8 percent of the composition of a cosmetic carrier material selected from the group consisting of C -C alcohol, C -C alcohol mixtures and C -C alcohol-water mixtures, said maximum amount of water present in the alcohol-water mixture being dependent upon the compatibility of the polyamide used; and allowing said composition to form a film on the skin.
2. The method of protecting human skin from erythema-causing radiation according to claim 1 wherein 7 v the polyamide material is a water insoluble, alcohol soluble, film forming polyacrylamide.
3. The method of protecting human skin from erythema-causing radiation according to claim 1 wherein the polyamide material is a water-insoluble, alcohol soluble, film forming condensation product of at least one polycarboxylic acid and at least onepolyamine.
4. The method of protecting human skin from erythema-causing radiation according to claim 1 wherein the cosmetic carrier is a fugitive C -C alcohol-aqueous mixture having the alcoholic content of said mixture in amounts of at least 50 percent.
5. A substantive composition for protecting skin from erythema-causing radiation comprising from about 0.1 to about percent by weight of an ultraviolet absorbing material having a maximum absorption peak between about 280 millimicrons and 320 millimicrons and from 0.1 to 50 percent based on the total weight of the composition of a polyamide resinous material which is water-insoluble, alcohol soluble and capable of forming a substantive film material, said'materials being incorporated in from about 40 to 99.8 percent by weight of a cosmetic carrier selected from the group consisting of C -C alcohol, C -C alcohol mixtures and C -C alcohol-water mixtures, said maximum amount of water present in the alcohol-water mixtures being dependent upon the compatibility of the polyamide used.
6. The substantive composition according to claim 5 wherein the polyamide resinous material is a condensation product of at least one polycarboxylic acid and at least one polyamine.
7. The substantive composition according to claim 5 wherein the polyamide resinous material is a polyacrylamide.
8. A substantive composition according to claim 5 wherein the cosmetic carrier is a C -C alcohol-water mixture having an alcohol content of said mixture in amounts of at least 50 percent.