U.S. patent number 3,864,473 [Application Number 05/261,621] was granted by the patent office on 1975-02-04 for substantive polymeric sunscreen composition.
This patent grant is currently assigned to Avon Products, Inc.. Invention is credited to Joseph P. Ciaudelli.
United States Patent |
3,864,473 |
Ciaudelli |
February 4, 1975 |
SUBSTANTIVE POLYMERIC SUNSCREEN COMPOSITION
Abstract
Sunscreening compositions for topical application to the skin
comprising a cosmetic carrier material containing a polymeric
reaction product of a para-dialkylamino benzoyl halide and a
polyethylenimine. These sunscreening compositions, when applied to
the skin of the user, form a film of the polymeric reaction product
which is highly effective in protecting human skin from
erythema-inducing ultraviolet radiation and is resistant to removal
from the skin by water or perspiration.
Inventors: |
Ciaudelli; Joseph P. (Ramsey,
NJ) |
Assignee: |
Avon Products, Inc. (New York,
NY)
|
Family
ID: |
22994111 |
Appl.
No.: |
05/261,621 |
Filed: |
June 12, 1972 |
Current U.S.
Class: |
424/60;
424/78.26; 424/78.08 |
Current CPC
Class: |
A61K
8/84 (20130101); A61Q 17/04 (20130101); A61K
2800/57 (20130101) |
Current International
Class: |
A61K
8/72 (20060101); A61K 8/84 (20060101); A61Q
17/04 (20060101); A61l 023/00 () |
Field of
Search: |
;424/59,60 ;260/78A |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Ore; Dale R.
Attorney, Agent or Firm: Pennie & Edmonds
Claims
What is claimed is:
1. A method of protecting the human skin from erythema inducing
ultraviolet radiation which comprises applying to the skin a
composition containing from 1 percent to about 75 percent based on
the total weight of the composition of a polymeric reaction product
of at least one p-di-C.sub.1 -C.sub.4 -alkylaminobenzoyl halide
with polyethylenimine having an average molecular weight ranging
from about 500 to 100,000 in a topical skin cosmetic carrier
material selected from the group consisting of water-lower alcohol
mixture, and an aminal, vegetable and mineral oil base.
2. A method according to claim 1 wherein the p-dialkylaminobenzoyl
halide is p-dimethylaminobenzoyl chloride.
3. A method according to claim 1 wherein the carrier material is a
lotion.
4. A method according to claim 1 wherein the polymeric reaction
product contains from 5 to 80 weight percent based on the total
weight of the polymeric material of the residue group of
p-dialkylaminobenzoyl halide.
5. A method according to claim 1 wherein the carrier material is a
water-lower alkyl alcohol mixture having up to 75 percent by weight
alcohol.
6. A substantive polymeric sunscreening composition comprising a
polymeric reaction product of a polyethylenimine and a di-C.sub.1
-C.sub.4 -alkylaminobenzoyl halide having an average molecular
weight of from about 500 to 100,000, wherein said product contains
the dialkylaminobenzoyl groups pendant to the polymeric backbone
and a topical skin cosmetic carrier material selected from the
group consisting of water-lower alcohol mixture, and an animal,
vegetable or mineral oil base.
7. A composition of claim 6 wherein the pendant dialkylaminobenzoyl
groups are in a concentration ranging from about 0.1 percent to
about 10.0 percent based on the total weight of the
composition.
8. A composition of claim 6 wherein the dialkylaminobenzoyl halide
is dimethylaminobenzoyl chloride.
9. A composition according to claim 6 wherein the cosmetic carrier
is a water-lower alkyl alcohol mixture having up to 75 percent by
weight alcohol.
Description
BACKGROUND OF THE INVENTION
It is widely desirable in our society to secure tanning of the skin
for purposes of appearance by sunbathing or other means. In order
to enable or aid a person to subject themselves to tanning by such
rays, several so-called sunscreening compositions have been made
available to diminish or avoid the discomfort and dangers of
erythema which may be simultaneously produced. It is well known
that the ultraviolet radiation produced by the sun between the
wavelengths of about 280 millimicrons to about 320 millimicrons are
responsible for the distressing burning which is suffered by
over-exposure. The ultraviolet radiation of longer wavelengths of
up to about 420 millimicrons causes the aesthetically desirable
tanning coloration of the skin.
It has been known by those skilled in the art that various
compounds are useful to absorb the undesirable ultraviolet
radiation ranging from 280 millimicrons to 320 millimicrons.
Various aminobenzoic acid and substituted aminobenzoic acids are
known to have the quality of absorbing the undesirable ultraviolet
rays while transmitting those more desirable sun tanning producing
rays. Also, the derivatives of para-aminobenzoic acid such as the
dimethyl aminobenzoic acids have been used in the past in sun
tanning compositions. It is also known that esters of
P-aminobenzoic acid such as the methyl, ethyl or propyl p-amino
benzoate as well as those esters formed from higher alkyl alcohols
have valuable sun-screening effects. Each of these compounds while
having desirable properties are not ideal for the purpose intended.
They lack one or more of such desirable characteristics as
solubility in cosmetic carriers at low temperatures, nonstaining of
fabrics, stability on storage, stability on exposure to ultraviolet
or visual radiation, resistance to oxidation to air. Moreover,
compounds useful in absorbing erythema-causing rays are, when
topically applied in the various known forms, easily removed from
the skin by salt or fresh water.
In as much as sunscreening compositions are generally used in hot
weather and at beach and water facilities where people enjoy
bathing activities, such compositions which are removed by water
have limited effectiveness. Even where artificially induced rays,
such as by commercially available sun lamps, are used the heat
causes the user to perspire which erodes the sunscreening agents
away.
Sunscreening formulations have been produced in attempts to
overcome the substantive instability of the foregoing described
sunscreening materials. Ethylenically unsaturated ultraviolet
absorbing compounds have been polymerized in attempts to make a
substantive sunscreening material. These materials have the
disadvantages in that they may contain small entrained quantities
of harmful monomeric material or are polymerized under conditions
which reduce the sunscreening ability of the resultant product.
SUMMARY OF THE INVENTION
It has now been found that sunscreening formulations which are
useful in absorbing the erythema-producing rays of the sun are
formed from a polymeric reaction product produced from para-dialkyl
aminobenzoyl halides and polyethylenimines. The polymeric product
thus formed can be encompassed into any of the various cosmetic
carrier materials known to be useful by the practitioner. Such
polymeric products, when topically applied to the human skin, will
form a film material which will resist removal from the skin by the
action of salt or fresh water or perspiration.
Sunscreening formulations containing the
polyethylenimine-paradialkylaminobenzoyl halide reaction product
are capable of screening harmful ultraviolet radiation while
permitting transmission of the beneficial rays. In this manner the
individual may subject himself to sunlight to cause the
aesthetically desirable tanning of the skin while alleviating the
problems of sunburn or erythema which is usually accompanied by
discomfort and pain. The formulations containing the polymeric
product described herein forms when, topically applied, a film
material which adheres to the skin and resists removal therefrom
even when subjected to the action of fresh or salt water or through
perspiration of the individual. These compositions are, therefore,
long lasting and need not be applied numerous times to insure
proper protection.
DETAILED DESCRIPTION OF THE INVENTION
The material which has herein been found to be an excellent
sunscreening agent is produced from the reaction of
polyethylenimine and a para-dialkylaminobenzoyl halide. The
para-dialkylaminobenzoyl halide may contain alkyl groups having
from 1 to 4 carbon atoms such as methyl, ethyl, n-propyl or n-butyl
groups and the like. The preferred compounds have alkyl groups each
having one or two carbon atoms. These alkyl groups are attached to
the nitrogen atom via a primary covalent bond and thus form a
dialkylamino radical which is preferably attached to the benzene
ring in the para position with respect to the halocarbonyl group.
The halogen atom of the halocarbonyl group may be chlorine,
bromine, flourine or iodine. the chloro derivative is preferred due
to its ease of handling, accessibility and reactivity.
Polyethylenimine is a commercially available material which is
produced by the catalytic reaction of the cyclic compound,
ethylenimine. Although the monomeric material, ethylenimine, is
highly toxic, polyethylenimine has been found to be nontoxic to
humans. This material is produced in a wide range of molecular
weights ranging from about 500 to about 100,000 average molecular
weight. The exact polyethylenimine used as the precursor for the
substantive sunscreen material described herein may be any of the
commercially available products. Lower molecular weight (about 500
to about 2,500) materials, available in anhydrous form, are
particularly useful due to ease of handling when reacting with
benzoyl halides.
The reaction product of polyethylenimine and a
para-dialkylaminobenzoyl halide forms a polymeric material which
may be described as poly(para-dialkylaminobenzoyl)ethylenimine. The
polymeric product may be formed in any conventional manner in which
halocarbonyls are reacted with primary and secondary amines. The
hydrogen chloride byproduct which is formed may be neutralized by
any known means such as by adding to the reaction mixture a
compound such as sodium carbonate which will react in situ with the
hydrogen chloride and will form products which can easily be
separated from the desired polymeric material. Alternately,
compounds may be added to the reaction mixture after the desired
product has been formed to neutralize any hydrogen chloride
by-product entrained in the mixture. This may be done by utilizing
ion exchange resins or by using alkalis such as sodium
hydroxide.
The resulting polymeric material found useful herein include
copolymers of polyethyleneimine containing copolymeric materials
used as poly(p-dimethylaminobenzoyl)ethylenimine,
poly(p-diethylaminobenzoyl)ethylenimine,
poly[p-di(n-propyl)aminobenzoyl]ethylenimine,
poly[p-di(isopropyl)aminobenzoyl]ethylenimine and the like as well
as interpolymers having two or more substituted polyethylenimines
in the same polymeric material such as poly[ethylenimine]
[(p-dimethylaminobenzoyl)ethylenimine]
[(p-diethylaminobenzoyl)ethylenimine] and the like.
The polymeric reaction products formed contain
paradialkylaminobenzoyl radicals pendant to the polyethylenimine
polymeric backbone. These pendant groups may be attached to the
primary and/or the secondary amines of the polymer backbone. All of
the polymeric reaction products have, when tested, highly selective
absorbtion qualities for radiation in the ultraviolet wavelength
range between about 280 millimicrons to about 320 millimicrons.
This range of radiation is known to cause the onset of sunburn or
erythema on human skin. Applicant's polymeric reaction products,
when applied to the skin, in any convenient form protects the skin
from these harmful radiations by forming a substantive film which
absorbs the undesirable radiation.
The amount of para-dialkyl aminobenzoyl halide which is allowed to
react with the polymeric backbone material may be of such quantity
as to cause the polymeric product formed to have from about 5 to
about 80 weight per cent dialkylaminobenzoyl radical pendant groups
based on the total weight of the polymeric reaction product. Higher
percentages of these pendant groups may be used although are not
normally necessary to form an effective material. The exact percent
of these pendant groups which may be incorporated onto the
polymeric backbone is only limited by the amount of amino groups
located thereon and the type of formulation onto which these
products are to be used. It is realized that the radicals
containing the higher alkyl groups will naturally be less in number
for the same weight percentage. Therefore, higher weight
percentages of these radicals will be needed to produce the same
protection as radicals containing lower alkyl groups such as the
dimethylaminobenzoyl radical.
Polyethylenimine may be reacted with one or more than one specie of
dialkylaminobenzoyl halide either simultaneously or successively
thereby forming a polymer reaction product having one specie of
pendant group or having a mixture of dialkylaminobenzoyl
groups.
Applicant's polymeric reaction product containing the selective
ultraviolet absorption groups have been found to be highly
effective sunscreening agents in that they selectively absorb the
harmful erythema producing rays while transmitting the more
desirable tanning rays to the skin. These polymeric products
readily form a film when applied to the skin which adheres thereto
and is resistant to removal from the skin by the action of fresh
water, perspiration, or salt water and, therefore, is more durable
under conditions which are most commonly found at the sea shore or
the poolside. The polyethylenimine substrate which acts as a binder
to the keratin surface of the skin and allows the
paradialkylbenzoyl pendant groups to impart sunscreening activity
is longlasting and need not be applied periodically by the
individual after each contact with the water nor periodically due
to the action of body perspiration. The polymeric sunscreening
agent may have pendant groups which are all the same such as the
dimethylaminobenzoyl radical or, alternatively, mixtures of
dialkylaminobenzoyl halides may be reacted with polyethylenimine to
form a mixed dialkylaminobenzoyl polyethylenimine polymeric
material.
The polymeric material containing from about 5 to about 80 weight
per cent pendant groups on the polymeric backbone may be combined
with additional materials to form a sunscreening composition. These
compositions may contain from 1 percent to about 50 percent of the
polymeric reaction product based on the weight of the total
composition. Compositions containing from 1 percent to 25 percent
of the polymer have been found satisfactory under normal
conditions. The exact amount of polymeric product incorporated in
the sunscreening compositions herein disclosed will depend upon the
exact amount of pendant groups in the polymeric backbone and the
degree of protection which is desired in a particular preparation.
The formulator of any particular preparation may calculate the
percent of reactive sunscreening groups which is ultimately in any
preparation by knowing the percentage of pendant groups in the
polyethylenimine polymer reaction product. The amount of pendant
groups which affords ample protection is from about 0.1 to 10
percent of the total formulation. For example, protection can be
attained by forming a sunscreening composition containing 1.0
percent dimethylaminobenzoyl radicals.
A vehicle material is combined with the polymeric reaction products
disclosed hereinabove to form sunscreening compositions which can
be readily dispensed onto the skin of the user. These materials may
be a water-alcohol mixture, water and oil cream or an oil base, as
customarily known to those skilled in the art. The water-alcohol
base may contain up to 75 percent of an alcohol material having
lower alkyl groups such as methanol, ethanol, propanol and the
like. Alternately, or in combination, the water-alcohol vehicle
material may contain dihydroxy alcohols such as ethylene glycol,
propylene glycol and the like. The oil base or the oil and water
cream materials may contain oils which are commonly used and are
known to those skilled in the art. Examples of such oils are
mineral, vegetable and animal oils. Emulsions of the sunscreening
polymeric reaction product may be made with any of these base
materials to form a homogenous mixture which can be subsequently
applied to the skin.
The compositions herein disclosed may, in addition, contain the
usual quantities of additional ingredients. These ingredients
include emulsifiers, fillers, perfumes, stabilizers, and the like
commonly used in such preparations.
The compositions thus formed can be easily applied to the skin of
the user and will readily form a film material which contains the
erythema-protecting polymeric agent. In the case of a water-alcohol
based material the volatile base will evaporate and leave on the
skin a continuous transparent film material. Such films will
provide complete and long lasting protection against
erythema-producing rays and it has been found that these films are
not easily removed by the action of fresh or salt water or through
the perspiration of the user. The oil base materials and the water
and oil base compositions will form a continuous oily film of the
desired polymeric sunscreening material. These films also provide
complete and long lasting protection against sun induced erythema.
Sunscreening compositions are generally used in hot weather and at
beaches where people enjoy bathing activities. It is therefore,
essential that the protective coating applied to the skin is not
appreciably effected by water or perspiration. The compositions
herein disclosed form a thin layer of protective coating on the
skin of the user and will form a long lasting material which is not
easily removed by the action of fresh or salt water or through
perspiration. Therefore, the compositions disclosed herein offer a
more complete and efficient protection than compositions known and
commonly sold on the market.
The following examples herein disclosed are for illustrative
purposes only and are not meant to be limiting upon the invention
concept except as set forth in the appended claims. All parts and
percentages are by weight unless otherwise indicated.
EXAMPLE I
A polymeric reaction product which is formed from the reaction of
dimethylaminobenzoyl chloride with a commercially available
polyethylenimine having an average molecular weight of 1,800 is
prepared. The resultant product having 15 percent pendant
dialkylaminobenzoyl radicals as determined by an oxygen analysis
has a maximum absorption peak at 298 millimicrons and is,
therefore, an ultraviolet radiation absorbing material useful in
preventing erythema conditions. An oil base sunscreen lotion is
prepared using the above polymeric reaction product as follows:
poly(p-dimethylaminobenzoyl)ethylenimine 10 parts mineral oil
(U.S.P.) 45 parts peanut oil 45 parts
The oily lotion is applied to the skin of a user. The film formed
offered complete protection to sunburning even after several hours
of bathing and being in the sun.
EXAMPLE II
A composition was prepared of the dimethylaminobenzoyl chloride and
polyethylenimine reaction product as described in Example I which
is incorporated into an aqueous alcoholic solution. A typical
example of such a composition is as follows:
poly(p-dimethylaminobenzoyl)ethylenimine 20 parts ethyl alcohol 30
parts water 50 parts
Such a composition is applied to the skin and when the volatile
vehicles evaporate sunscreening polymeric material forms a
continuous film on the skin of the user and is found to be
resistant to water and perspiration and, therefore, forms an
effective longlasting protection to erythema-causing rays.
EXAMPLE III
A polymeric reaction product was prepared by reacting
diethylaminobenzoyl chloride with polyethylenimine of 1,800 average
molecular weight. The resultant product contained 20 percent by
weight, based on the total weight of the polymeric material, of the
diethylaminobenzoyl radical as determined by an oxygen analysis of
the product. The product is incorporated into a cosmetic lotion to
form an emulsion and is applied to the skin to produce a continuous
film of the polymeric product upon evaporation of the more volatile
vehicles. This film is durable to water and perspiration and was
found to give longlasting protection to erythema causing rays.
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.
* * * * *