U.S. patent number 3,697,643 [Application Number 05/098,464] was granted by the patent office on 1972-10-10 for cosmetic preparations.
This patent grant is currently assigned to National Patent Development Corporation. Invention is credited to Francis E. Gould, Thomas H. Shepherd.
United States Patent |
3,697,643 |
Shepherd , et al. |
October 10, 1972 |
COSMETIC PREPARATIONS
Abstract
Mascara is prepared by adding a hydrophilic acrylate or
methacrylate polymer to the selected cosmetic preparations.
Inventors: |
Shepherd; Thomas H. (Hoepwell,
NJ), Gould; Francis E. (Princeton, NJ) |
Assignee: |
National Patent Development
Corporation (New York, NY)
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Family
ID: |
26794769 |
Appl.
No.: |
05/098,464 |
Filed: |
January 15, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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567856 |
Jul 26, 1966 |
3520949 |
|
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650259 |
Jun 30, 1967 |
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654044 |
Jul 5, 1967 |
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743626 |
Jul 10, 1968 |
3574822 |
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Current U.S.
Class: |
424/70.7; 424/63;
424/70.16 |
Current CPC
Class: |
C08F
220/26 (20130101); C08L 51/00 (20130101); A61K
8/8152 (20130101); A23L 27/74 (20160801); C09D
4/00 (20130101); A61K 8/24 (20130101); C09D
4/00 (20130101); G02B 1/043 (20130101); A61Q
1/10 (20130101); G02B 1/043 (20130101); A01N
25/10 (20130101); A61Q 15/00 (20130101); A61Q
17/02 (20130101); A61Q 1/02 (20130101); A61Q
17/04 (20130101); A61Q 5/06 (20130101); A61Q
11/00 (20130101); A61Q 1/06 (20130101); A61Q
19/00 (20130101); A61Q 19/10 (20130101); A61K
2800/56 (20130101); A61Q 1/12 (20130101); A61Q
3/02 (20130101) |
Current International
Class: |
A01N
25/10 (20060101); A23L 1/22 (20060101); A61K
8/72 (20060101); A61K 8/81 (20060101); A61K
8/19 (20060101); A61K 8/24 (20060101); C09D
4/00 (20060101); A61Q 11/00 (20060101); G02B
1/04 (20060101); A61k 007/02 () |
Field of
Search: |
;424/63,81 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rose; Shep K.
Parent Case Text
The present application is a continuation-in-part of application
Ser. No. 567,856, filed July 26, 1966, now U.S. Pat. No. 3,520,949;
application Ser. No. 650,259, filed June 30, 1967 and now
abandoned; application Ser. No. 654,044, filed July 5, 1967 and
application Ser. No. 743,626, filed July 10, 1968 now Pat. No.
3,574,822.
The present application relates to novel cosmetic preparations.
Claims
What is claimed is
1. In a process of improving the external natural pigment and
appearance of the areas of the eyes of the human body by applying a
cosmetic mascara pigment preparation thereto, in mascara cakes,
roll-on mascaras, cream mascaras, eye shadow sticks, eye liner
pencils or eyebrow pencils and the like the improvement whereby
said eye mascara does not run when wet, and is removable cleanly by
moistening and rubbing comprising applying to the eye areas a
cosmetic preparation suitably colored with mascara pigments in
mascara form consisting essentially of said mascara pigments
dispersed in a polymer of an acrylate or methacrylate selected from
the group consisting of hydrophilic polymer of hydroxy lower alkyl
acrylates, hydroxy lower alkyl methacrylates, hydroxy lower alkoxy
lower alkyl acrylates and hydroxy lower alkoxy lower alkyl
methacrylates.
2. A process according to claim 1 wherein the polymer is a member
of the group consisting of hydroxy-ethyl acrylate, hydroxyethyl
methacrylate, hydroxypropyl acrylate and hydroxypropyl
methacrylate.
3. A mascara pigment cosmetic composition useful for applying
around the eyes consisting essentially of mascara pigments
dispersed in a polymer of an acrylate or methacrylate selected from
the group consisting of hydrophilic polymer of hydroxy lower alkyl
acrylates, hydroxy lower alkyl methacrylates, hydroxy lower alkoxy
lower alkyl acrylates and hydroxy lower alkoxy lower alkyl
methacrylates.
4. A mascara composition according to claim 3 wherein the polymer
is a member of the group consisting of hydroxyethyl acrylate,
hydroxy ethyl methacrylate, hydroxypropyl acrylate and
hydroxypropyl methacrylate.
5. A mascara composition according to claim 4 including carbon
black pigment.
Description
Cosmetic manufacturers have sought in the past to produce
compositions for use on human hair and skin which may be easily
applied, exhibit no detrimental effect on the skin and retain their
stability for a reasonable period of time. Some progress has been
made in producing products of this type. However, there remains
inherent defects in prior preparations such as creams, lotions,
shampoos, dressings, sticks, and the like which impairs their
cosmetic effectiveness. One example of this is the well-known
tendency of conventional mascara to run when wet by tears or
water.
As is well known the various creams used on the body have a
tendency to soil clothing, bed clothes and the like. Lipsticks and
suntan creams have a tendency to be greasy and essences (e.g.
perfume) and other volatile components present in lipstick, creams
and lotions have a tendency to be lost on standing.
It has hitherto been proposed to employ lacquers for imparting a
temporary set to the hair. However, since lacquers include a
water-insoluble film-forming ingredient, it has been extremely
difficult to remove them from the hair. When it is desired to
change the hair style, it sometimes becomes necessary to employ a
special solvent or a powerful detergent composition, neither of
which is readily available in the home. Lacquers have generally
been considered unsatisfactory for application to the hair for this
reason. A number of water-soluble film-forming resinous materials
have also been proposed for application to the hair in order to set
it. However, such water-soluble materials have not been completely
satisfactory because of the tendency for the resultant film to
become tacky and for the hair to lose its set when exposed to
conditions of high humidity.
Furthermore, at present there is no satisfactory method for
straightening kinky hair.
Accordingly, it is an object of the present invention to prepare
novel cosmetic compositions.
Another object is to improve the application of cosmetic
compositions to the body.
An additional object is to overcome the tendency of mascara to run
when wet.
A further object is to protect the body against the drying effects
of cosmetics comprising alcohol solutions.
Yet another object is to overcome the greasiness present in various
cosmetic creams, sticks, and lotions.
A still further object is to reduce the staining or soiling
property of cosmetic creams and lotions.
An additional object is to reduce the loss of flavors or essences
from cosmetic compositions.
A corollary object is to develop cosmetic compositions which
release a flavor or essence when wet.
An important object of the invention is to straighten kinky or
curly hair so that it can be manipulated as desired.
A related object is to set hair of any type.
A further object is to develop a hair setting composition and
method which will provide a "permanent" set even under conditions
of high humidity.
A related object is to give hair a "permanent" that does not result
in the treated hair developing static electrical charges under
conditions of low humidity.
Another object is to apply a film having one or more of the above
characteristics in relation to hair, but which can be readily
removed.
A still further object is to develop novel aerosol compositions
useful for application to the body.
Still further objects and the entire scope of applicability of the
present invention will become apparent from the detailed
description given hereinafter; it should be understood, however,
that the detailed description and specific examples, while
indicating preferred embodiment of the invention, are given by way
of illustration only, since various changes and modifications
within the spirit and scope of the invention will become apparent
to those skilled in the art from this detailed description.
It has now been found that these objects can be attained by
employing certain hydrophylic acrylate and methacrylate polymers in
cosmetic compositions. For liquid cosmetics the hydrophylic polymer
should not have substantial cross-linking (i.e. the cross-linking
should not be sufficient to render the polymer insoluble in the
solvent) while for powdered or creamy compositions cross-linked
copolymers can be employed.
The term cosmetic is intended to embrace all types of products
which are to be applied in any manner directly to the person for
the purpose of cleansing or embellishment, including altering the
appearance. Toilet soap and shaving soaps and creams are intended
to be included in this definition as well as deodorants,
depilatories, suntan and sunscreen preparations.
The hydrophylic monomer used to prepare the hydrophylic polymer is
preferably a hydroxyalkyl monoacrylate or methacrylate such as
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene
glycol monoacrylate, diethylene glycol monomethacrylate,
hydroxypropyl acrylates and methacrylates, e.g. 2-hydroxypropyl
acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,
3-hydroxypropyl methacrylate, tetraethylene glycol
monomethacrylate, pentaethylene glycol monomethacrylate,
dipropylene glycol monomethacrylate, dipropylene glycol
monoacrylate. Acrylamide, methacrylamide, diacetone acrylamide,
methylolacrylamide and methylol methacrylamide also are useful
hydrophylic monomers. The most preferred monomer is 2-hydroxyethyl
methacrylate and the next most preferred monomer is 2-hydroxyethyl
acrylate.
In preparing hydroxyalkyl acrylates and methacrylates a small
amount of the diacrylate or dimethacrylate is also formed. This
need not be removed as it does not cause undue cross-linking.
When it is desired to shampoo out the hydrophylic polymer there are
desirably included 0.1 to 15 percent of an ethylenically
unsaturated acid to provide free acid groups. Typical examples of
such acids include acrylic acid, methacrylic acid, itaconic acid,
aconitic acid, cinnamic acid, crotonic acid, citraconic acid,
measaconic acid, maleic acid and fumaric acid. Less preferably
there can also be used partial esters of polybasic acids such as
mono 2-hydroxypropyl itaconate, mono 2-hydroxyethyl itaconate, mono
2-hydroxyethyl citraconate, mono-2-hydroxypropyl aconitate, mono
2-hydroxyethyl maleate, mono-2-hydroxypropyl fumarate, monomethyl
itaconate, monoethyl itaconate, mono Methyl Cellosolve ester of
itaconic acid (methyl Cellosolve is the monomethyl ether of
diethylene glycol), mono Methyl Cellosolve ester of maleic
acid.
The use of such acid containing groups does not result in
substantial cross-linking unless the polymer is heated for a
substantial time above normal operating conditions for cosmetics or
unless the polymerization time is prolonged using relatively high
amounts of catalysts.
When cross-linked or cross-linkable hydrophylic polymers are
prepared normally the cross-linking agent is preferably present in
an amount of 0.1 to 2.5 percent, most preferably 0.1 to 1.0
percent, of the total monomers, although up to 15 percent of
cross-linking agent can be used. Typical examples of cross-linking
agents include ethylene glycol diacrylate, ethylene glycol
dimethacrylate, 1,2-butylene dimethacrylate, 1,3-butylene
dimethacrylate, 1,4-butylene dimethacrylate, propylene glycol
diacrylate, propylene glycol dimethacrylate, diethylene glycol
dimethacrylate, dipropylene glycol diacrylate, divinyl benzene,
divinyl toluene, diallyl tartrate, allyl pyruvate, allyl malate,
divinyl tartrate, triallyl melamine, N,N'-methylene-bis-acrylamide,
glycerine trimethacrylate, diallyl maleate, divinyl ether, diallyl
mono ethylene glycol citrate, ethylene glycol vinyl allyl citrate,
allyl vinyl maleate, diallyl itaconate, ethylene glycol diester of
itaconic acid, divinyl sulfone, hexahydro-1,3,5-triacryltriazine,
triallyl phosphite, diallyl ester of benzene phosphonic acid,
polyester of maleic anhydride with triethylene glycol, polyallyl
sucrose, polyallyl glucose, e.g. diallyl sucrose and triallyl
glucose, sucrose diacrylate, glucose dimethacrylate,
pentaerythritol diacrylate, sorbitol dimethacrylate.
The cross-linked polymers are characterized by being insoluble in
the solvents. Typical examples of suitable cross-linked hydrophilic
polymers are those in Wichterle U.S. Pat. No. 2,976,576, Wichterle
U.S. Pat. No. 3,220,960, e.g. examples III, V, VI, VII, and IX,
Wichterle U.S. Pat. No. 3,361,858, examples 1, 2, 3, 6, 8, 9, 10,
and 11, as well as copolymers of 30 parts ethylene glycol with 0.1
part ethylene glycol bis-methacrylate; 54.7 parts ethylene glycol
monomethacrylate, 17.2 parts diethylene glycol monomethacrylate and
0.6 parts of diethylene glycol dimethacrylate; 80 parts ethylene
glycol monomethacrylate, 15 parts methacrylamide and 0.4 parts of
ethylene glycol bis-methacrylate; 97 parts ethylene glycol
monomethacrylate, 0.25 part diethylene glycol dimethacrylate and
0.25 part ethylene glycol bis-methacrylate; 60 parts ethylene
glycol monomethacrylate, 19.7 parts diethylene glycol
monomethacrylate, 0.3 part ethylene glycol bis-methacrylate, 99.6
parts ethylene glycol monomethacrylate and 0.4 part ethylene glycol
bis-methacrylate, 99.5 parts ethylene glycol monomethacrylate and
0.4 part ethylene glycol bis-methacrylate, 99.7 parts ethylene
glycol monomethacrylate and ethylene glycol bis-methacrylate; 98.7
parts ethylene glycol monomethacrylate and 0.3 part diethylene
glycol dimethacrylate. They can also be prepared using the
procedures set forth in our parent application Ser. No. 654,044 or
the procedures employed in the specific examples below.
Unless otherwise indicated all parts and percentages are by
weight.
The hydrophylic polymers of this invention possess unique
properties which are capable of improving a wide range of cosmetic
products. In particular, they impart to such products a wide range
of unusual and desirable properties and effects on the skin and
hair, such as lubricity, emolliency, softening and smoothing,
resistance to and protection against the drying effects of alcohol
solutions, resistance to water and/or soap or detergents and water,
freedom from tactile greasiness or oiliness due to mineral and/or
vegetable oils, marked solvency and coupling effects for lanolin,
lanolin isolates and derivatives either alone or in the presence of
mineral and vegetable oils and freedom from tackiness or greasiness
in preparations containing any of the above-mentioned
materials.
Considering specific applications of the hydrophilic polymers; they
are useful in creams, which essentially comprise an oleaginous
base, either as an addition thereto or to replace, at least in
part, oily fatty and/or waxy ingredients of the creams. For
example, the polymers may partly replace the almond oil, mineral
oil, lanolin, beeswax, paraffin wax, oleic acid, or spermaceti, and
the like, which are conventionally used in creams, whether of the
cleansing, emollient, or finishing types, and including cold cream,
quick-liquefying cream, liquid cleanser cream, night cream, massage
cream, vanishing cream, foundation cream, and various special
creams. An advantage of replacing at least part of such materials
is that the soiling tendency of the creams is reduced, that is to
say, the creams after being spread over the skin by the user are
less apt to pick up or attract soil or foreign particles,
similarly, the deposited creams transfer off the user's skin less
readily, as by contact with clothing, bed sheets, and the like.
This last advantage is of particular importance in other creams
such as deodorants, including deodorizer and anti-perspirant
creams, which are used under the arms and on the palms and soles
and which are quite apt to come in contact with clothing and to
soil it to such an extent that the garments are frequently ruined.
The lanolin, petrolatum, cresin, beeswax, cocoa butter, and/or
stearic acid contents of emollient and vanishing creams, and also
of cream and paste rouges, can be partly supplanted to reduce their
soiling tendency, and more particularly to reduce their oily or
greasy feel while yet retaining their power of free motion over the
skin. Because they are lubricitous in a cream preparation without
increasing its oleaginous character, cross-linked polymers are
suitable for addition to creams to be applied to the oily skin.
Special creams such as protective creams can usefully incorporate
the polymers of this invention. The creams can be of any suitable
type, such as a mixture of fats and oils, a jelly containing a
physical barrier, an emulsion, or a soap base. These creams are of
particular value for protecting the hands from injury, or from
soiling, in carrying out many processes and procedures in
industrial plants. These creams containing physical barriers are
particularly adapted to receive the hydrophylic polymers, which
being available in various particle sizes, may form protective
barriers on the skin of varying degrees of fineness and
smoothness.
Make-up powders for the face may benefit from the presence of the
polymers. These powders usually comprise an opacifying agent (clay,
titania, magnesia zinc oxide, etc.,) a slip material (talk, metal
stearates, etc.,), an adherent material (stearates, clay, etc.) and
an absorbent (chalk, calcium carbonate, kaolin, etc.). The
hydrophilic polymers are capable of replacing in whole or in part,
metal salts and oxides like chalk, kaolin, magnesium carbonate,
talc, titania, magnesium stearate, zinc oxide, zinc oxide, zinc
stearate and the like. An advantage of such a substitution is the
reduced incidence of undesirable dermatological reactions. For
example, in the case of magnesium carbonate, a widely used
ingredient, it is known that some persons are sensitive to the
presence of trace amounts of elements like selenium, arsenic, or
mercury which tend to be present in the magnesium carbonate owing
to the difficulty of purifying it. The gravity of the problem is
underlined by the fact that amounts of selenium as low as 1 part
per million may be detrimental. Other conventional ingredients, if
not sufficiently fine, may give rise to mechanical irritation. In
the case of ingredients like talc, by omitting it there is
eliminated its characteristic earthy odor, which otherwise must be
masked. Of further interest is the effectiveness of the polymers
for sorbing oil, this properly being useful in face powders for
combating oily skin, especially on the nose. By sorption is meant
the capacity of the polymeric powder to absorb oily, fatty, greasy,
waxy and aqueous materials.
In addition to the foregoing capabilities, the polymers are of
benefit to loose face powder compositions by virtue of their
excellent adherence to surfaces including the skin, by the degree
to which their particle size may be varied, and by the extent to
which their fluffiness or bulk density may be changed. Therefore,
they are useful in place of the adherent agents noted. By
incorporating conventional amounts of a desired color and a desired
perfume, a complete, esthetically suitable face powder may be made
which will inherently have a mat effect, and which may be used per
se or serve as a base, with or without the color and perfume, to
which only minor additions need be made to obtain desired finished
powders to suit different types of skin.
In compact powders, including face powder and rouge, which are
pressed after the addition of a binder like gum arabic, gum
tragacanth, glycerine, sorbitol, etc., the use of the hydrophilic
polymers can eliminate the need for the binder as they are
inherently compressible in the dry or wet state to any desired
degree.
The polymers are also useful in lipstick compositions and can
replace one or more oleaginous ingredients in whole or part, such
as the fats and waxes, with the advantage or decreased greasiness
without loss of lubricity, and improved consistency retention. Fats
and waxes which are commonly used in lipstick compositions include
beeswax, carnauba wax, ceresin, lanolin, lard, mineral oil,
petrolatum, etc. Conventionally used lipstick flavors, usually
comprising a volatile, water-immiscible organic ester, may be
better retained in the lipstick owing to the good sorptive capacity
of the polymers for such compounds. The polymers form free-
flowing, apparently dry mixes with flavors, and thus can facilitate
lip-stick manufacture by serving as a carrier for introducing these
volatile compounds to the production batch and losses of the
flavors may be reduced.
In mascara preparations such as mascara cake, the polymers can
supplant conventional soaps like triethanolamine stearate,
triethanolamine, oleate, etc., and thereby render the preparation
less irritating to the eyes. The waxes frequently used in these
preparations, and also in roll-on mascara and cream mascara, can be
at least partly replaced with advantages similar to those described
in wax substitutions. The hydrophylic polymers of this invention
are also capable of imparting a cleaner effect to eyelashes,
avoiding the thick, pasty, or crumbly look resulting from the use
of some conventional preparations or the startling effect imparted
by some enamel-like preparations. Use of the polymers permits a
wider selection of colors to be employed as mascara pigments and
thus may avoid dependence on the conventional but somewhat
dangerous use of silver nitrate with sodium thiosulfate. Suitable
colors for mascara pigments include natural pigments, e.g. carbon,
ochers, siennas, umbers, ultramarine, etc. In similar ways, the
polymers are of value to other cosmetics for use around the eye, as
in eye shadow sticks, eye liner pencils, and eyebrow pencils.
The hydrophylic polymers of the invention can improve shaving
creams, soaps and sticks of the lathering type by strengthening and
stabilizing the lather.
In sunscreen products, including suntan products and leg paints,
the hydrophylic polymers provide lubricity without greasiness, and
in addition, the adherence of the product to the skin is enhanced,
and its water-removability improved. As these preparations are
frequently in dispersion form, a further advantage resides in the
stability which is imparted to the dispersions by the presence of
the polymers. Of interest in this connection are simple 2-, 3-, or
4- component suncreen preparations made by mixing a base like
petrolatum or zinc oxide or lanolin with the hydrophilic polymer
and water. A sunburn preventive can be added to help block out
harmful radiation, including such agents as acetanilide,
cholesterol, p-aminobenzoic and salicylic acid salts, quinine
salts, and the like. These components form compatible mixtures.
Suntan make-up, whether in loose powder form for the face and other
areas, or in cake form, can be benefited in the manner described
for make-up powders.
In manicure compositions, water removable nail coating compositions
can be prepared comprising simply a hydrophilic polymer of this
invention, a coloring agent, and solvent. The polymer provides the
necessary adherence to the nails. Such compositions are of value
for application to the nails for a single occasion of short
duration, after which the coatings are removable by simply washing
the hands in water.
The polymers of this invention are also effective in hair
preparations.
The present invention overcomes the disadvantages pointed out supra
of previous hair preparations. Even though the hydrophylic polymers
of the invention are insoluble in water, they are easily removed,
e.g. with conventional shampoo.
Hair sprays produced according to this invention comprise a soluble
hydrophylic polymer such as previously described and a non-toxic
organic solvent When an aerosol is to be prepared then a propellant
is also used. As the organic solvent there can be employed
alcohols, particularly lower aliphatic saturated alcohols e.g.
ethyl alcohol, isopropyl alcohol, propyl alcohol, glycols, e.g.
ethylene glycol diethylene glycol, propylene glycol and dipropylene
glycol, glycerine, ethylene glycol methyl ether, ethylene glycol
ethyl ether, n-propylene glycol monomethyl ether, n-propylene
glycol monoethyl ether, isopropylene glycol monomethyl ether,
isopropylene glycol monoethyl ether, ethyl acetate. Mixtures of
these solvents with minor amounts of water, e.g. up to 30 percent
water, can be also employed. Glycols and glycerine and similar
polyhydric alcohols act as plasticizers for the hydrophylic
polymer.
Generally the amount of hydrophylic polymer will be about 0.5 to 10
percent, preferably 0.75 to 5 percent, by weight of the total hair
spray composition.
Hair setting and hair straightening compositions are also produced
according to the invention using 0.5 to 10 percent of the
hydrophylic polymer in the solvent.
Such compositions not only provide the desired temporary
set-holding characteristics and maintains the hair in the desired
configuration until removed, but do so even when the hair is
exposed to conditions of high humidity without the development of
any appreciable surface track. In addition, the hair thus treated,
despite its resistance to moisture, is remarkably free from any
tendency to develop static electrical charges when combed or
brushed under conditions of low humidity. Furthermore, the treated
hair is capable of being reset merely by use of water-dampened
comb. Finally, the film on the hair may readily be removed, despite
its resistance to moisture, by a mild shampoo.
The hydrophylic polymers can be used not only in solution, but also
in compositions having the form of stable gels, creams and the like
without requiring the presence of an emulsifying agent. They can
have the physical form of a jelly, paste, plastic mass, or the like
and generally comprise the hydrophylic polymer in an amount of 2 to
15 percent by weight of the total composition. Advantageously there
can be included 7 to 20 percent of a thixotropic agent such as
Carbopol 961 (sucrose acrylate having free acid groups).
The amount of solvent is usually 10 percent or more of the total
hair preparation. When a propellant is present the solvent is
normally not over 60 percent and is preferably 25 to 40 percent of
the total hair preparation by weight.
When the hydrophylic polymer is packaged in an aerosol container
the propellant should be sufficient to force the composition out of
the container as a spray. The propellant can vary considerably, but
usually is about 25 to 85 percent, preferably 50 to 70 percent, of
the total hair spray composition. As the aerosol propellants there
can be used compressed gasses such as carbon dioxide, nitrous oxide
and nitrogen, liquified volatile hydrocarbons such as propane,
n-butane, isobutane, 2-methyl butane and fluorinated compounds
including perhalo-genated compounds and fluorinated hydrocarbons
such as dichlorodifluoromethane, trichlorofluoromethane,
1,2-dichlorotetrafluoroethane, octofluorocyclobutane,
chlorodifluoromethane, 1,1-difluoroethane,
1-chloro-1,1-difluoroethane. These fluorinated compounds are
available under the names Freon and Genetron. The propellant should
contain a substantial amount of volatile material boiling at not
over 20.degree. C., but there can also be present a significant
amount of less volatile material boiling up to 50.degree. C., e.g.
methylene chloride can be present as a substantial part of the
propellant. Of course perfumes or other essences can be included in
the formulations.
As catalysts for carrying out the polymerization there is employed
free radical catalyst in the range of 0.05 to 1 percent of the
polymerizable hydroxyalkyl ester, for example, the preferred amount
of catalyst is 0.1 to 0.2 percent of the monomer. Typical catalysts
include t-butyl peroctoate, benzoyl peroxide, isopropyl
percarbonate, methylethylketone peroxide, cumene hydroperoxide and
dicumylperoxide. Irradiation, e.g., by ultra violet light or gamma
rays, also can be employed to catalyze the polymerization.
Polymerization can be done at 20.degree. to 150.degree. C., usually
40.degree. to 90.degree. C.
When cross-linked polymers are prepared the method of
polymerization is not critical and the monomers can be polymerized
in water, by suspension polymerization, in organic solvent or
without any solvent. However, when hydrophylic soluble
thermoplastic polymers are desired they are preferably prepared by
suspension polymerization of the hydrophylic monomers in a
non-polar medium such as silicone oil, mineral oil, xylene,
toluene, benzene or the like. Alternatively they can be polymerized
while in solution in ethyl alcohol, methyl alcohol, propyl alcohol,
isopropyl alcohol, formamide, dimethyl sulfoxide or other
appropriate solvent.
In the suspension polymerization procedure the catalyst containing
monomer is dispersed in the non-polar medium in the form of small
droplets which are polymerized to form finely divided spheres or
beads. The beads are dissolved in the polar organic solvents, e.g.,
ethyl alcohol, isopropyl alcohol, ethyl alcohol-water (e.g. 95:5 or
70:30), glycols and glycol ethers for use as sprays, etc. or are
mixed with other ingredients to make creams, powders or the
like.
Suspension polymerization is preferably carried out at
50.degree.-105.degree. C. until bead formation is completed. The
ratio of suspension oil to monomer can be varied widely, but
preferably is from 5:1 to 20:1. As stated the catalyst to monomer
ratio is preferably from 0.05 to 1.0 parts per 100 parts of
monomer.
One method of incorporating the hydrophylic polymeric powders with
cosmetic ingredients or essences dissolved in an appropriate
solvent is to place the mixture on a mechanical roller so that the
solution becomes intimately mixed with the powder. The mixture is
dried by air evaporation or forced heat. Upon evaporation of the
solvent the cosmetic ingredients and/or essences are retained by
the powder.
EXAMPLE 1
Into a flask equipped with an agitator and a heating mantle was
charged 1000 grams of silicone oil; polydimethyl silicone) 100
grams of 2-hydroxyethyl methacrylate and 0.33 grams of isopropyl
percarbonate. The flask was placed under a nitrogen atmosphere and
the contents were rapidly agitated and heated to 100.degree. C.
After 15 minutes at 100.degree. C , the polymer slurry obtained was
filtered hot to isolate the polymer. The polymer powder was
reslurried in 300 ml. of xylene, filtered and dried. A 98 percent
yield of 2 to 5 micron particle size powder was obtained.
EXAMPLE 2
The thermoplastic, solvent soluble poly-(2-hydroxyethyl
methacrylate)polymeric powder formed in example 1 was mixed with an
oil of orchids perfume essence and the resultant mixture placed on
a mechanical roller for approximately 8 hours. The polymeric powder
thus absorbed the essence. The mixture was filtered and the residue
dried at room temperature.
EXAMPLE 3
Example 1 was repeated using xylene in place of the silicone oil.
The amount of 2-hydroxyethyl methacrylate was increased from 100
grams to 300 grams and the quantity of isopropyl percarbonate was
increased to 0.99 gram. An 85 percent yield of polymer beads was
obtained.
EXAMPLE 4
Example 1 was repeated using mineral oil in place of the silicone
oil, the amount of 2-hydroxyethyl methacrylate was increased from
100 grams to 200 grams and the quantity of isopropyl percarbonate
was increased from 0.33 to 0.66 gram. A 98 percent yield of polymer
beads ranging in diameter from 2 to 5 microns was obtained.
EXAMPLE 5
800 grams of ethylene glycol monomethyl ether, 180 grams of
2-hydroxyethyl methacrylate, 20 grams of acrylic acid and 2 grams
of t-butyl peroctoate were charged into a flask. The solution was
heated and stirred under a carbon dioxide atmosphere at 85.degree.
C. for 6 hours. The thermoplastic hydrophylic polymer formed was
precipitated by pouring the reaction solution into 10 liters of
rapidly agitated water. The precipitated polymer was isolated by
filtration and dried. The product of this example while
thermoplastic and solvent soluble has the capability of curing to
cross-linked solvent insoluble polymer by further heating,
particularly if additional catalyst is added. In contrast, the
polymers of examples 1, 3, and 4 are permanently thermoplastic and
solvent soluble. The copolymers formed in examples 7-13 are all
cross-linked.
EXAMPLE 6
The procedure of example 1 was repeated replacing the
2-hydroxyethyl methacrylate by 100 grams of 2-hydroxypropyl
methacrylate to produce a thermoplastic solvent soluble hydrophylic
finely divided bead polymer.
EXAMPLE 7
This example shows the preparation of a cross-linked polymer
prepared with the aid of a foaming agent. The use of a foaming
agent, e.g. sodium bicarbonate, potassium bicarbonate,
azodicarbonamide, benzene sulfonyl hydrazide,
azo-bisisobutyronitrile, etc. aids in preparing polymers which are
in the form of a foam which is easily disintegrated to form a fine
powder by means of a shearing action. Quantities of 0.5 to 10 grams
of foaming agent per 100 grams of reactants are adequate
100 grams of 2-hydroxyethyl methacrylate, 0.15 grams of t-butyl
peroctoate, 0.20 grams of ethylene glycol dimethacrylate and 1 gram
of sodium bicarbonate were heated to 70.degree. C. and the
resulting solid friable polymeric foam ground into a powder of 80
mesh size (U.S. Standard Sieve).
EXAMPLE 8
100 grams of purified 2-hydroxyethyl methacrylate was mixed with
0.2 grams of ethylene glycol dimethacrylate and 1 gram of benzoyl
peroxide. The mixture was sprayed via a nozzle which forms fine
droplets into a chamber containing nitrogen at 150.degree. C. After
spraying of the monomer was concluded, 36 grams of polymer beads
were recovered.
EXAMPLE 9
An aqueous solution was prepared from 15 percent acrylamide, 10
percent ethylene glycol monomethacrylate, 0.1 percent ethylene
glycol dimethacrylate and the balance water. One liter of this
solution was mixed with 10 ml. of an aqueous 2 percent solution of
sodium thiosulfate and 15 ml. of an aqueous 2 percent solution of
ammonium persulfate and the mixture allowed to polymerize at room
temperature. The resulting gel was then finely divided to give a
cross-linked hydrophylic polymer.
EXAMPLE 10
A polymerization mixture was prepared from 15 parts methacrylamide,
80 parts ethylene glycol monomethacrylate, 0.4 parts ethylene
glycol bis-methacrylate and 5 parts of dibenzoyl peroxide. The
mixture was rotated at 400 r.p.m. in a helium atmosphere at
80.degree. C. for 6 hours to give a cross-linked copolymer The
polymer was then finely divided (below 100 mesh).
EXAMPLE 11
97 parts of ethylene glycol monomethacrylate, 0.25 part ethylene
glycol bis-methacrylate, 0.25 part diethylene glycol
bis-methacrylate, 2 parts ethylene glycol and 0.2 part diisopropyl
percarbonate were rotated 80 minutes at 420 r.p.m. in a carbon
dioxide atmosphere at 60.degree. C. to produce a cross-linked
hydrophylic copolymer The polymer was then finely divided, i.e. to
less than 100 mesh.
EXAMPLE 12
15 parts of a monomer mixture consisting of 99.7 percent ethylene
glycol monomethacrylate and 0.3 percent ethylene glycol
bis-methacrylate as a cross-linking agent, 85 parts glycerol and
0.1 part diethyl percarbonate as a catalyst was heated at
65.degree. C. for 20 minutes to form a cross-linked hydrophylic
polymer.
EXAMPLE 13
50 ml. of a mixture of 98 percent ethylene glycol monomethacrylate,
0.3 percent diethylene glycol bis-methacrylate and 1 percent
ethylene glycol were mixed with 50 ml. formamide and an amount of
azo-bis-isobutyronitrile corresponding to 0.2 percent of the
combined monomers. Polymerization was performed at 75.degree. C.
for 50 minutes to give a cross-linked hydrophylic polymer.
EXAMPLE 14
30 grams of the solvent soluble, thermoplastic hydrophylic
poly(2-hydroxyethyl methacrylate) prepared in example 1 was
dissolved in 70 ml. of methanol. To the solution was added 4.0
grams of peppermint oil. The viscous solution was coated on an
impervious plate and allowed to dry to form a film 1.0 mil thick.
The dry film was stripped from the plate and ground to form minute
platelets. These were incorporated in an amount of about 1 percent
in Crest-type toothpaste devoid of flavoring to provide prolonged
release of the peppermint flavor on contact of the product with an
aqueous medium, e g. in the normal brushing of teeth.
The toothpaste formula was:
Hydrophylic polymer platelets containing peppermint oil 1 part
Calcium pyrophosphate 39 parts Sodium caroxymethyl cellulose 1.20
parts Magnesium aluminum silicate 0.40 part Sorbitol 20.00 parts
Sodium coconut monoglyceride sulfonate 0.81 part Sodium lauryl
sulfate 0.70 part Saccharin 0.12 part Stannous pyrophosphate 1.00
part Water 25.77 parts
EXAMPLE 15
A hair setting composition was prepared from 1.90 parts of the poly
2-hydroxyethyl methacrylate prepared in example 1, 0.10 part of
perfume (oil of orchids) and 28 parts of ethyl alcohol. This
solution (50 percent of the total formulation) was packaged in a
conventional aerosol pressure can container together with 45.5
parts (32 percent of the total formulation) of
monofluorotrichloromethane and 24.5 parts (18 percent of the total)
of methylene chloride.
The aerosol was sprayed on hair held in a desired configuration and
allowed to dry, the formulation was found to provide satisfactory
set-holding characteristics even under conditions of high humidity.
The sprayed hair was natural looking, non-sticky, non-static and
exhibited holding power for a relatively long period of time.
EXAMPLE 16
A 5 percent solution of the polymeric 2-hydroxyethyl methacrylate
prepared in example 1 in 95 percent ethyl alcohol (95 percent
alcohol, 5 percent water) was applied to kinky hair. The hair was
relaxed and then rolled on rollers and held intension until dried.
When dry the hair was set and could be combed in conventional
fashion. The permanent remained until the hair was wet.
Drying can be accomplished with or without a conventional hair
dryer. In place of the rollers any other conventional means for
holding the hair in tension can be employed.
EXAMPLE 17
A more flexible wave can be obtained by incorporating 5 to 100
percent, based on the polymer, of glycerol, sorbitol, diethylene
glycol, dipropylene glycol, ethylene glycol, propylene glycol or
other liquid polyhydric alcohol as a plasticizer.
Thus a more flexible wave than that of example 16 was obtained by
applying to the hair, a solution of 5 parts of the poly
2-hydroxyethyl methacrylate, 100 parts of 95 percent ethyl alcohol
and 0.75 part of glycerol. After the hair was relaxed it was held
in tension until dried using a hair dryer. The hair was thus set
and was combed in conventional manner Not only was a more flexible
wave obtained, but the use of glycerol prevented flaking of the
polymer when the hair was combed
EXAMPLE 18
To impart greater sheen to the hair a small amount, e.g. 2--3
percent, of silicone oil can be added to the formulation. Thus the
formulation of example 17 was modified by adding 3 percent of
dimethyl polysiloxane oil based on the 2-hydroxyethyl methacrylate
polymer to give a flexible permanent wave having a high sheen.
The hair straightener compositions can be brushed on the hair,
poured on the hair or combed on the hair. The preferred solvent is
ethyl alcohol with or without minor amounts of water. There can
also be employed other solvents such as isopropyl alcohol,
monomethyl ether of ethylene glycol, monoethyl ether of ethylene
glycol, normal or isopropylene glycol monomethyl ether, normal or
isopropylene glycol monoethyl ether.
EXAMPLE 19
A hair setting gel was produced having the following
formulation:
Hydrophylic 2-hydroxyethyl methacrylate polymer of example 1 10
parts 95% ethyl alcohol 144 parts Water 36 parts Carbopol 940
(sucrose acrylate polymer having free acrylic acid groups 1.2 part
Glycerine 1.4 part Solulan 98 (acetylated polyoxyethylated lanolin)
1.0 part Triton X-100 (polyoxyethylene (10)-nonylphenol condensate)
2.0 parts Essence (lavender oil) 0.6 part
The polymer was dissolved in the alcohol-water mixture to form a
solution. The solution was then mixed with the remaining
ingredients by rapid stirring and the pH of the mixture adjusted to
a pH of about 7.2 by adding a 10 percent solution of
diisopropanolamine in 95 percent ethyl alcohol. This gel was
suitable for setting hair. Thus a sample of curly hair was
straightened by heat and pressure, coated with the above gel and
soaked in water. A control sample of the curly hair was also
straightened, but remained uncoated when soaked in water. The
control sample returned to its original curly configuration after
30 seconds while the coated sample remained straight for about 3
minutes.
In place of the diisopropanolamine there can also be used
triethanolamine, diethanolamine or tripropanolamine as a gelling
agent in this example.
EXAMPLE 20
Into a bottle equipped with an agitator and a heating mantle was
charged 20 liters of 2-hydroxy ethyl methacrylate, 50 liters of
methanol, 30 liters of water and 10 grams of t-butyl peroctoate.
The kettle was flushed with carbon dioxide and the contents were
rapidly agitated and heated to 75.degree. C. After 8 hours at
75.degree. C. the polymer, representing an 85 percent polymeric
conversion, was isolated. The polymer solution was precipitated
from 500 liters of water, filtered and dried at room
temperature.
EXAMPLE 21
A cosmetic emulsion with the following formulation was
prepared.
Two solutions were formulated:
Solution A Polymer produced according to example 20 30 parts Water
95% ethanol Essence .5 part Solution B Mineral oil 30 parts Atlas
polysorbate 80 2.96 parts Triton X 100 0.68 part part
Solution A is added slowly to solution B with rapid stirring for 5
minutes. A stable emulsion results which could be applied to the
hands or face. Polysorbate 80 is polyoxyethylene (20) sorbitan
monooleate.
EXAMPLE 22
An insect repellant sun screen lotion was prepared with the
following formulation:
Hydrophylic polymer of example 1 1 part 95% ethanol 60 parts Water
38 parts 2-ethyl-1,3-hexandiol 0.5 part 2-ethyoxyethyl-p-methoxy
cinnamate 0.5 part
EXAMPLE 23
100 parts of the hydrophylic polymer prepared in example 1
containing 10 parts of essence (oil of orchids) was homogeneously
mixed with 5 parts of hexachlorophene. 75 parts of the resulting
mixture was mixed with a conventional toilet soap (Ivory) to
provide a composit soap having a pleasant smell, antiseptic and
increased lubricity characteristics.
EXAMPLE 24
The hydrophylic polymers of the present invention in powder form
can be incorporated in a fat or oil or lanolin in an amount of 1 to
40 percent to release a fragrance on contact with water. Thus 1
part of perfume was absorbed in 10 parts of the cross-linked
hydrophylic polymer prepared in example 7 and this was incorporated
with 100 parts of lanolin.
EXAMPLE 25
A sun screen aerosol was made from 1 part of the poly
2-hydroxyethyl methacrylate prepared in example 1, 30 parts of 95
percent ethyl alcohol, 0.5 part of 2-ethoxyethyl-p-methoxy
cinnamate and 68.5 parts of dichlorotetrafluoroethane. The aerosol
was sprayed from the container onto the body and acted as an
effective sun screen.
EXAMPLE 26
1 part of hexachlorophene was absorbed on 10 parts of the finely
divided cross-linked hydrophylic methacrylate polymer prepared in
example 11. There was blended in 20 parts of talc and the deodorant
powder was packaged in an aerosol container together with 30 parts
of chlorotrifluoromethane and 10 parts of methylene chloride.
The ratio of polymer to talc can range from 10 to 90 parts of
polymer to 90 to 10 parts of talc or the talc can be omitted.
EXAMPLE 27
20 parts of aluminum chlorohydrol, in 100 parts of water, 10 parts
of hydroxyethyl methacrylate containing 1 part of perfume (e.g.
rose oil) and 0.04 part of isopropyl percarbonate were polymerized
at 70.degree. C. for 2 hours. The solid obtained was ground to a
powder -- less than 300 mesh and was useful as a deodorant by
applying the same to the body.
EXAMPLE 28
A nail enamel was prepared by making a 10 percent solution of the
polymer prepared in example 1 in alcohol together with a small
amount of red dye. The resulting solution was applied to
fingernails and allowed to dry.
EXAMPLE 29
A cleansing cream was prepared from a mixture of 5 parts almond
oil, 15 parts lanolin, 5 parts of the hydrophylic 2-hydroxyethyl
methacrylate polymer prepared in example 1, 30 parts paraffin wax,
5 parts borax and 35 parts distilled water.
EXAMPLE 30
Another cleansing cream was prepared from 25 parts almond oil, 10
parts beeswax, 15 parts lanolin, 8 parts spermaceti, 12 parts of
the hydrophylic cross-linked polymer of example 11 and 30 parts of
rose water.
EXAMPLE 31
A cleansing cream was prepared from 7 parts beeswax, 30 parts
mineral oil, 15 parts soyabean oil, 10 parts spermaceti, 1 part
borax, 8 parts of the hydrophylic polymer prepared in example 6 and
29 parts of rose water.
EXAMPLE 32
A vanishing foundation cream was prepared from 8 parts glycerol, 1
part potassium hydroxide, 20 parts stearic acid, 0.5 part perfume,
7 parts of the hydrophylic polymer of example 1 and 63.5 parts of
water.
EXAMPLE 33
A vanishing cream was prepared from 0.5 part cetyl alcohol, 5 parts
glycerol, 4 parts lanolin, 3 parts mineral oil, 20 parts stearic
acid, 2 parts triethanolamine, 0.5 part part oil of orchids, 3
parts of the hydrophylic polymer prepared in example 5 and 62 parts
of water.
EXAMPLE 34
A quick-liquefying hand cream was made from 12 part cresin, 85
parts mineral oil and 3 parts of the hydrophylic polymer prepared
in example 4.
EXAMPLE 35
An emollient cream for softening the skin was prepared from 5 parts
lanolin, 4 parts beeswax, 10 parts cocoa butter, 10 parts almond
oil, 35 parts solid petrolatum, 5 parts spermaceti, 3 parts of the
hydrophylic polymer prepared in example 1, 0.5 part of perfume, 0.2
part preservative and 27.3 parts water.
EXAMPLE 36
A face powder was made from 10 parts precipitated chalk, 75 parts
talc, 5 parts of the hydrophylic polymer of example 1, 5 parts zinc
oxide and 5 parts zinc stearate.
EXAMPLE 37
A loose face powder was prepared from 3 parts kaolin, 70 parts
talc, 1.5 parts magnesium stearate, 2 parts of D & C Red No. 2
(lake) 20 percent in talc, D & C Red No. 3 (lake) 10 percent
talc, 1 part yellow iron oxide 20 percent in talc and 1 part rose
oil absorbed in 4.5 parts of the hydrophylic polymer of example
7.
EXAMPLE 38
A cake type face powder was prepared from 10 parts kaolin, 5 parts
zinc stearate, 10 parts zinc oxide, 3 parts magnesium carbonate, 61
parts talc (French), 1.4 parts of the hydrophylic polymer prepared
in example 1, 2 parts light mineral oil, 1 part cetyl alcohol, 0.3
part lanolin, 2.7 parts D & C Orange No. 4 (lake), 10 percent
in talc, 0.8 part D & C No. 2 (lake), 20 percent in talc, 1
part brown iron oxide, 20 percent in talc and 0.8 part perfume.
EXAMPLE 39
A baby powder was prepared from 80 parts talc, 9 parts zinc
stearate, 5 parts boric acid and 0.25 part perfume absorbed in 5.75
parts of the hydrophylic polymer prepared in example 1.
EXAMPLE 40
A lipstick was prepared from 12 parts beeswax, 3 parts of the
hydrophilic polymer of example 1, 5 parts Carnauba wax, 20 parts
cresin, 5 parts lanolin, 28 parts lard, 15 parts mineral oil, 2
parts of dibromo fluorescein and 10 parts of lakes (a mixture of
equal parts of D & C No. 9 and D & C Orange No. 4).
As indicated previously, there can be employed copolymers of
hydroxy lower alkyl acrylates or methacrylates with copolymerizable
monomers which are either hydrophobic, e.g., alkyl acrylates and
methacrylates such as methyl acrylate, ethyl acrylate, butyl
acrylate, 2-ethylhexyl acrylate, octyl acrylate, butyl
methacrylate, octyl methacrylate, methyl methacrylate or
hydrophilic, e.g., lower alkoxy lower alkyl acrylates and
methacrylates such as methoxyethyl acrylate, ethoxyethyl acrylate,
methoxyethyl methacrylate, ethoxyethyl methacrylate, acrylamide,
methacrylamide, acrylic acid, methacrylic acid, crotonic acid,
vinylpyrrolidone, etc. There can also be added hydrophilic polymers
such as polyvinylpyrrolidone and polyvinyl alcohol, e.g., in an
amount of 1 to 50 percent by weight of the polymer made from the
hydroxyalkyl acrylate or methacrylate.
Examples 41-45 illustrate additional mascara preparations.
EXAMPLE 41
In a 1 liter flask there were placed 80 grams of hydroxyethyl
methacrylate, 20 grams of butyl acrylate and 600 grams of ethanol.
T-butyl-peroctoate (0.5 gram) was added and the solution was heated
at 80.degree. C. for 16 hours under an inert atmosphere (nitrogen)
to effect polymerization. The resulting polymer solution was
diluted with an equal volume of water and was extracted three times
with n-hexane. After extraction the polymer was precipitated by
adding excess water to the polymer-water layer. The polymer was
isolated by filtration and dried at 45.degree. C. An 83 percent
yield of polymer having an intrinsic viscosity of 0.38 in methyl
Cellosolve was obtained.
A portion of the polymer was dissolved in a solvent mixture of 50
wt. percent ethanol, 40 wt. percent water and 10 wt. percent
glycerol to provide a solution of 15 wt. percent polymer
concentration.
To the solution, 5 wt. percent (based on polymer) of carbon black
pigment was added and the suspension was ball-milled to provide
good pigment dispersion.
This formulation was applied in the area of the eye and was found
to be non-irritating. Moreover, after drying, it did not run when
wet. It could be removed cleanly by moistening and rubbing.
EXAMPLE 42
To the formulation prepared in example 41 there were added 3 wt.
percent (based on the total formulation) of polyvinylpyrrolidone
having a molecular weight of 1,5000. After milling to dissolve the
polymer, a formulation which applied more smoothly in the area of
the eye and was easier to remove than the formulation of example 41
was obtained.
EXAMPLE 43
To 600 grams of ethanol in a reaction flask there were added 50
grams of 2-hydroxyethyl methacrylate, 45 grams of ethoxyethyl
acrylate and 5 grams of methacrylic acid. 0.15 grams of t-butyl
peroctoate was added and the solution was subjected to
polymerization in accordance with Example 41. The polymer was
isolated from solution by precipitation with n-hexane. After
drying, an 88 percent yield of polymer having an intrinsic
viscosity in methyl Cellosolve of 0.45 was obtained.
This polymer was dissolved at an 18 wt. percent solids level in a
solvent mixture consisting of 45 wt. percent ethanol, 20 wt.
percent diacetin and 35 wt. percent water. Carbon black pigment was
dispersed by ball-milling in the solution at a 5 wt. percent level
to provide a formulation which when applied to the eyelid and
eyelashes was non-streaking with water but easily removed as a
coherent film when wet.
EXAMPLE 44
To the formulation prepared in example 43 there was added 1 wt.
percent of fumed silica. This aided in maintaining pigment
dispersion and improved covering properties of the pigment without
detracting from the easy removal from around the eye and
non-streaking qualities of the formulation.
EXAMPLE 45
A copolymer was prepared as in example 41 from a monomer mixture
consisting of 60 wt. percent hydroxyethyl methacrylate and 40 wt.
percent butyl acrylate. The polymer was formulated with the solvent
mixture and pigment of example 41. The formulation when applied to
the eyelid and eyelashes was soft, flexible and non-irritating and
showed slightly greater water resistance than the formulation of
example 41.
* * * * *