Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
36
. .
The present inventlon relates to certain alkylvinyl-
ether/maleic ester copolymer-based nail coating compositions,
their concentrates, a method for their preparation, and
processes for their use.
Nail-coating compositions (hereafter called "nail
enamels'l) are applied on keratinous nails, e.g., fingernails
and toenails (hooves are also included and hereafter finger-
nails, toenails and hooves will collectively be referred to -
as "nails"), to coat nails with a film, primarily for cosmetic
purposes and in addition, the film provides prot~ction against
chipping and breaking of the nails. The character of, and
requirements for, nail enamels which provide such films
are multifaceted and complex.
Nail enamels preferably should possess certain rheological
characteristics, e.g., thixotropic behaviour, for ease of
application (heavy-bodied but spreading easily and not running
at the edges~, particularly since a brush is generally used
to apply the composition; be non-allergenic; have an acceptable
odor; not "body~up" in the bottle; be compatible with
color imparting ingredients such as soluble dyes, insoluble
pigments, or both; deposit a smooth film which will (a) dry
quickly at ambient temperatures, (b) be flexible to withstand
the flexin~ of the nails; (c) strongly adhere to the surface
of the nail; (d) not shrink; (e~ be long-wearing; (f) be
durable from the standpoint of abrasion resistance (due to
mechanical wear) and freedom from cracking, chipping and
peeling tendencies; (g? not discolor; (h) be tack-free;
;~ (i) be stable with respect to dye-tinting and pigmentation;
(j) be glossy; (k) not deleteriously affect "breathing" of
the nalls; and (1) be removable with ease without adverse
physiological effect to the nail or surrounding tissues.
-2--
:,'. ~ .
3~
Moreover, the e.f fect of components employed in such compo-
sitions is empirical. For instance, an alteration in a
nail enamel formulation to overcome one problem (e.g., obtain
quick-drying) may result in other problems (sacriflce of
smoothness, flexibility and adhesion characteristics).
Nail enamels are composed of several basic ingredients,
viz, (1) a film-former, ~2) a plasticizer, and (3) a solvent
system, with or without (4) a colorant. The most common
film-former is ni-trocellulose (cellulose nitrate), modified
with a suitable resin, e.g., formaldehyde resin, or other
additive to provide sufficient hardness, resistance to chipping, ~'
and to improve adhesion and gloss. The solvent system employed
as the volatile portion of the enamel generally includes (a) one
or more active solvents, (b~ couplers or latent solvents and
(c) diluents. Typical active solvents for nitrocellulose
include, for example, ethyl acetate and n-butyl acetate; i~
typical latent solvents include, for example, alcohols such
as ethanol and butanol; and typical diluents include, for
example, toluene and xylene.
Nitrocellulose is a fire and explosive hazard. Many
localities have ordinances which forbid manipulation of it
within their jurisdictions. The use of solvents with it to
formulate nail enamels increases the fire and explosive hazard.
Thus nitrocellulose can only be formulated into nail enamels
under very restrictive conditions and then only in plants
adapted for that puxpose. Most cosmetic plants are not ad~pted
to handle nitrocellulose as such. As a result, a number of
specialists exlst in the chain of manufacture. One such
specialist manufactures nitrocellulose chips. These chips
are generally composed of nitrocellulose~ a pigment and a
plasticizer. They serve as the source of color in the final
_
336
nall enamel. Another specialist, using these chips, manufac-
tures the nail enamel bulk in many shades. Cosmetic makers
purchase this nail enamel bulk and then bottle, package and
distribute. Considering the inherent lack of stability of
nitrocellulose nail enamel, the cosmetic makers are confronted
with scheduling and inventory contro:l problems ~urther com~
plicated by the many shades oE nail enamel involved. Fre-
quently, complaints arise in the field.
The incorporation of colorants in nitrocellulose-based
nail enamels also presents major problems. These multifaceted
problems are described, for example, ln "~laking and Coloring
Nail Varnishes Made From Chips", Grizzo, Cosmetics and
Toiletries, Vol. 92, pp. ~3-65, April 1977. Pigments,
although they must meet many criteria, are generally used
with nitrocellulose.
The complex "solution and dilution" procedure involved ~ `
in the formulation of nail enamels from nitrocellulose chips
is described on page 65 of the Grizzo article. This procedure
is not only cumbersome and time-consuming but it also fails `
to provide uniformity in the composition of nail enamels.
The necessity of making the chips in the first instance for
later solution and dilution into nail enamels is expensive.
The nitrocellulose in nail enamels normally deteriorates
(chemical breakdown) on aging and results in enamels which
discolor and which exhiblt loss of the characteristic of
drying to a hard film and loss of viscosity. These enamels
are often characterized as having sharp, unpleasant odors ~-
which are disagreeable to the user. Moreover, the removal
of the film deposited by these nail enamels on the nail has
required the use of acetone or ethyl acetate, both of which
~,,1,
are odoriferous, volatile liquids and are generally considered
to be moderately toxic by inhalation and skin absorption.
Accordingly, alternatives to these conventional nitro-
cellulose-based nail enamels have been sought. However, ; -~
despite the long recognized shortcomings of these enamels, ~;
no previous alternative composition has as yet been commer-
cially acceptable so as to supplant them as the primary type
of nail enamel on the market. This is due to the demanding
requirements, described supra, placed on the performance of
10 nail enamels. There are certain minimum criteria which can
delineate "nail enamel characteristics," i.e., the nail
enamel when applied to the nail should dry sufficiently in
about one minute or so to permit an additional coating; form a
liquid coating on the nail which solidifies without flowing;
appear as a nail enamel in about thirty seconds to one
minute with glossiness flow, level and deposit a uniform
smooth, non-lumpy coating which hardens within about five
minutes; and provide a coating exhibiting nail enamel~
lasting quality for at least about two days.
An object of the present invention is to provide a
nail enamel which obviates the use of nitrocellulose as
a film-former; employs a simple solvent system; uses ingre-
dients which are safe and easy to use; is stable with respect ;~
to color, viscosity and film-forming characteristics; does not
exhibit an offensive odor; provides an effective coating of
film on nails; is easily removed from nails; and can be
~ manufactured with facility, even in concentrates which can
; be later diluted with facility, to provide uniform but
`' ~' ' '
.
.::
33~
versatile compositions exhibiting na11 enamel characteristics.
Another object is the provision of such enamel which deposits
a film which is clear when color-imparting ingredients are
absent; can incorporate color-imparting ingredients with
facility; is durable; will "breathe"; will hold its integrity
(not crack or chip); is flexible and relatively soft but tack-
free, tough and very adhesive; and employs a simple, physiologi-
cally acceptable (problem-free) solvent system.
The nail enamel and nail enamel concentrate compositions
of the present invention essentially include a particular
alkylvinylether/maleic anhydride ester~based resin film-former;
and a plasticizer which can be either a hydroxy fatty acid oil,
an alkyl phthalate, an abietyl alcohol or mixtures of these
plasticizers; and solvent. Such compositions can optionally
include modified resins, supplemental plasticizers, colorants
and other conventional cosmetic product adjuvants. The basis
components, except the solvent system, in the compositions
herein are non-volatile materials. Such non~volatile materials
are referred to herein as "solids".
The essential film-forming material of the compositions
of the invention comprlses an alcohol miscible, linear half
ester of an aliphatic, e.gO, alkyl, vinyl ether-maleic anhydride
copolymer. The ester moiety may be alkyl of, e.g., 1 to about 10
or more, preferably lower alkyl of about 2 to 6j carbon atoms,
e.g., ethyl, isopropyl, butyl, amyl and hexyl. The alkyl viny-
lether may be a lower alkyl vinylether, e.g., in which the alkyl
group contains 1 to about 4 carbon atoms, and preferably is methyl
vinylether. Generally, the molecular weight of the copolymer is
at least about 200, e.g., within the range of about 200 to 500,000
e.g., 51 to 500,000 or about 10,000 to 100,000, and preferably
from about 300 to 100,000.
~6--
~;~
3~
Preferred copolymers for use herein are the water
insoluble, normally liquid, monoesters of methyl vinyl-
ether-maleic anhydride copolymers which are available from
the GAF Corporation under the tradename GANTREZ ES monoester ~ ~-
resins. Monoester resins of this type have been characterized
as having the general structural formula:
fCH
- CEI2 CH fH- - fH - - ;~
o= f ~=o
OH R n ~
. `' ''
wherein R is the ester moiety of 1 to about 10 (preferably 2 to
6) carbon atoms and n is selected to provide resins having
molecular weights within the range of from about 300 to
70,000. Such preferred copolymers often have an acid
number (100% solids) of about 245 to 300. Generally, such
; monoester resins are available in a viscous alcoholic, e.g.,
ethanol or isopropanol, solutions of about 50 percent by weight
solids, are water-resistant (e.g., essentially non-neutralized),
and have a specific gravity within the range of about 0.95 to
0.99. Examples of such preferred monoester resins include the
butyl monoester of a me~hylvinylether/maleic anhydride
copolymer having a weight average. molecular weight (Mw) of
about 7850 and a number average molecular weight (Mn) of
about 3150; the ethyl monoester of a methylvinyl ether/maleic
anhydride copolymer having an MW of about 4075 and an Mn of about
1785; and the isopropyl monoester of a methylvinylether/ ~-
.
~ 7 ~ ~
3~i
maleic anhydride copolymer having an ~w of about 11200 and an
Mn of about 4050. (Such molecular weight determinations
are made by gel permeation chromatography.) Combinations
of the monoester resins can be employed as the essential
film-former.
In addition to the above described essential film-
forming resins, the nail enamel compositions of the present
invention can optionally include modifier resins. Modifier-
resins can be incorporated to modify the characteristics
of the essential film-former employed, for instance, to
modify hardness, resistance to chipping, adhesive charac-
teristics, viscosity and the like. Such resin-modifiers
include synthetic resins such as arylsulfonamide-formaldehyde
resins (e.g., Santolite MS-80go or Santolite MHP, products
of Monsanto); alcohol-soluble, hydrolyzed protein (e.g.,
Crotein ASC or Crotein AD-X, products of Croda); hydroxy-
propyl cellulose (e.g., Klucel, a product of Hercules); ~ `
ethyl cellulose (e.g., Ethocel, a product of Dow Chemical);
amino-functional silicones (eOg., DC531 and DC536, products
. ~ .
of Dow Corning) and polyamide resin (e.g., Versamid 940,
a product of General Mills). The resin modifiers are employed
in resin modifying amounts, generally from about 20 to 90,
preferably 30 to 70, weight percent based upon the essential
resin film-former (solids basis~.
A second essential component of the nail enamel and
nail enamel concentrate compositions herein is a plasticizer
selected from the group consisting of alcohol-soluble,
hydroxy fatty acid oils, alkyl phthalates wherein each
alkyl group contains from 1 to about 15 carbon atoms, abietyl
~lcohol and mixtures of such plasticizers.
-8-
;.
3~ ~
The alcohol-soluble fatty oil (e.g., hydroxy fatty acid
oil~ which can serve as the essential plasticizer in the com-
positions herein is a triglyceride of a hydroxy-substituted fatty,
i.e. C12 22' acid. Such an oil is normally liquid at ambient
temperatures and is a non-drying, non-volatile triglyceride.
The preferred hydroxy fatty acid oil is castor oil, the
chief constituent of which is the triglyceride of ricinoleic
(12-hydroxy-9-octadecanoic) acid. Castor oil, in addition
to performing a plasticizing function, also acts as an
emollient and imparts gloss to the film-coatings formed on
the nail substrate by the nail enamel compositions of the
present invention. Castor oil can also serve as a suspending
medium ~or pigments which can optionally be introduced into
the present compositions and in this connection can also serve
as a medium for pigment grinding and dispersion. Furthermore,
castor oil enhances the solubility of o-ther plasticizers such
as alkyl phthalates or abietyl alcohols in the nail enamel
systems of the present invention.
Alkyl phthalates can also serve as the essential -
plasticizer in the nail enamels o~ the present invention.
The alkyl phthalate employed can include, e.g., alkyl aryl ;
; phthalates (e.g., butyl benzyl phthalate), dialkyl phthalates
for instance, wherein each alkyl group contains from 1 to
about 15 carbon atoms including the dimethyl, diethyl,
dlbutyl and dioctyl phthalates. The di-lower alkyl
phthalates are preferred. Dibutyl phthalate and butyl
benzyl phthalate (e.~., Santicizer~160, a product of Mon-
santo) are especially preferred plasticizers.
Abietyl alcohols can also serve as the essential plas-
ticizer in the compositions herein. Abietyl alcohols are
derivatives of abietic acid which has the empirical formula
_g_
3~
C19H29COOH. Such a material ineludes a phenanthrene ring
system in its structure and is derived from rosin. Abietyl
alcohols are commercially available under -the tradename
Abitol from Hercules. Abitol~is a mixture of tetra-, di-
and dehydro abietyl alcohols.
Mixtures of hydroxy fatty acid oils,alkyl phthalates and
abietyl alcohols can also serve as the essential plasticizer
in the nail enamels herein and, in fact, such mixtures con-
stitute the preferred essential plasticizer component.
Mixtures of castor oil and butyl benzyl phthalate are especially
preferred. The essential plasticizers employed herein
must, of course, be present in plasticizing amounts.
In addition to the essential hydroxy fatty acid oil,
alkyl phthalate, abietyl alcohol or mixed essential plas-
ticizers, the nail enamel and nail enamel concentrate com-
positions herein can optionally include a variety of
supplemental plastieizers which must, of course, be compatible
with the film-forming resin. Optional supplemental
plasticizers include non-volatile organic liquids and low- ;
melting (melting point below 1~0C) organic solids such
as polyols (e.g., polyethylene glycol and its derivatives);
polysiloxanes (alcohol-soluble, silicone oils, e.g.,
alkyl aryl polysiloxanes, e.g., methyl phenyl polysiloxane,
also known as phenyl dimethicone); saturated and unsaturated
mono- and dicarboxylic aeids, esters and fatty alcohols
having at least about 10, perferably about 12 to 24,
carbon atoms (e.g., stearic acid, oleic acid, lauric acid,
ricinoleic acid, linoleic acid, vegetable oils such as
almond, corn, cottonseed and olive oils, Citroflex A2,
cetyl alcohol, myristyl alcohol and the like); and
--10--
3~ ~
lanolin and lanolin derivatives (e.g., acetylated, ethoxylated
compounds). Citroflex A2 is acetyl triethyl citrate and is a
product of Chas. Pfizer & co.
Silicone oils are the pre~erred supplemental plasticizer
in that they improve the brushing characteristics (flow and
leveling~ of the nail enamel and enhance the glossiness o~ the
film deposited on the nail. Combinations of supplemental
plasticizers can also be advantageously employed.
The third essential component of the nail enamel and na
enamel concentrate compositions herein is a solvent. The
solvent system employed is one that is physiologically acceptable
and nail enamel compatible (e.g., is solvent for the resin film
formers, and essential and supplemental plastici~ers while not
; deleteriously affecting the purpose and characteristics of nail
enamels)~ It can advantageous]y be a simple solvent, expediently
a lower alkanol, e.g., ethanol, and/or isopropanol. Combinations
of solvents can also be used. Solvent can be provlded in part
- by the solution in which commercial resin film-former is provided.
Other operable solvents include ethyl acetate, butyl acetate,
toluene, xylene and acetone.
The nail enamel compositions of the present invention
exhibit nail enamel characteristics which include a brushing
viscosity, e.g., a heavy-bodied brushing viscosity which picks
up a substantial amount of the nail enamel without dripping and
yet flows freely when applied to provide a smooth coating on the
nails. Viscosity of the nail enamel compositions of the present
invention generally ranges from about 20 centipoises (cps.) to
~ 1500 centipoises (cps.) or more, advantageously from about 50 cps.
-~ to 1400 cps., and preferably from about 200 cps. to 500 cps.
Such viscosity values are established at 70-72F using a Model
~VT Brookfield Viscosimeter. (No. 2 spindle at 10 rpm)
--11--
`'t~
.
36
The nail enamel characteristics exhibited by the com-
positions herein also include a solids content, provided by
the resin film-former (which includes the total of essential
resin film-former present and, also when present, modifier~
resin) and the essential and supplemental plasticizer(s).
Such a solids content should be sufficient to impart nail
enamel constitution but insuf~icient to prevent brush-
application of the enamel on nails. These solid, i.e.,
non-volatile, contents will generally be in the range of
about 10 to 45, preferably from about 12 to 35 or 40, weight
percent based upon the total of the resin film-former(s),
plasticizer(s) and solvent(s) present. The solids content
is basically provided by the resin film-former(s) and the
balance by plasticizer(s) which are incorporated in nail
enamel-plasticizing amounts, e.gO, to enhance flexibility
or durability of the film deposited by the nail enamel. The
part of the solids content provided by film-former i5
generally from about 40 to 96, preferably from about 60 to
95, and that provided by the plasticizer(s) is generally
from about 1 to 40, preferably from 2 to 35, weight percent
based upon the solids content provided by resin film-former(s),
and plasticizer(s) on a solven-t-free (dry) basis. The weight
- ratio of resin film-formers (solvent-free basis) to total
plasticiæer is preferably about 2:1. When a hydroxy fatty
acid oil îs present in combination with another essential
plasticizer, the hydroxy fatty acid oil generally constitutes
from about 0.1 to 25, preferably from about 1 to 20, weight
percent of the solids content of the nail enamel. The
balance of the nail enamel constitutes the other optional ~;~
non-volatile materials and the solvent(s).
` ::
-12- ~
' ' ' ~ '
,36
The solvent(s) is employed in nail enamel-solvent amounts,
e.g., amounts sufficient to solubilize resin film-former(s),
essential and supplemental plasticizer(s), and
other ingredients present while not deleteriously a~fecting
the viscosi-ty of the nail enamel. These amounts generally
- range from about 55 to 90, usually from about 65 to 8~
weigh-t percent, based upon resin film former(s), essential
and supplemental plasticizer(s) and solvent.
~` The nail enamels of this invention may also contain
conventional ad~uvants such as diluents (hydrocarbons, e.g.,
toluene and xylene); colorants including dyes and pigments
including iron oxides, organic and nacreous pigments; fillers;
stabilizers; thickeners; leveling agents; conditioners;
perfumes; antiseptics; bacteriostats and the like. These
adjuvants, when employed, are provided in minor amounts
sufficient to impart the intended qualities to, but not
adverse to, the desired properties of the nail enamels~
The colorant is generally employed in amounts of about
0.01 to 5, usually about 0.5 to 2, weight percent based upon
the nail enamel composition. One of the advantages provided
by the present invention resides in the provision of nail
: ~ i
enamels which can utilize either dyes or pigment colorants.
Suitable colorants include pigments such as, for example, iron
oxide, xanthene red organic, titanium dioxide, and ferric
;~ ferrocyanide in a blue nacreous pigment; and alcohol-soluble
- dyes such as, for example, triphenylmethane blue dye, xanthene
-
red dye, and ~luoran yellow dye.
In a particular advantageous aspect of the present in-
~ vention, nail enamel concentrates can be formed which can be
-~ 30 later diluted with facility by formulators to provide the
ultimate nail enamel ~or use by consumers. The concentrates
~-
.
3~
advantageously contain the plasticizer(s), all or partial
amounts of the film-forming resinls) and partial amounts of
solvent. This is particularly significant when pigment
colorants are desired in the nail enamels since the pigments
can be pre-dispersed in the hydroxy fatty acid oil. ~he
employment of the relatively simple solvent system in the
nail enamels of this invention enables the preparation of
concentratesr e.g. r as low as about 8 or 10 percent, e.g.,
from about 10 to 45 percent concentrate, which are uniform,
clear and viscous concentrate solutions. Such numerical
"percent concentrate" values refer to ~he percentage of
the complete nail enamel composition which the concentrate
components comprise. The nail enamel concentrates generally
contain partial amounts of solvent which comprise from
- about 15 to 50 weight percent of the conc~ntrate, and when
containing partial amounts of resin film-former, generally
the film-former is present in the concentrate in amounts
from about 15 to 50 weight percent, based on the concentrate.
The nail enamels of the present invention are advan-
tageously prepared by a method which comprises mixing, under
ambient conditions, the essential and supplemental
plasticizers with resin film-former to provide a homogenous
mixture, and diluting the mixture with mixture-dissolving
amounts of alcohol solvent to provide a nail enamel. When
colorants are incorporated into the enamel, pigment-colorants
are advantageously pre-dispersed in the hydroxy fatty acid oil,
(if present in sufficient amounts, otherwise in hydroxy
fatty acid oil and other essential or supplemental plasti-
~izer) and dyes are advantageously pre-dissolved in the
alcohol solvent before, respectively, the pigment dispersion
and alcohol are contacted with resin film-former. The
pigments are advantageously dispersed in the hydroxy fatty
acid oil, e.g., castor oil, which is stable and not volatile
3~ `
under roller mill conditions, using a roller mill,
usually water-cooled, at pressures up to about 4,000
p.s.i. to obtain a substantially uniform dispersion. `
The concentrates can be prepared by combining partial
amounts of one or more of the components, preferably the
solvent or resin film-former which are to form the ultimate ~-
nail enamel, with the essential and supplemental plastici-
zers. For instance, amounts of solvent or resin and solvent
can be advantageously withheld for later dilution. The
pigments can be ground in 25~ and higher concentrations in
the hydroxy fatty acid oil, e.g., castor oil, or other
plasticizer to provide a dispersion and the resulting
dispersion can be used in making concentrates containing
resin film-former and plasticizer with dispersed pigment
which on further dilution, for instance with solvent, or
solvent and resin, results in the final nail enamel.
The process of using the nail enamels to cosmetically
improve nails comprises applying nail enamel to a nail
substrate in nail-coating amounts to coat the nail, and
; 20 drying applied nail enamel to form a film-coating on the ;~
nail. The enamel is conveniently applied, e.g., by brushing
it, on the portion of the nail intended to be coated. The
coating dries rapidly on the substrate to form an adherent,
tough, glossy film which is water-resistant. When desired,
the coating is easily removed by applying an alcoholic or
alkaline solution to soften the coating and the softened
~; coating can be conveniently wiped off.
- The invention is further illustrated by the following
- illustrative examples, which are not in limitation of the
invention. All parts and percentages are by weight unless
otherwise indicated.
-15-
.
3~
,:
Example I
The following nail enamel is prepared by mixing the ~:
castor oil and resin film-Eormer and dissolving the mixture
with the solvent to produce a uniform, viscous solution
having a brushing viscosity (92 cps.) and a total solids
content of 23 weight percent:
Component Percent
*GANTREZ ~S-425 (resin film-former) 40
Castor Oil (hydroxy fatty acid oil
plasticizer) 3
**Alcohol SD 40 (solvent) 57
100%
*GANTREZ ES-425 is a 50 percent ethanol solution of
the monobutylester of methyl vinylether-maleic anhydride
copolymer available from GAF Corporation.
**A 95 percent ethyl alcohol solution.
On application to the fingernail, a smooth glossy coat
~ was obtained. On the first application, the enamel dried
l; sufficiently in about a minute to permit a second application.
On the secona application, the enamel showed very little
tack in two minutes and was tack-free in three minutes. The
~; enamel lasted over two days and retained good gloss.
Example II
The following horse hoof enamel is prepared by grinding
the iron oxide pigment together with the castor oil in a
mortar and the mix is added to a solution composed of the
resin film-former and solvent~
Component Percent
GANTREZ ES-425 Resin 50
Castor Oil 3
Alcohol SD40 45 ;
Iron Oxide Pigment (black)2
100%
-16-
~:
36
The enamal is applied to a hoof or nail to provide a
good film with excellent sheen and color coverage. The
pigment which separates on standing is readily redispersed
by shaking prior to use.
- Example III
The following horse hoof enamel is prepared:
Component Percent
GANTR~Z ES-425 Resin 30
Castor Oil 1
Ethyl Alcohol SD40 67.95
*FD&C Blue #1 0.15
**FD&C Red ~3 0.30
***D&C Yellow y7 0.60
100. 00%
*An alcohol-soluble tripenylmethane blue dye (Chem.
Abstracts Service Number ("CAS"): 2650-18-2)~
**An alcohol-soluble xanthene red dye (CAS: 563-63-8). `
***An alcohol-soluble fluoran yellow dye (CAS: 518-45-6).
A good black film with blue violet overtones and good
gloss was obtained. It is best with two applicationsD ;~
; The colors were added to the alcohol und~r ambient
conditions and dissolved by stirring. The solution may
be warmed to 40C to facilitate solution. The solution
was then filtered and added to a mix of the GANTREZ ES-425
and the castor oil. The mix was stirred until the solution
was uniform.
Example IV
.
The procedure of Example I is essentially followed
to prepare the following nail enamel:
-17
.
3~ ~
Component Percent ,
GANTREZ ES Resin 36.0
*Castor Oil 1.6
*D&C Red #19 Aluminum Lake Mix 0.4
**Klucel M 0.6
**Ethanol 30 9
Toluene 30 5 ;
100~0%
*An organic xanthene red pigment (RD No. 977054~33-3)
(Kohnstamm K-7040), the colorant was ground in castor -~
oil at a 25 percent concentration.
**Solubilized in ethanol to provide a two percent solution.
:
` The castor oil-pigment mix was added to the Gantrez and ~`
mixed thoroughly. The Klucel-alcohol solution was mixed
in -thoroughly and then toluene was stirred in. A good film ~ ~
was produced. The color--a pretty pink, was somewhat trans- ~ ~;
parent on one application~ The enamel had a good brushing
~iscosity (1360 cps.).
.; :
This example shows that toluene is compatible in the
nail enamel and can be used to modify (cut) the viscosity
of the enamel. Klucel can be used to increase the viscosity
of the enamel without significantly increasing the solids
content, the increase in viscosity being desired to stabilize
the dispersion of pigment in the enamel.
Example V
~ The procedure of Example I is essentially followed
; to prepare the following nail enamel: -
Component Percent
Gantrez ES-425 ~esin 30.0
Castor Oil 1.0
; Alcohol SD40 65.0
Diethyl Phthalate 4.0
100. 0%
-18-
3~6i
This exemplifies a combination of castor oil as the
hydroxy fatty acid oil plasticizer, and diethyl phthalate
as a supplemental plasticizer. Such a composition has a
viscosity of about 60 cps.
Example VI
The procedure of Example I is essentlally followed,
except the Silicone 556 and dimethyl phthalate are adde~
in turn after the castor oil, to prepare the following
nail enamel:
Component Percent
Gantrez ES-425 Resin 36
Castor Oil
*Silicone 556 2
- Dimethyl Phthalate 2
~ Alcohol SD40 59
:. ~ 100~
*Silicone 556 is an alcohol-soluble, methylphenyl
polysiloxane, a product of Dow Corning (It has also
been designated phenyl dimethicone CTFA). It has
a viscosity at 25C of 22.5 centistokes.
, ..
The enamel, when applied to a fingernail, provided
; a very glossy finish. The silicone, in addition to
plasticizing, also enhances the brushing characteristics
(flow and leveling) of the nail enamel. The nail enamel
composition has a viscosity of about 72 cps.
Example VII
The procedure of Example VI is essentially followed
to prepare the following nail enamel:
~'
~ .
:` :
.'~
36
Component Percent
Gantrez ES-425 Resin 36.0
Castor Oil 2.0
*Santolite MS-80% Resin 12.0
Alcohol SD40 46.0
Sil7cone 556 2.0
Diethyl Phthalate 2 0
100. 0% ,"
*Santolite MS~80% is an 80 percent sulfonamide-
formaldehyde resin in butyl acetate solution, a
product of Monsanto Industrial Chemicals.
~;
Good clear films were deposited upon application of
this enamel to nails.
A white taffy-like mix resulted when the Gantrez and
Santolite were combined. The final addition of the alcohol
resulted in a clear bright solution.
A coat of the enamel on fingernails lasted almost
five days. ~;
Examples VIII to X
These examples, A Group Examples, show concentrate
preparations in the 38 to 44 weight percent range, e.g.,
41 to 43 percent, which are diluted with ethanol to produce
the corresponding final nail enamels set forth in B Group
Examples:
A Group
Componen-t Parts
~IIIA IXA XA
Gantrez ES-425 Resin 36.0 36.0 36.0
` *Castor Oil 1.0 2.0 1.75
Silicone 556 2.0 2.0 2.0
Diethyl Phthalate 2.0 2.0 2.0
**4500 Chromalite Light Blue - 1.0 - ;
*D&C Red #19 (Kohnstamm K-7040) - - 0.25
~ a336
*In Example XA, two parts of a 25% color mix of D&C
Red ~19 ground in castor oil was used.
**A blue nacreous pearlescent pigment using fQrric
ferrocyanide, a product of Mallinckrodt, Inc.
` Concentrate VIIIA on dilution to 100 parts by the
addition of Alcohol SD 40 formed a clear polish, the
composition of which is set forth below in B Group~
Concentrates IXA and XA formed colored nail polishes on
dilution to 100 parts using Alcohol SD40 and stirring,
and the compositions of these are also set forth in
B Group below.
B Group
;~ Component Parts
VIIIB IXB XB
Gan-trez ES-425 Resin 36.0 36.0 36.0
~ ,: . :.
*Castor Oil 1.0 2.0 1.75
; Silicone 556 2.0 2.0 2.0
Diethyl Phthalate 2.0 2.0 2.0
4500 Chromalite Light Blue - 1.0
*D&C Red #19 (Kohnstamm K-7040) - - 0.25
.. .
-Alcohol SD40 59.0 57.0 58.0
~ _
100.0 100.0 100.0
*In XB, 2.0 parts of 25% color mix of D&C Red #19
in castor oil was used.
~xamples XI to XIII
,
These examples show 20 percent concentrates, which
are diluted with resin and solvent to produce the corres-
ponding final nail compositions.
~-
-21-
'':
Component Parts
XI XII XIII ;~
Gantrez ES-425 Resin 13.0 14.0 14.0
Castor Oil Z.0 2.0 3.0
Silicone 556 2.0 2.0 2.0
Diethyl Phthalate 2.0 - -
4500 Chromalite Light Blue 1~0 2.0 -
D & C Red #19 (Kohnstamm K-7040) - - 1.0
Nail enamels XI through XIII are 20% concentrates. All
formed uniform heavy-bodied products (just barely flowing).
By diluting to 100 parts by the addition of 22 parts Gantrez
ES-425 and 58 parts Alcohol SD40, final nail polishes were
formed.
The additional Gantrez in the concentrate solubilized
all the components (except the colors which were held in
stable suspension).
Examples XIV to XIX
These examples show nail enamels using combinations
of resin film-formers.
Component Percent
XIV XV XVI XVII XVIII XIX
: :
*Gantrez ES-225 Resin 18.0 36.0
Gantrez ES-425 Resin 18.0 - - - 18.0
**Gantrez ES-435 Resin - - 36.036.018.0 36.0
Castor Oil 2.0 2.0 20 0 2.0 2~0 2.0
Silicone 556 2.0 2.0 - - 2.0 2.0
Diethyl Phthalate 2.0 2.0 - - 2.0 2.0
Isopropyl Alcohol - - 62.0
Alcohol SD40 58.0 58.0 - 62.0 58.0 58.0 ~-
, ;. :
-~ 30 100.0% 100.~% 100.0% 100.0% 100.0% 100.0%
-22-
.
3~
*Is a 50 weight percent ethanol solution of the mono- `
ethyl ester of methyl vinylether maleic anhydride co-
polymer available from GAF.
**Is a 50 weight percent isopropanol solution of the
monobutyl ester of methyl vinylether maleic anhydride
copolymer available from GAF.
Nail enamels XIV to XIX produced brilliant clear nail
polishes that deposited good glossy films; XV had least gloss;
XVI had best gloss; XIV had intermediate gloss. Nail polish
produced by XVII lasted at least 4 days with good gloss; after
4 days, fine crazin~ was observed under 10X magnification
which was not visible to eye, and no chipping was observed.
The sheen of the polish produced by nail enamel XV disappeared
after the second day of wear. Nail polishes produced by
nail enamels XIV and XVI lasted about 4 days. Nail polishes
produced by nail enamels XVIII and XIX both lasted 3 days with
fine cracking seen.
Examples XX and XXI
These examples, A Group Examples, present particularly
advantageous embodiments of the present invention involving
the preparation of unique concentrates which are as low as
about 10 percent concentrate.
A Group
Component Parts
XXAXXIA
Gantrez ES-435 5.05.0
Castor Oil 3O03.0
D&C Red #7 (Rohnstamm K-7044) - 1.0
Chromalite Magenta
(Mallinckrodt) 45051.25
Isopropyl Alcohol 1.01.0
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336
In connection with XXA, the isopropyl alcohol was
stirred into the Gantrez ES-435 followed by the castor oil
and the pigment. A heavy-bodied concentrate (carmine color)
resulted.
In connection with XXIA, the procedure of XXA was
followed except that a mixture of D&C Red #7 ground in the
castor oil was added to the Gantrez ES-435. A smooth heavy-
bodied pink-colored concentrate resulted.
Component Parts
XXB XXIB
Gantrez ES-435 38.0 38.0
Castor Oil 3.0 3.0
Dibutyl Phthalate - 2.0
.
Alcohol SD40 56.75 55.0
Isopropyl Alcohol 1.0 1.0
; D&C Red #7 (Kohnstamm K-7044) - 1.0
Chromalite Magenta 1.25
(Mallinckrodt) 4505
100.0 100.0
Nail enamel XXB was made by diluting 10.25 parts of
Concentrate XXA with 5.0 parts of ethyl alcohol while stirring.
Then 33.0 parts of Gantrez ES-435 were added while stirring.
The balance of the ethyl alcohol~ 51.75 parts was added while
stlrrlng.
Nail enamel XXIB was made by diluting 10.0 parts of
Concentrate XXIA with 5.0 parts of ethyl alcohol while stirring.
Then 33.0 parts of Gantrez ES-435 were added while stirring
followed by addition of 2.0 parts of dibutyl phthalate with
-24-
stirring. The balance of the ethyl alcohol, 50.0 parts, was
added while stirring.
These examples present particularly advantageous
concentrates containin~ ground and dispersed pi~ment, having
flexibility, and whicn can be easily processed into final
nail enamels. The use of isopropanol is advantageous in that
a concentrate as low a~ about 10 percent can be prepared.
Although the isopropyl ester of the resin is employed, there
is no restriction on use of other resin film-formers of the
present invention in making the final nail enamel since the
isopropyl ester is used in the concentrate in small amounts
which are compa~ible with larger amounts of other resins.
These concentrates advantageously serve the purpose of
introducing pigments into the final nail enamel which have
been properly ground and dispersed in the concentrate.
Examples XXII and XXIII
The following nail enamel compositions are formulated
to illustrate compositions employing relatively high solids
contents.
Component Concentration (Wt
XXIIXXIII
Gantrez ES-435 (resin~ 40.0 50.0
Castor Oil (plasticizer) 5.0 5.0
*Santicizer 160 (plasticizer) 5.0 5.0
Silicone 556 (plasticizer) 2,0 2.0
SD-40-A Al¢~hol(solvent) ~8.0 38.0
(Anhydrous)
100.0%100.0
*Butyl benzyl phthalate available commercially from
Monsanto.
Notwithstanding the relatively high solids contents,
both Rxamples XXII and XXIII exhibit acceptable brushing
viscosities (XXII = 240 cps~ and XXIII = 320 cps.). These
nail enamel compositions employing a mixed ethanol/isopropanol
solvent system also exhibited acceptahle drying time charac-
teristics once applied to the nail substrates.
Compositions of subtantially similar nail enamel
characteristics are realized when in 1he Example XXII and XXIII `~
compositions the Santicizer 160 plasticizer is
replaced with an equivalent amount of Abitol , a mixture of
abietyl alcohols commercially available from ~ercules~
Example XXIV
The following nail enamel is prepared by mixing the
butyl benzyl phthalate and resin film former and dissolving
the mixture with the solvent to produce a uniform, viscous
solution having a brushing viscosity and a total solids
content of 22 weight percent~
Component Percent
*GANTREZ ES-425 (r-sin film-former) 36
Butyl Benzyl Phthalate (plasticizer) 4
Isopropanol (solvent) 60
1009
*A 50 weight percent isopropanol solution of the
monobutyl ester of methylvinylether/maleic anhydride
copolymer available from GAF Corporation.
.:
The nail enamel is applied to fingernails to provide
a smooth, clear, glossy coat on the nails.
A nail enamel composition of substantially similar
characteristics is realized if, in the Example XXIV composition,
the butyl benzyl phthalate plasticizer is replaced with an
equivalent amount of Abitol~, a commercially-available
-26-
133~
.
mix-ture of tetra-, di- and dehydro-abietyl alcohol.s.
The nail enamel coating formed on the nail by the
Example XXIV composition is removed by applying isopropanol
to the coating and 3 minutes thereafter wiping the softened
coating from the nail.
Example XXV
The following nail enamel is prepared by mixing the
dimethyl phthalate and resin film-former and dissolving the
mixture with the solvent to produce a uniform, viscous
10solution having a brushing viscosity and a total solids
content of 22 weight percent:
_mponent Percen
*GANTREZ~ ES-425 (resin film-former) 36
Dime~hyl Phthalate 4
**Alcohol SD40 (solvent) 60
100
*GANTREZ ES-425 is a 50 percent ethanol solution of
the monobutylester of methyl vinylether-maleic
anhydride copolymer available from General Aniline &
Film Corporation ("GAF").
**A 95 percent ethyl alcohol solution.
The nail enamel is applied to a fingernail to provide `
a smooth, clear, glossy coat on the nail.
Examples XXVI to XXVIII ~.
The procedure of Example XXV is essentially followed to
prepare the following nail enamel.:
_omponent Percent
XXVI XXVII XXVIII
GANTREZ ES-425 Resin 36 36 36
Dibutyl Phthalate 4 4 - ~.
Dioctyl Phthalate - - 4
Alcohol SD40 60 - -
Isopropyl Alcohol - 60 60
100 %10~ %100 %
-27-
3 Ei
Example XXIX
This example, A Part E~ample, shows a concentrate
preparation in the 38 to 44 weight percent range, which
is diluted with ethanol to produce the corresponding final
nail enamel set forth in B Part Example:
A Part
Component Parts
XXIXA -
Gantrez ES-425 Resin 36.0
Dimethyl P.hthalate 4.0
Nail polish concentrate XXIXA was clear. ~;
B Part
_omponent Parts
XXIXB
Gantrez ES-425 Resin 36.0 ~ ~
Dimethyl Phthalate 4.0 ~ :
Alcohol SD40 60.0 :
100.O
~, . ,
'' :' :'
,.' ' ~ :'
. ~ -: . .:
' ' ` '
.;', ~'
-28-
