U.S. patent application number 16/007177 was filed with the patent office on 2018-12-13 for nail color coating system.
This patent application is currently assigned to Elementis Specialties, Inc.. The applicant listed for this patent is Elementis Specialties, Inc.. Invention is credited to Yanhui CHEN, Prashant DESHMUKH, Maurice GRAY, Rajni GUPTA, James A. HECK, Wayne HOYTE, Wouter IJDO.
Application Number | 20180353400 16/007177 |
Document ID | / |
Family ID | 64562140 |
Filed Date | 2018-12-13 |
United States Patent
Application |
20180353400 |
Kind Code |
A1 |
IJDO; Wouter ; et
al. |
December 13, 2018 |
NAIL COLOR COATING SYSTEM
Abstract
A nail polish composition containing a crosslinkable coating
composition. The composition comprises ingredient A that has at
least two protons that can be activated to form a Michael carbanion
donor; ingredient B that functions as a Michael acceptor having at
least two ethylenically unsaturated functionalities each activated
by an electron-withdrawing group; and a carbonate initiator of
Formula (1) ##STR00001## wherein R.sub.7 is selected from hydrogen,
a linear or branched substituted or unsubstituted alkyl group
having 1 to 22 carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon
atoms; and A.sup.n+ is a cationic species or polymer and n is an
integer equal or greater than 1 with the proviso that A.sup.n+ is
not an acidic hydrogen; at least one colorant independently
selected from the group consisting of (i) a dye; (ii) an inorganic
pigment; or an (iii) a lake; and optionally further comprising
ammonium carbamate
(H.sub.2NR.sub.8R.sub.9+--OC.dbd.ONR.sub.8R.sub.9), wherein R.sub.8
R.sub.9 are each independently selected from hydrogen, a linear or
branched substituted or unsubstituted alkyl group having 1 to 22
carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms.
Inventors: |
IJDO; Wouter; (Yardley,
PA) ; CHEN; Yanhui; (Princeton, NJ) ;
DESHMUKH; Prashant; (Plainsboro, NJ) ; GUPTA;
Rajni; (Princeton, NJ) ; HECK; James A.;
(Robbinsville, NJ) ; HOYTE; Wayne; (Parlin,
NJ) ; GRAY; Maurice; (Saint Albans, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Elementis Specialties, Inc. |
East Windsor |
NJ |
US |
|
|
Assignee: |
Elementis Specialties, Inc.
East Windsor
NJ
|
Family ID: |
64562140 |
Appl. No.: |
16/007177 |
Filed: |
June 13, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62518791 |
Jun 13, 2017 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 63/21 20130101;
C09D 7/63 20180101; C08J 3/24 20130101; C08K 5/109 20130101; C08J
2367/02 20130101; A61K 8/494 20130101; A61K 2800/95 20130101; C09D
4/06 20130101; A61K 8/44 20130101; A61K 8/4986 20130101; A61K 8/731
20130101; A61K 8/416 20130101; C09D 7/20 20180101; A61K 8/33
20130101; A61K 8/85 20130101; C08K 5/17 20130101; A61Q 3/02
20130101; C09D 7/45 20180101; C09D 167/02 20130101; C09D 4/06
20130101; C08F 265/06 20130101 |
International
Class: |
A61K 8/33 20060101
A61K008/33; A61Q 3/02 20060101 A61Q003/02; A61K 8/44 20060101
A61K008/44; A61K 8/41 20060101 A61K008/41; A61K 8/73 20060101
A61K008/73; A61K 8/85 20060101 A61K008/85; A61K 8/49 20060101
A61K008/49 |
Claims
1. A nail polish composition containing a crosslinkable coating
composition comprising: ingredient A that has at least two protons
that can be activated to form a Michael carbanion donor; ingredient
B that functions as a Michael acceptor having at least two
ethylenically unsaturated functionalities each activated by an
electron-withdrawing group; and a carbonate initiator of Formula
(1) ##STR00005## wherein R.sub.7 is selected from hydrogen, a
linear or branched substituted or unsubstituted alkyl group having
1 to 22 carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms; and
A.sup.n+ is a cationic species or polymer and n is an integer equal
or greater than 1 with the proviso that A.sup.n+ is not an acidic
hydrogen; at least one colorant independently selected from the
group consisting of (i) a dye; (ii) an inorganic pigment; or an
(iii) a lake; and optionally further comprising ammonium carbamate
(H.sub.2NR.sub.8R.sub.9+--OC.dbd.ONR.sub.8R.sub.9), wherein R.sub.8
R.sub.9 are each independently selected from hydrogen, a linear or
branched substituted or unsubstituted alkyl group having 1 to 22
carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms.
2. The nail polish composition according to claim 1, wherein the
dye is selected from the group consisting of D&C Red 21,
D&C Red No. 22, D&C Red No. 28, D&C Red No. 30, D&C
Red No. 40, D&C Red No. 33, D&C Black No. 2, D&C Yellow
No. 5, D&C Green No. 5, Annatto, Caramel and combinations
thereof.
3. The nail polish composition according to claim 1, wherein the
inorganic pigment is selected from the group consisting of red iron
oxide; yellow iron oxide; titanium dioxide; brown iron oxide;
chromium oxide green; iron blue (ferric ferrocyanide blue);
ultramarine blue; ultramarine violet; ultramarine pink; black iron
oxide; bismuth oxychloride; aluminum powder; manganese violet;
mica; bronze powder; copper powder; guanine and combinations
thereof.
4. The nail polish composition according to claim 1, wherein the
lake is a D&C lake.
5. The nail polish composition according to claim 1, wherein
ingredient A is selected from the group consisting of compounds,
oligomers or polymers.
6. The nail polish composition according to claim 5, wherein the
ingredient A is independently selected from a malonate group
containing compound, a malonate group containing oligomer, a
malonate group containing polymer, an acetoacetate group containing
compound, an acetoacetate group containing oligomer, an
acetoacetate group containing polymer or combinations thereof.
7. The nail polish composition according to claim 6, wherein the
malonate group containing compound, malonate group containing
oligomer, malonate group containing polymer, an acetoacetate group
containing compound, acetoacetate group containing oligomer, or
acetoacetate group containing polymer are each selected from the
group consisting of: polyurethanes, polyesters, polyacrylates,
epoxy polymers, polyamides, polyesteramides or polyvinyl polymers,
wherein such compounds, oligomers or polymers have a malonate group
or acetoacetate group located in a main chain of such compound or
oligomer or polymer or a side chain of such compound or oligomer or
polymer.
8. The nail polish composition according to claim 7, wherein
ingredient B is selected from the group consisting of acrylates,
fumarates, maleates and combinations thereof.
9. The nail polish composition according to claim 8, wherein the
acrylate is independently selected from the group consisting of
hexanediol diacrylate, trimethylol propane triacrylate,
pentaerythritol triacrylate, di-trimethylolpropane tetraacrylate,
bis(2-hydroxyethyl acrylate), trimethylhexyl dicarbamate,
bis(2-hydroxyethyl acrylate) 1,3,3-trimethylcyclohexyl dicarbamate,
bis(2-hydroxylethyl acrylate) methylene dicyclohexyl dicarbamate
and combinations thereof.
10. The nail polish composition according to claim 9, wherein
ingredient B is independently selected from the group consisting of
polyesters, polyurethanes, polyethers and/or alkyd resins each
containing at least two pendant ethylenically unsaturated groups
each activated by an electron-withdrawing group.
11. The nail polish composition according to claim 10, wherein
ingredient B is independently selected from the group consisting of
polyesters, polyurethanes, polyethers and/or alkyd resins each
containing at least one pendant acryloyl functional group.
12. The nail polish composition according to claim 1, further
comprising an ingredient D having one or more reactive protons that
are more acidic than the two protons of ingredient A, with respect
to pKa.
13. The nail polish composition according to claim 12, wherein the
one or more reactive protons of ingredient D are less acidic than
the ammonium cation of the optional ammonium carbamate, with
respect to pKa.
14. The nail polish composition according to claim 1, further
comprising water concentration selected from the group consisting
of less than 10 wt. %, less than 5 wt. %; less than 1 wt. %; less
than 0.1 wt. %; less than 0.01 wt. % water.
15. The nail polish composition coating composition according to
claim 1, further comprising an organic solvent.
16. The nail polish composition according to claim 15, wherein the
organic solvent is independently selected from the group consisting
of an alcohol, ester, ether, glycol ether, ketone, aromatic and
combinations thereof.
17. The nail polish composition according to claim 16, wherein the
alcohol is independently selected from the group consisting of
methanol, ethanol, iso-propanol, butanol, iso-butanol, t-butanol
and combinations thereof.
18. The nail polish composition according to claim 1, wherein
A.sup.n+ is a monovalent quaternary ammonium compound of Formula
(2) ##STR00006## wherein R.sub.3, R.sub.4 and R.sub.5 are
independently selected from linear or branched alkyl chains having
from 1 to 22 carbon atoms; or 1 to 8 carbon atoms; or 1 to 4 carbon
atoms and combinations thereof and wherein R.sub.6 is independently
selected from the group consisting of: methyl, an alkyl group
having from 2 to 6 carbon atoms or a benzyl group.
19. The nail polish composition according to claim 1, wherein the
dormant carbonate initiator initiates Michael Addition to achieve
crossing linking when the crosslinkable coating composition is
applied to a surface.
20. The nail polish composition according to claim 1, wherein
ingredient A, ingredient B and the carbonate initiator are
contained in a container having two or more chambers, which are
separated from one another.
21. The nail polish composition according to claim 20, wherein
ingredient A and ingredient B are contained in separate chambers to
inhibit any reaction.
22. The nail polish composition according to claim 20, wherein the
carbonate initiator is contained in the chamber having ingredient
A, and optionally containing CO.sub.2 and/or ammonium
carbamate.
23. The nail polish composition according to claim 20, wherein
ingredient A and ingredient B are contained in the same chamber and
the carbonate initiator is contained in a separate chamber to
inhibit any reaction and said separate chamber optionally
containing CO.sub.2 and/or ammonium carbamate.
24. The nail polish composition according to claim 1 wherein
ingredient A and ingredient B and carbonate initiator are contained
in a container having a single chamber, wherein the container
optionally (i) contains CO.sub.2 and/or ammonium carbamate.
25. The nail polish composition according to claim 20, further
comprising at least one solvent selected from the group consisting
of acetone, ethyl acetate, butyl acetate, isopropyl alcohol,
ethanol, methyl ethyl ketone, and combinations thereof.
26. The nail polish composition according to claim 1, further
comprising a rheological additive to modify rheology.
27. The nail polish composition according to claim 1, further
comprising a wetting agent.
28. The nail polish composition according to claim 1, further
comprising an adhesion promotor.
29. The nail polish composition according to claim 1, further
comprising nitrocellulose, polyvinylbutyral, tosylamide
formaldehyde and/or tosylamide epoxy resins.
30. The polymerizable nail coating composition according to claim
1, further comprising a cellulose acetate alkylate selected from
the group consisting of cellulose acetate butyrate, cellulose
acetate propionate, and mixtures thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority benefit from U.S.
Provisional Patent Application 62/518,791 filed Jun. 13, 2017 which
is incorporated by reference herein in its entirety.
FIELD OF THE INVENTION
[0002] The invention provides for a crosslinkable composition for
use in nail coating compositions containing dyes, inorganic
pigments or lakes.
BACKGROUND
[0003] The coatings industry continues to develop new chemistries
as performance requirements for decorative and functional coatings
evolve. Drivers for change are varied and these can include:
regulatory controls to reduce VOC emissions, concerns about toxic
hazards of coating raw materials, a desire for cost reduction,
commitments to sustainability, and a need for increased product
effectiveness.
[0004] UV nail gel coatings have gained rapid popularity with
fashion conscious individuals who apply nail polish to fingernails
or toenails to decorate and protect nail plates. UV nail gels can
produce coatings that exhibit phenomenal chip resistance and
durability when properly applied and cured in comparison to those
nail coatings derived from traditional solvent based nail lacquers.
The performance difference particularly becomes apparent when the
coating is applied on human finger nails and tested for durability.
UV nail gel coatings can easily last for two weeks or more and
still look like new whereas conventional nail polishes are easily
scratched and will chip or peel from the natural nail in one to
five days. UV nail gels are typically based on acrylates that cure
quickly into dense, crosslinked thermoset coatings within half a
minute or so. This is an advantage as the coating becomes almost
immediately resistant to denting and scratching. Conventional nail
lacquers show significant sensitivity to denting while the solvent
evaporates from the coating and this requires great care by the
individual as the coating dries and hardens; a process that can
take easily fifteen to twenty minutes. However, conventional nail
polish is easily removed with solvent whereas it can take some
effort to remove a fully cured UV nail gel from the nail surface.
An expensive UV light also is required for UV nail gel application
and this has limited the success of UV nail gels in the mass market
for home use. The expense of a UV light is less of an issue for
professional salons where a right balance between service rate and
a customers' perception of service is more important. As such,
there is a need in the consumer market place for durable nail
coatings that can cure quickly but do not require procurement of an
UV light.
[0005] Highly crosslinked, durable coating compositions can be
achieved using Michael addition chemistry. The Michael addition
reaction involves the nucleophilic addition of a Michael donor,
such as a carbanion or another nucleophile to a Michael acceptor,
such as an .alpha.,.beta.-unsaturated carbonyl. As such, the base
catalyzed addition of activated methylene moieties to electron
deficient C.dbd.C double bonds are known in coatings applications.
Representative examples of suitable materials that can provide
activated methylene or methine groups are generally disclosed in
U.S. Pat. No. 4,871,822, which resins contain a methylene and/or
monosubstituted methylene group in the alpha-position to two
activating groups such as, for example, carbonyl, cyano, sulfoxide
and/or nitro groups. Preferred are resins containing a methylene
group in the alpha-position to two carbonyl groups, such as
malonate and/or acetoacetate group-containing materials, malonates
being most preferred. The .alpha.,.beta.-unsaturated carbonyl
typically is an acrylate material and representative materials have
been disclosed in U.S. Pat. No. 4,602,061. The Michael reaction is
fast, can be carried out at ambient temperatures and gives a
chemically stable crosslinking bond without forming any reaction
by-product.
[0006] A typical crosslinkable coating composition comprises a
resin ingredient A (Michael donor), a resin ingredient B (Michael
acceptor) and a base to start and catalyze the Michael addition
reaction. The base catalyst should be strong enough to abstract,
i.e. activate a proton from resin ingredient A to form the Michael
donor carbanion species. Since the Michael addition cure chemistry
can be very fast, the coating formulator is challenged to control
the speed of the reaction to achieve an acceptable balance of pot
life, open time, tack free time and cure time. Pot life is defined
as the amount of time during which the viscosity of a mixed
reactive system doubles. Working life or working time informs the
user how much time they have to work with a reactive two-part
system before it reaches such a high state of viscosity, or other
condition, that it cannot be properly worked with to produce an
acceptable application result. Gel time is the amount of time it
takes for a mixed, reactive resin system to gel or become so highly
viscous that it has lost fluidity. The open time of a coating is a
practical measure of how much time it takes for a drying or curing
coating to reach a stage where it can no longer be touched by brush
or roller when applying additional coating material without leaving
an indication that the drying or curing coating and newly applied
coating did not quite flow together. These indications normally
take the form of brush or roller marks and sometimes a noticeable
difference in sheen levels. The tack free time is the amount of
time it takes for a curing or drying coating to be no longer sticky
to the touch, i.e. the time for a system to become hard to the
touch, with no tackiness. Cure time is the amount of time it takes
for a coating system to reach full final properties.
[0007] The Michael reaction starts the very moment when coating
resin ingredients A and B are mixed together with a suitable base.
Since it is a fast reaction, the material in a mixing pot starts to
crosslink and the fluid viscosity starts to rise. This limits the
pot life, working time and general use as a coating. A dormant
initiator that is essentially passive while coating material
remains in a mixing vessel but that activates the Michael addition
reaction upon film formation allows for longer pot life and working
time, yet would show good open time, tack free time and cure time.
Hence, the application of dormant initiator technology can provide
the formulator with tools to control the speed of the reaction in
order to achieve desirable cure characteristics.
[0008] U.S. Pat. No. 8,962,725 describes a blocked base catalyst
for Michael addition, which is based on substituted carbonate
salts. Preferred Michael donor resins are based on malonate and
Michael acceptor resins are acrylates. The substituted carbonates
can bear substituents, but these should not substantially interfere
with the crosslinking reaction between malonate and acrylate. The
carbonate salts release carbon dioxide and a strong base upon
activation by means of film formation. The base is either hydroxide
or alkoxide. Before practical pot life and gel times are achieved
with acceptable curing characteristics, the carbonate requires
presence of a certain amount of water in the coating formulation
for the blocking of the base to become effective. All disclosed
blocked carbonate examples utilize methanol and/or water. However,
malonate esters are known to be susceptible to base hydrolysis,
particularly when water is present. Hence, the water necessary to
block the carbonate base can thus degrade malonate oligomers or
polymers at the same time, which in turn can lead to altered
coatings performance. The hydrolysis product furthermore can result
in undesirable destruction of base catalyst by means of formation
of malonate salt; a reaction which is cloaked as longer pot life
and gel time. Presence of water can also be quite problematic in
certain coatings applications. Wood grain raising is a significant
problem when water is present in wood coatings; water penetrates
into wood, which causes swelling and lifting of fibers and this
leaves a rough surface. Water also can cause flash rust, i.e.
appearance of rust spots on a metal surface during drying of newly
applied paint that contains water. Longer term rust formation in
terms of corrosion may also be a problem when dealing with
formulations that contain water.
SUMMARY OF INVENTION
[0009] In one embodiment, the present invention provides for a nail
polish composition containing a crosslinkable coating composition
comprising: ingredient A that has at least two protons that can be
activated to form a Michael carbanion donor; ingredient B that
functions as a Michael acceptor having at least two ethylenically
unsaturated functionalities each activated by an
electron-withdrawing group; and a carbonate initiator of Formula
(1)
##STR00002##
wherein R.sub.7 is selected from hydrogen, a linear or branched
substituted or unsubstituted alkyl group having 1 to 22 carbon
atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms; and A.sup.n+ is a
cationic species or polymer and n is an integer equal or greater
than 1 with the proviso that A.sup.n+ is not an acidic hydrogen; at
least one colorant independently selected from the group consisting
of (i) a dye; (ii) an inorganic pigment; or an (iii) a lake; and
optionally further comprising ammonium carbamate
(H.sub.2NR.sub.8R.sub.9+--OC.dbd.ONR.sub.8R.sub.9), wherein R.sub.8
R.sub.9 are each independently selected from hydrogen, a linear or
branched substituted or unsubstituted alkyl group having 1 to 22
carbon atoms; 1 to 8 carbon atoms; 1 to 3 carbon atoms.
[0010] In one embodiment, the present invention provides a nail
polish composition wherein a dye is selected from the group
consisting of D&C Red 21, D&C Red No. 22, D&C Red No.
28, D&C Red No. 30, D&C Red No. 33, D&C Red No. 40,
D&C Black No. 2, D&C Yellow No. 5, D&C Green No. 5,
Annatto and Caramel. In one such embodiment, the inorganic pigment
is selected from the group consisting of red iron oxide; yellow
iron oxide; titanium dioxide; brown iron oxide; chromium oxide
green; iron blue (ferric ferrocyanide blue); ultramarine blue;
ultramarine violet; ultramarine pink; black iron oxide; bismuth
oxychloride; aluminum powder; manganese violet; mica; bronze
powder; copper powder; guanine and combinations thereof. In another
such embodiment, the lake is a D&C lake.
[0011] In one embodiment, the present invention provides a nail
polish composition wherein ingredient A is selected from the group
consisting of compounds, oligomers or polymers. In one such
embodiment, ingredient A is independently selected from a malonate
group containing compound, a malonate group containing oligomer, a
malonate group containing polymer, an acetoacetate group containing
compound, an acetoacetate group containing oligomer, an
acetoacetate group containing polymer or combinations thereof. In
another such embodiment, the malonate group containing compound,
malonate group containing oligomer, malonate group containing
polymer, an acetoacetate group containing compound, acetoacetate
group containing oligomer, or acetoacetate group containing polymer
are each selected from the group consisting of: polyurethanes,
polyesters, polyacrylates, epoxy polymers, polyamides,
polyesteramides or polyvinyl polymers, wherein such compounds,
oligomers or polymers have a malonate group or acetoacetate group
located in a main chain of such compound or oligomer or polymer or
a side chain of such compound or oligomer or polymer.
[0012] In one embodiment, the present invention provides a nail
polish composition wherein wherein ingredient B is selected from
the group consisting of acrylates, fumarates, maleates and
combinations thereof. In one such embodiment, the acrylate is
independently selected from the group consisting of hexanediol
diacrylate, trimethylol propane triacrylate, pentaerythritol
triacrylate, di-trimethylolpropane tetraacrylate bis(2-hydroxyethyl
acrylate), trimethylhexyl dicarbamate, bis(2-hydroxyethyl acrylate)
1,3,3-trimethylcyclohexyl dicarbamate, bis(2-hydroxyethyl acrylate)
methylene dicyclohexyl dicarbamate and combinations thereof.
[0013] In one embodiment, the present invention provides a nail
polish composition wherein ingredient B is independently selected
from the group consisting of polyesters, polyurethanes, polyethers
and/or alkyd resins each containing at least two pendant
ethylenically unsaturated groups each activated by an
electron-withdrawing group.
DETAILED DESCRIPTION
[0014] The invention disclosed here is a crosslinkable composition
comprising a resin ingredient A (Michael donor), a resin ingredient
B (Michael acceptor) and a carbonate initiator ingredient C. The
invention generally is useful as a decorative and/or functional
coating, and the invention particularly is useful as a coating for
human finger nails or toe nails.
[0015] Resin Ingredient A (Michael Donor):
[0016] Resin ingredients A are compounds, oligomers or polymers
that contain functional groups that have reactive protons that can
be activated to produce a carbanion Michael donor. In one
embodiment, the functional group can be a methylene or methine
group and resins have been described in U.S. Pat. No. 4,602,061 and
U.S. Pat. No. 8,962,725 for example. In one embodiment, resin
ingredients A are those derived from malonic acid or malonate
esters, i.e. malonate. Oligomeric or polymeric malonate compounds
include polyurethanes, polyesters, polyacrylates, epoxy resins,
polyamides, polyesteramides or polyvinyl resins each containing
malonate groups, either in the main chain or the side chain or in
both.
[0017] In one embodiment, polyurethanes having malonate groups may
be obtained, for instance, by bringing a polyisocyanate into
reaction with a hydroxyl group containing ester or polyester of a
polyol and malonic acid/malonates, by esterification or
transesterification of a hydroxyfunctional polyurethane with
malonic acid and/or a dialkyl malonate. Examples of polyisocyanates
include hexamethylenediisocyanate, trimethylhexamethylene
diisocyanate, isophorone diisocyanate, toluene diisocyanate and
addition products of a polyol with a diisocyanate, such as that of
trimethylolpropane to hexamethylene diisocyanate. In one
embodiment, the polyisocyanate is selected from isophorone
diisocyanate and trimethyhexamethylene diisocyanate. In another
embodiment, the polyisocyanate is isophorone diisocyanate. In some
embodiments, hydroxyfunctional polyurethanes include the addition
products of a polyisocyanate, such as the foregoing
polyisocyanates, with di- or polyvalent hydroxy compounds,
including diethyleneglycol, neopentyl glycol, dimethylol
cyclohexane, trimethylolpropane, 1,3-propandiol, 1,4-butanediol,
1,6-hexanediol and polyether polyols, polyester polyols or
polyacrylate polyols. In some embodiments, the di- or polyvalent
hydroxy compounds include diethyleneglycol, 1,3-propanediol,
1,4-butanediol and 1,6-hexanediol. In other embodiments, the di- or
polyvalent hydroxy compounds include diethyleneglycol and
1,6-hexanediol.
[0018] In one embodiment, malonic polyesters may be obtained, for
instance, by polycondensation of malonic acid, an alkylmalonic
acid, such as ethylmalonic acid, a mono- or dialkyl ester of such a
carboxylic acid, or the reaction product of a malonic ester and an
alkylacrylate or methacrylate, optionally mixed with other di- or
polycarboxylic with one or more dihydroxy and/or polyhydroxy
compounds, in combination or not with mono hydroxy compounds and/or
carboxyl compounds. In some embodiments, polyhydroxy compounds
include compounds containing 2-6 hydroxyl group and 2-20 carbon
atoms, such as ethylene glycol, diethyleneglycol, propylene glycol,
trimethylol ethane, trimethylolpropane, glycerol, pentaerythritol,
1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol,
1,12-dodecanediol and sorbitol. In some embodiments, the
polyhydroxyl compounds include diethylene glycol, propylene glycol,
1,4-butanediol and 1,6-hexanediol. In other embodiments, the
polyhydroxyl compounds include propylene glycol and 1,6-hexanediol.
In certain embodiments, the polyhydroxy may be a primary alcohol
and in certain other embodiments, the polyhydroxy may be a
secondary alcohol. Examples of polyols with secondary alcohol
groups are 2,3-butanediol, 2,4-pentanediol and 2,5-hexanediol and
the like.
[0019] In one embodiment, malonate group-containing polymers also
may be prepared by transesterification of an excess of dialkyl
malonate with a hydroxy functional polymer, such as a vinyl
alcohol-styrene copolymer. In this way, polymers with malonate
groups in the side chains are formed. After the reaction, the
excess of dialkyl malonate may optionally be removed under reduced
pressure or be used as reactive solvent.
[0020] In one embodiment, malonate group or acetoacetate group
containing polymers may also be obtained from reaction with
malonate or acetoacetonate with polyols, such as those polyols that
are commercially sold for reaction with isocyanates to form
polyurethane coatings.
[0021] In one embodiment, malonic epoxy esters may be prepared by
esterifying an epoxy polymer with malonic acid or a malonic
monoester, or by transesterifying with a dialkylmalonate,
optionally in the presence of one or more other carboxylic acids or
derivatives thereof.
[0022] In one embodiment, polyamides having malonate groups may be
obtained in the same manner as polyesters, at least part of the
hydroxy compound(s) being replaced with a mono- or polyvalent
primary and/or secondary amine, such as cyclohexylamine, ethylene
diamine, isophorone diamine, hexamethylene diamine, or diethylene
triamine.
[0023] In some embodiments, such polyamide compounds can be
obtained when 12-hydroxystearic acid is reacted with a diamine such
as ethylenediamine. Such polyamides have secondary alcohol groups,
which can be esterified with malonic acid or malonate in a second
reaction step. In some embodiments, other diamines may also be used
in the reaction with 12-hydroxystearic acid, for example:
xylylenediamine, butylenediamine, hexamethylenediamine,
dodecamethylenediamine, and even dimer amine, which is derived from
dimer acid. Polyamines may also be used, but in a right
stoichiometric ratio as to avoid gelling of the polyamide in the
reactor. Lesquerolic acid may also be used in reactions with
polyamines to yield polyamides bearing secondary alcohol groups,
which can be used in reactions with malonate to form malonate
containing compounds. Reactions that yield malonamides are much
less desirable.
[0024] In some embodiments, the above mentioned malonate resins may
be blended together to achieve optimized coatings properties. Such
blends can be mixtures of malonate modified polyurethanes,
polyesters, polyacrylates, epoxy resins, polyamides,
polyesteramides and the like, but mixtures can also be prepared by
blending various malonate modified polyesters together. In some
other embodiments, various malonate modified polyurethanes can be
mixed together, or various malonate modified polyacrylates, or
malonate modified epoxy resins, or various malonate modified
polyamides, malonate modified polyesteramides.
[0025] In certain embodiments, malonate resins are malonate group
containing oligomeric esters, polyesters, polyurethanes, or epoxy
esters having 1-100, or 2-20 malonate groups per molecule. In some
such embodiments, the malonate resins should have a number average
molecular weight in the range of from 250 to 10,000 and an acid
number not higher than 5, or not higher than 2. Use may optionally
be made of malonate compounds in which the malonic acid structural
unit is cyclized by formaldehyde, acetaldehyde, acetone or
cyclohexanone. In some embodiments, molecular weight control may be
achieved by the use of end capping agents, typically monofunctional
alcohol, monocarboxylic acid or esters. In one embodiment, malonate
compounds may be end capped with one or more of 1-hexanol,
1-octanol, 1-dodecanol, hexanoic acid or its ester, octanoic acid
or its esters, dodecanoic acid or its esters, diethyleneglycol
monoethyl ether, trimethylhexanol, and t-butyl acetoacetate, ethyl
acetoacetate. In one such embodiment, the malonate is end capped
with 1-octanol, diethyleneglycol monoethyl ether, trimethylhexanol,
t-butyl acetoacetate and ethyl acetoacetate. In another such
embodiment, the malonate is end capped t-butyl acetoacetate, ethyl
acetoacetate and combinations thereof.
[0026] Monomeric malonates may optionally be used as reactive
diluents, but certain performance requirements may necessitate
removal of monomeric malonates from resin ingredient A.
[0027] In some embodiments, resin ingredients A include oligomeric
and/or polymeric acetoacetate group-containing resins. In some
embodiments, such acetoacetate group-containing resins are
acetoacetic esters as disclosed in U.S. Pat. No. 2,759,913,
diacetoacetate resins as disclosed in U.S. Pat. No. 4,217,396 and
acetoacetate group-containing oligomeric and polymeric resins as
disclosed in U.S. Pat. No. 4,408,018. In some embodiments,
acetoacetate group-containing oligomeric and polymeric resins can
be obtained, for example, from polyalcohols and/or
hydroxy-functional polyether, polyester, polyacrylate, vinyl and
epoxy oligomers and polymers by reaction with diketene or
transesterication with an alkyl acetoacetate. Such resins may also
be obtained by copolymerization of an acetoacetate functional
(meth)acrylic monomer with other vinyl- and/or acrylic-functional
monomers. In certain other embodiments, the acetoacetate
group-containing resins for use with the present invention are the
acetoacetate group-containing oligomers and polymers containing at
least 1, or 2-10, acetoacetate groups. In some such embodiments,
such acetoacetate group containing resins should have Mn in the
range of from about 100 to about 5000 g/mol, and an acid number of
about 2 or less. Resins containing both malonate and acetoacetate
groups in the same molecule may also be used.
[0028] In another embodiment, the above mentioned malonate group
containing resins and acetoacetate group-containing resins may also
be blended to optimize coatings properties as desired, often
determined by the intended end application.
[0029] Structural changes at the acidic site of malonate or
acetoacetate can alter the acidity of these materials and
derivatives thereof. For instance, pKa measurements in DMSO show
that diethyl methylmalonate (MeCH(CO.sub.2Et).sub.2) has a pKa of
18.7 and diethyl ethylmalonate (EtCH(CO.sub.2Et).sub.2) has a pKa
of 19.1 whereas diethyl malonate (CH.sub.2(CO.sub.2Et).sub.2) has a
pKa of 16.4. Resin ingredient A may contain such substituted
moieties and therewith show changes in gel time, open time, cure
time and the like. For example, resin ingredient A may be a
polyester derived from a polyol, diethyl malonate and diethyl
ethylmalonate.
[0030] Resin Ingredient B (Michael Acceptor):
[0031] Resin ingredients B (Michael acceptor) generally can be
materials with ethylenically unsaturated moieties in which the
carbon-carbon double bond is activated by an electron-withdrawing
group, e.g. a carbonyl group in the alpha-position. In some
embodiments, resin ingredients B are described in: U.S. Pat. No.
2,759,913, U.S. Pat. No. 4,871,822, U.S. Pat. No. 4,602,061, U.S.
Pat. No. 4,408,018, U.S. Pat. No. 4,217,396 and U.S. Pat. No.
8,962,725. In certain embodiments, resin ingredients B include
acrylates, fumarates and maleates.
[0032] In some embodiments, resin ingredients B are the acrylic
esters of chemicals containing 2-6 hydroxyl groups and 2-20 carbon
atoms. These esters may optionally contain hydroxyl groups. In some
such embodiments, examples of such acrylic esters include
hexanediol diacrylate, trimethylolpropane triacrylate,
pentaerythritol triacrylate, di-trimethylolpropane tetraacrylate.
In one such embodiment, acrylic esters include trimethylolpropane
triacrylate, di-trimethylolproane tetraacrylate, dipentaerythritol
hexaacrylate, pentaerythritol ethoxylated (EO).sub.n tetraacrylate,
trimethylolpropane ethoxylated(EO).sub.n triacrylate and
combinations thereof. In another embodiment, acrylamides may be
used as a resin ingredient B.
[0033] In other embodiments, resin ingredients B are polyesters
based upon maleic, fumaric and/or itaconic acid (and maleic and
itaconic anhydride), and chemicals with di- or polyvalent hydroxyl
groups, optionally including materials with a monovalent hydroxyl
and/or carboxyl functionality.
[0034] In other embodiments, resin ingredients B are resins such as
polyesters, polyurethanes, polyethers and/or alkyd resins each
containing at least two pendant ethylenically unsaturated groups
each activated by an electron-withdrawing group. These include, for
example, urethane acrylates obtained by reaction of a
polyisocyanate with an hydroxyl group-containing acrylic ester,
e.g., an hydroxyalkyl ester of acrylic acid or a resins prepared by
esterification of a polyhydroxyl material with acrylic acid;
polyether acrylates obtained by esterification of an hydroxyl
group-containing polyether with acrylic acid; polyfunctional
acrylates obtained by reaction of an hydroxyalkyl acrylate with a
polycarboxylic acid and/or a polyamino resin; polyacrylates
obtained by reaction of acrylic acid with an epoxy resin; and
polyalkylmaleates obtained by reaction of a monoalkylmaleate ester
with an epoxy polymer and/or an hydroxy functional oligomer or
polymer. In certain embodiments, polyurethane acrylate resins may
be prepared by reaction of hydroxyalkyl acrylate with
polyisocyanate. Such polyurethane acrylate resins independently
include bis(2-hydroxyethyl acrylate) trimethylhexyl dicarbamate
[2-hydroxyethyl acrylate trimethylhexamethylene diisocyanate (TMDI)
adduct], bis(2-hydroxyethyl acrylate) 1,3,3-trimethylcyclohexyl
dicarbamate [2-hydroxyethyl acrylate 1,3,3-trimethylcyclohexyl
diisocyanate/isophorone diisocyanate (IPDI) adduct],
bis(2-hydroxyethyl acrylate) hexyl dicarbamate [2-hydroxyethyl
acrylate hexamethylene diisocyanate (HDI) adduct],
bis(2-hydroxyethyl acrylate) methylene dicyclohexyl dicarbamate
[2-hydroxyethyl acrylate methylene dicyclohexyl diisocyanate (HMDI)
adduct], bis(2-hydroxylethyl acrylate) methylenediphenyl
dicarbamate [2-hydroxyethyl acrylate methylenediphenyl diisocyanate
(MDI) adduct], bis(4-hydroxybutyl acrylate)
1,3,3-trimethylcyclohexyl dicarbamate [4-hydroxybutyl acrylate IPDI
adduct], bis(4-hydroxybutyl acrylate) trimethylhexyl dicarbamate
[4-hydroxybutyl acrylate TMDI adduct], bis(4-hydroxybutyl acrylate)
hexyl dicarbamate [4-hydroxybutyl acrylate HDI adduct],
bis(4-hydroxybutyl acrylate) methylene dicyclohexyl dicarbamate
[4-hydroxybutyl acrylate HMDI adduct], bis(4-hydroxybutyl acrylate)
methylenediphenyl dicarbamate [4-hydroxybutyl acrylate MDI
adduct].
[0035] In other embodiments, resin ingredients B have unsaturated
acryloyl functional groups. In other certain embodiments, resin
ingredient B is independently selected from the group consisting of
polyesters, polyurethanes, polyethers and/or alkyd resins each
containing at least one pendant acryloyl functional group.
[0036] In certain embodiments, the acid value of the activated
unsaturated group-containing material (resin ingredient B) is
sufficiently low to not substantially impair the Michael addition
reaction, for example less than about 2, and further for example
less than 1 mg KOH/g.
[0037] As exemplified by the previously incorporated references,
these and other activated unsaturated group containing resins, and
their methods of production, are generally known to those skilled
in the art, and need no further explanation here. In certain
embodiments, the number of reactive unsaturated group ranges from 2
to 20, the equivalent molecular weight (EQW: average molecular
weight per reactive functional group) ranges from 100 to 2000, and
the number average molecular weight Mn ranges from 100 to 5000.
[0038] In one embodiment, the reactive part of resin ingredients A
and B can also be combined in one A-B type molecule. In this
embodiment of the crosslinkable composition both the methylene
and/or methine features as well as the .alpha.,.beta.-unsaturated
carbonyl are present in the same molecule, be it a monomer,
oligomer or polymer. Mixtures of such A-B type molecules with
ingredient A and B are also useful.
[0039] Each of the foregoing embodiments of resin ingredient A and
resin ingredient B may be combined with the various embodiments of
a dormant carbonate initiator ingredient C, described below, to
arrive at the inventions described herein. In one embodiment, resin
ingredient A is a polyester malonate composition and resin
ingredient B is a polyester acrylate. In another embodiment, resin
ingredient A is a polyurethane malonate composition and resin
ingredient B is a polyester acrylate. In another embodiment, resin
ingredient A is a polyurethane malonate composition and resin
ingredient B is a polyester acrylate. In another embodiment, resin
ingredient A is a polyurethane malonate composition and resin
ingredient B is a polyurethane acrylate. In another embodiment,
resin ingredient A is a polyester malonate having acetoacetate end
groups and resin ingredient B is a polyester acrylate. In yet
another embodiment, resin ingredient A is a polyester malonate
having acetoacetate end groups and resin ingredient B is a
polyurethane acrylate. In still yet another embodiment, resin
ingredient A is a polyester malonate having acetoacetate end groups
and resin ingredient B is a mixture of polyester acrylate and
polyurethane acrylate.
[0040] In the foregoing embodiments, the number of reactive protons
for resin ingredients A, and the number of
.alpha.,.beta.-unsaturated carbonyl moieties on resin ingredient B
can be utilized to express desirable ratios and ranges for resin
ingredients A and B. Typically, the mole ratio of reactive protons
of ingredient A that can be activated with subsequent carbanion
formation relative to the activated unsaturated groups on
ingredient B is in the range between 10/1 and 0.1/1, or between 4/1
and 0.25/1, or between 3.3/1 and 0.67/1. However, the optimal
amount strongly depends also on the number of reactive groups
present on ingredients A and/or B.
[0041] The amount of dormant carbonate initiator used, expressed as
mole ratio of protons that can be abstracted to form an activated
Michael donor species (e.g. the methylene group of malonate can
provide two protons for reactions, while a methine group can
provide one proton to form an activated species) relative to
initiator, ranges from about 1000/1 to 1/1, or from 250/1 to 10/1,
or from 125/1 to 20/1 but the optimal amount to be used depends
also on the amount of solvent present, reactivity of various acidic
protons present on resin ingredients A and/or B.
[0042] Carbonate Initiator Ingredient C:
[0043] Ingredient C may be a carbonate initiator having a structure
as shown in Formula 1:
##STR00003##
R.sub.7 can be independently selected and is hydrogen or a linear
or branched alkyl group with 1 to 22 carbon atoms; 1 to 8 carbon
atoms; or 1 to 3 carbon atoms. In some such embodiments, R.sub.7 is
an unsubstituted alkyl group. In other such embodiments, R.sub.7 is
a substituted alkyl group including hydroxyl substituted alkyl
groups. In some embodiments, R.sub.7 is independently selected from
a methyl group, an ethyl group, a propyl group, or a butyl group.
For the foregoing embodiments, A.sup.n+ is a cationic material and
n is an integer equal or greater than 1; A.sup.+n is not an acidic
hydrogen. In some embodiments, A.sup.n+ can be a monovalent cation,
such as an alkali metal, earth alkali metal or another monovalent
metal cation, a quaternary ammonium or a phosphonium compound. In
some embodiments, A.sup.n+ can also be a multivalent metal cation,
or a compound bearing more than one quaternary ammonium or
phosphonium groups, or can be a cationic polymer. In certain
embodiments, A.sup.n+ is a monovalent quaternary ammonium compound
where n is 1. A.sup.n+ cannot have acidic protons that can
protonate the carbanion Michael donor derived from resin ingredient
A.
[0044] In a certain embodiment, A.sup.n+ of formula 1 is a
monovalent quaternary ammonium compound and as shown in formula 2.
A large selection of such quaternary ammonium compounds is
commercially available from various manufacturers. In one
embodiment, quaternary ammonium compounds are derived from tertiary
amines and quaternized with a methyl or benzyl group. In other
embodiments, tetra alkyl ammonium compounds also can be used. R3,
R4 and R5 are independently selected and are linear or branched
alkyl chains having from 1 to 22 carbon atoms; or 1 to 8 carbon
atoms. In such foregoing embodiments, R6 is selected from a methyl
or a benzyl group or an alkyl group having from 2 to 6 carbon
atoms. Such quaternary ammonium compounds are commercially
available as salts and the anion typically is chloride, bromide,
methyl sulfate, or hydroxide. Quaternary ammonium compounds with
methylcarbonate or ethylcarbonate anions are also available.
##STR00004##
[0045] Examples of A.sup.n+ of formula 1 include dim ethyl
diethylammonium, dimethyldipropylammonium, triethylmethylammonium,
tripropylmethylammonium, tributylmethylammonium,
tripentylmethylammonium, trihexylmethylammonium tetraethylammonium,
tetrapropylammonium, tetrabutyl ammonium, tetrapentylammonium,
tetrahexylammonium, benzyltrimethylammonium,
benzyltriethylammonium, benzyltripropylammonium,
benzyltributylammonium, benzyltripentyammonium, and
benzyltrihexylammonium.
[0046] The crosslinkable composition of this invention preferably
contains some solvent. The coating formulator may choose to use an
alcohol, or a combination of alcohols as solvent for a variety of
reasons. Other solvents like ethylacetate or butylacetate may also
be used, potentially in combination with alcohol solvents. Ethanol
is a preferred solvent. Isopropyl alcohol also is a preferred
solvent. Methanol is not preferred as a solvent because of health
and safety risks, and is particularly not preferred and cannot be
used when the crosslinkable composition is used as a coating for
finger nails and toe nails. Other oxygenated, polar solvents such
as ester or ketones for instance, are also suitable and can be
used, potentially in combination with alcohol. Other organic
solvents may also be used.
[0047] In some embodiments of the crosslinkable composition, water
may be added to the composition. further comprising water
concentration selected from the group consisting of less than 10
wt. %, less than 5 wt. %; less than 1 wt. %; less than 0.1 wt. %;
less than 0.01 wt. % water.
[0048] Some embodiments of the crosslinkable composition of this
invention may also be formulated without solvent in some cases. In
other embodiments, the crosslinkable coating contains typically at
least 5 wt % of solvent, preferably between 5% and 45%, more
preferable between 5% and 35%, but preferable not more than 60%
because of VOC restrictions. In such embodiments, the organic
solvent is independently selected from the group consisting of an
alcohol, ester, ether, glycol ether, ketone, aromatic and
combinations thereof. In certain embodiments the alcohol is
independently selected from the group consisting of methanol,
ethanol, iso-propanol, butanol, iso-butanol, t-butanol and
combinations thereof.
[0049] The crosslinkable composition useful as a coating can be
formulated as a one component, a two component system or a three
component system. In an embodiment of a two component system,
initiator ingredient C is added to a mixture of ingredients A and B
just prior to use; ingredient D may optionally be added to the
initiator ingredient C or the mixture of ingredients A and B. In an
alternative embodiment, ingredients A and C are mixed, and
ingredient B is added prior to use ingredient; D may optionally be
added to the mixture of ingredient A and initiator ingredient C or
ingredient B. In yet another embodiment, ingredient A is added to a
mixture of ingredients B and C prior to use; ingredient D may
optionally be added to ingredient A or the mixture of ingredient B
and initiator C. In certain embodiments, pot life, working time and
gel time can be adjusted by selection of the initiator structure,
the amount used in the crosslinkable composition, presence of
additional ammonium carbamate and to a certain extent the amount of
solvent and/or water. A gel time of hours, and even days can be
readily achieved, and gel times of weeks are possible. As such, the
dormant initiator allows for an opportunity to formulate a three
component paint system. In such embodiment of a one component
system, ingredients A, B, C and D are mixed together, optionally
with other ingredients to formulate a paint, which is then canned
and stored until use. In certain embodiments, a one component
system can be enhanced by means of using excess carbon dioxide gas
over the crosslinkable composition as to further improve pot life
and gel time. For instance, a paint composition formulated
according to the invention may have a protective atmosphere of
carbon dioxide over the paint volume; and in yet another
embodiment, a container containing the crosslinkable composition
may even be pressurized with carbon dioxide. In another embodiment,
a one component system containing ingredients A, B and C are in a
container filled to capacity with essentially no space remaining
for other solids, liquid or gaseous ingredients and optionally
containing ammonium carbamate. In yet another embodiment,
additional ammonium carbamate may further enhance stability in such
one component coating formulations.
[0050] In another embodiment, the present invention provides for
the crosslinkable coating composition wherein ingredient A,
ingredient B and the carbonate initiator are contained in a
container having two or more chambers, which are separated from one
another. In one such embodiment, ingredient A and ingredient B are
contained in separate chambers to inhibit any reaction. In another
such embodiment, the carbonate initiator is contained in the
chamber having ingredient A, and optionally containing CO.sub.2
and/or ammonium carbamate. In another such embodiment, the
carbonate initiator is contained in the chamber having ingredient
B, and optionally containing CO.sub.2 and/or ammonium
carbamate.
[0051] In another embodiment, the present invention provides for
the crosslinkable coating composition such that ingredient A and
ingredient B are contained in the same chamber and the carbonate
initiator is contained in a separate chamber to inhibit any
reaction and said separate chamber optionally containing CO.sub.2
and/or ammonium carbamate.
[0052] Malonate esters are known to be susceptible to base
hydrolysis, particularly when water is present. Water potentially
can lead to undesirable destruction of initiator by means of
formation of malonate salt and it can degrade malonate oligomers or
polymers, which in turn can lead to altered coatings performance.
Transesterification reactions also can occur with malonate esters
and alcohol solvent. These reactions potentially can be limiting to
the formulation of an acceptable working life, as a coatings
formulator seeks to increase pot life and gel time for a
crosslinkable composition formulated either as a one or two
component system. However, primary alcohols such as methanol and
ethanol are much more active in transesterification reactions than
secondary alcohols such as isopropanol, while tertiary alcohols are
generally least active. Furthermore, additional resistance towards
hydrolysis and transesterification can be obtained when malonate
polyester resins are derived from malonic acid, or a
dialkylmalonate such as diethylmalonate, and polyols bearing
secondary alcohol groups; such as 2,3-butanediol, 2,4-pentanediol
and 2,5-hexanediol and the like. The combination of such polyester
resins and non-primary alcohol solvents, such as isopropanol or
butanol, is particularly useful in achieving desirable resistance
towards transesterification reactions. In a preferred approach,
resin ingredient A comprises malonate moieties that have been
esterified with polyols bearing secondary alcohol groups and where
secondary alcohol is present as solvent in the crosslinkable
composition of this invention. In yet another approach, tertiary
alcohols are used as solvent or solvents as used that do not
participate in transesterification reactions. Other resins may also
be formulated using such stabilizing approaches towards resin
breakdown and such approaches are well known to one skilled in the
art and need not be further described here.
[0053] The number of reactive protons for ingredients A, and the
number of .alpha.,.beta.-unsaturated carbonyl moieties on resin
ingredient B can be utilized to express desirable ratio's and
ranges for ingredients A and B. Typically, the mole ratio of
reactive protons of ingredient A that can be activated with
subsequent carbanion formation relative to the activated
unsaturated groups on ingredient B is in the range between 10/1 and
0.1/1, preferably between 4/1 and 0.25/1, and more preferably 3.3/1
and 0.67/1. However, the optimal amount strongly depends also on
the number of such active functionalities present on ingredients A
and/or B. Although good tack free time may be obtained over a wide
ratio range, coatings properties, such as hardness for instance may
show a smaller preference range.
[0054] The crosslinkable composition of this invention comprising
ingredients A, B and C may optionally contain an additional
ingredient D, which once activated, can react with the Michael
acceptor. Ingredient D has one or more reactive protons that are
more reactive, i.e. more acidic than those of ingredient A (the pKa
of ingredient D is lower than that of ingredient A). The reactive
protons of ingredient D are present at a fraction based on the
reactive protons of ingredient A. The fraction ranges from 0 to
0.5, more preferably from 0 to 0.35, even more preferable between 0
and 0.15.
[0055] Examples of ingredient D include; succinimide, isatine,
ethosuximide, phthalimide, 4-nitro-2-methylimidazole,
5,5-dimethylhydantioin, phenol, 1,2,4-triazole, ethylacetoacetate,
1,2,3-triazole, ethyl cyanoacetate, benzotriazole, acetylacetone,
benzenesulfonamide, 1,3-cyclohexanedione, nitromethane,
nitroethane, 2-nitropropane, diethylmalonate,
1,2,3-triazole-4,5-dicarboxylic acid ethyl ester,
1,2,4-triazole-3-carboxylic acid ethyl ester,
3-Amino-1,2,4-triazole, 1H-1,2,3-triazole-5-carboxylic acid ethyl
ester, 1H-[1,2,3]triazole-4-carbaldehyde, morpholine, purines such
as purine, adenine, guanine, hypoxanthine, xanthine, theobromine,
caffeine, uric acid and isoguanine; pyrimidines, such as thymine
and cytosine; uracil, glycine, ethanimidamide, cysteamine,
allantoin, N,N-dimethylglycine, allopurinol, N-methylpyrrolidine,
benzeneboronic acid, salicyl aldehyde, 3-hydroxybenzaldehyde,
1-naphthol, methylphenidate and Vitamin E.
[0056] In other embodiments, ingredient D may be incorporated into
resin ingredient A. In such embodiments, substituted succinimides,
including hydroxyl group containing succinimide derivatives,
3-hydroxy-2,5-pyrrolidinedione and
3-(hydroxymethyl)-2,5-pyrrolidinedione, or carboxylic acid group
containing succinimide derivative,
2,5-dioxo-3-pyrrolidinecarboxylic acid can undergo condensation
reactions with either acid/ester groups or hydroxyl groups at the
end of resin A polymer chain, where the succinimide moiety will be
incorporated into the polymer backbone as end cap.
[0057] The amount of carbonate initiator used, expressed as mole
ratio of protons that can be abstracted to form an activated
Michael donor species (e.g. the methylene group of malonate can
provide two protons for reactions, while a methine group can
provide one proton to form an activated species) relative to
initiator, ranges from about 1000/1 to 1/1, more preferably from
250/1 to 10/1, even more preferable from 125/1 to 20/1 but the
optimal amount to be used depends also on the amount of solvent
present, reactivity of various acidic protons present on ingredient
A and, if present, ingredient D, on pigments or dyes present in the
system, on the number of active functionalities present on
ingredients A and/or B and the like. Hence, the optimal amount
needs to be determined experimentally to arrive at preferred curing
characteristics.
[0058] The crosslinkable coating composition of this invention can
comprise one or more pigments, dyes, effect pigments,
phosphorescent pigments, flakes and fillers. Metal flake effect
pigments may also be used in the crosslinkable coating composition
of this invention and this is an advantage over UV curable nail gel
coatings as the UV cure process is hindered by such pigments and
these metal flakes are therefore typically not used in such long
lasting nail coatings. The cross-linkable coating composition of
this invention can comprise other Michael addition reactive and
non-reactive resins or polymers, for instance to facilitate
adhesion, and/or aid in coating removal. Such removal aids may be
solvent-dissolvable compounds, resins, oligomers or polymers, which
are dispersed in the polymerized structure and can be easily
dissolved by a solvent to facilitate solvent absorption and
migration during removal of the coating.
[0059] The crosslinkable coating compositions of this invention may
contain one or more of FD&C or D&C dyes, pigments and/or
lakes. Lakes are colorants where one or more of the FD&C or
D&C dyes are adsorbed on a substratum, such as alumina, blanc
fixe, gloss white, clay, titanium dioxide, zinc oxide, talc, rosin,
aluminum benzoate or calcium carbonate. In certain embodiments, the
D&C dye is independently selected from D&C Red 21, D&C
Red No. 22, D&C Red No. 28, D&C Red No. 30, D&C Red No.
40, D&C Red No. 33, D&C Black No. 2, D&C Yellow No. 5,
D&C Green No. 5, Annatto, Caramel and combinations thereof. In
certain embodiments, the inorganic pigment is selected from the
group consisting of red iron oxide; yellow iron oxide; titanium
dioxide; brown iron oxide; chromium oxide green; iron blue (ferric
ferrocyanide blue); ultramarine blue; ultramarine violet;
ultramarine pink; black iron oxide; bismuth oxychloride; aluminum
powder; manganese violet; mica; bronze powder; copper powder;
guanine and combinations thereof.
[0060] Certain embodiments of the formulation may optionally
comprise resins, such as, but not limited to nitrocellulose,
polyvinylbutyral, tosylamide formaldehyde and/or tosylamide expoxy
resins. Certain other embodiments, the crosslinkable coating
compositions may comprise a cellulose acetate alkylate selected
from the group consisting of cellulose acetate butyrate, cellulose
acetate propionate, and mixtures thereof.
Such resins may act as film formers, adhesion promoters, and aids
to removal. These resins may also qualify as solvent-dissolvable
resins.
[0061] The cross-linkable coating composition of this invention can
comprise additives such as wetting agents, defoamers, rheological
control agents, ultraviolet (UV) light stabilizers, dispersing
agents, flow and leveling agents, optical brighteners, gloss
additives, radical inhibitors, radical initiators, adhesions
promotors, gloss additives, radical inhibitors, radical initiators,
plasticizers and combinations thereof. The selection of these
materials and additives will, of course, depend on the intended use
of the coating composition. However, all these materials need to be
carefully screened as some of these may react with the carbonate
initiator and therefore are not suitable for use in the
crosslinkable composition should such a reaction occur and
significantly interfere with the curing process. The above
described materials and additives are commonly used in the coatings
industry and are well known to one skilled in the art and need not
be further described here.
[0062] In certain embodiments, the crosslinkable composition of
this invention formulated as a nail polish may be packaged in a
single unit package good for one time use. Such single serve units
contain enough coating material to decorate all finger and toe
nails. A single use package may contain a nail polish formulated as
a one component system where all ingredients are mixed in one
chamber, potentially with extra ammonium carbamate and carbon
dioxide to push back on the dormant carbonate initiator in one
chamber filled to capacity with essentially no space remaining for
other solid, liquid or gaseous ingredients. The single unit package
may contain more than one chambers when the nail polish system is
formulated as a multi component system, e.g. two chambers when the
nail polish is formulated as a two component system, or three
chambers when ingredients A, B and C are all kept separate until
use. Packages are known where a seal between chambers is broken to
allow for materials to be mixed in the merged chambers and a proper
ratio of components is maintained by virtue of the design of the
package. Flexible packages and more rigid containers such as
bottles that have more than one chamber where contents can be mixed
upon demand are known and are readily available. Single unit
packages may also include a brush for application. In another
approach deviating from a single use concept, material may be
dispensed from a single chamber (flexible) package that can be
resealed. Multi chamber package that utilize plungers are also
known and proper mixing of components can be insured by use of a
mixing nozzle for instance. Material may be dispensed multiple
times provided the time between uses does not exceed the working
life of the nail polish in a mixing chamber or if the working life
is to be exceeded, the mixing nozzle is removed and the package
capped and stored until future use when a new mixing nozzle will be
used. Many packaging solutions are available from packaging
providers and these are well known to one skilled in the art.
[0063] In certain embodiments, the cross-linkable coating
composition of this invention is particularly useful to decorate
finger and toe nails, and can be applied as a three coat nail
polish system, with a base coat applied directly on top of the base
nail surface, followed by a color coat and finished with a glossy
top coat. In another preferred approach, the nail polish system is
formulated as a two coat system, where a color coat is applied
directly on the bare nail surface, and finished with a glossy top
coat, but in yet another approach, and base coat is applied to the
nail surface to provide adhesion for a glossy color coat. Another
particularly useful approach to decorate nails is where the
cross-linkable coating composition of this invention is used as a
single coat system, which has good adhesion to the nail surface,
color and gloss all in a one coat system. It is understood that
multiple coats can be applied over a same coat for any of these
one, two or three coat systems.
[0064] The following examples further describe and demonstrate
illustrative embodiments within the scope of the present invention.
The examples are given solely for illustration and are not to be
construed as limitations of this invention as many variations are
possible without departing from the spirit and scope thereof.
Coating Testing
[0065] Tack free time was evaluated by lightly pressing a gloved
index finger periodically onto the coating. The time when visible
marks in the film are no longer left by the pressed finger, was
then recorded as the tack free time.
[0066] Gel time was taken as the amount of time it takes for a
mixed, reactive resin system to gel or become so highly viscous
that it has lost fluidity. Typically, the various ingredients were
charged into a 4 ml vial and closed with headspace volume as
constant as possible to allow for comparison and the sample was
kept at room temperature and tilted at regular time intervals to
determine whether the material still flows. If no flow is observed
during tiling, the vial was held upside down and if no further flow
occurs the materials is gelled.
[0067] Fineness of Grind was evaluated with a Hegman Gauge
according to the ASTM D1210 test method.
Example 1
[0068] General Synthesis of Carbonate Catalyst from
Diethylcarbonate.
[0069] Most of the methanol solvent from a 40 g tetrabutylammonium
hydroxide (TBA OH) solution in methanol (1 M) was removed with a
rotary evaporator. The material was not allowed to become
completely dry without solvent as dry quaternary ammonium hydroxide
base is susceptible to decomposition. Next, 40 grams of ethanol was
added and most of the solvent was again removed. This procedure was
repeated at least two more times until the methanol effectively had
been replaced as determined by NMR. The solution strength is
determined by titration (typically 1.7 mmol base/g solution). Next,
a precise amount of the TBA OH in solution was mixed with diethyl
carbonate (DEtC) in a 1:5 molar ratio respectively and stirred for
1 hour at room temperature using magnetic stirrer. The final clear
initiator solution was analyzed by means of titration and NMR. In a
similar manner, clear solutions were obtained in 1-propanol and
2-propanol. A solution made using the TBA OH base in methanol
resulted in white precipitate which is removed by centrifuge
followed by filtration using 0.45.mu. syringe filter.
Transesterification reaction products were observed in the NMR for
all cases where the carbonate alkyl group was different from the
solvent, e.g. ethanol formation was observed when DEtC was added to
TBA OH in isopropanol and isopropyl groups associated with
carbonates were also observed.
Example 2
Malonate Resin (I) Synthesis.
[0070] A 500 ml reactor was charged with 149.8 g of Polyethylene
glycol (PEG 300), 100 g of diethyl malonate (DEM), 32.5 g of
1-octanol and 4-5 drops of titanium (IV) butoxide. The reactor was
equipped with a Dean-Stark apparatus, mechanical stirrer, nitrogen
flow and heating equipment. The mixture was heated to about
180.degree. C. with stirring under nitrogen atmosphere. During an
eight-hour reaction time, about 70 ml of ethanol was collected. The
final product was a lightly yellow colored liquid with less than
0.15 wt. % of residual DEM as determined by gas chromatography
(GC). Gel permeation chromatography (GPC) analysis showed Mw/Mn
(PDI) of 4191/2818 (1.49) in gram/mole and a malonate methylene
equivalent molecular weight of 360 g/mole.
Example 3
Basic Nail Color Formulation
[0071] FD&C and D&C dyes commonly used in nail enamel
formulations were evaluated in Michael addition based crosslinkable
compositions. Such colorants may also be used in other coating
application industries such as automotive and industrial paints,
architectural paints, plastics, adhesives and others. Concentrated
dispersions of dye in Malonate resin from example 2 were prepared
first. Said dispersions were then used to formulate simple nail
enamel color coat formulations. All nail enamel color coats were
formulated to contain dye concentrations at 3% dye loading by
weight. Finally, nail enamel coatings of controlled thickness are
prepared to evaluate certain applications and color properties. The
following is an example how a dye dispersion and color nail enamel
coat is prepared and serves as general preparative example:
Dye Dispersion:
[0072] First, 10.04 g of Malonate resin (I) from example 2 was
weighed directly into a tared 60 ml capacity mortar and 3.00 g of
D&C Red 30 Indigoid dye was weighed in next. A spatula was
briefly used to hand blend the dye into the resin and a pestle was
then used to grind the paste in the mortar to a fine consistency.
The mixture was ground/milled by hand for approximately 10-25
minutes using the pestle and mortar until a Hegman Fineness of
Grind value of 7 was achieved. The pigment dispersion was then
transferred to a glass jar and sealed for later use.
Nail Enamel Color Coat:
[0073] Into a 20 ml glass vial, 0.65 g of the above D&C Red 30
dye dispersion was added. An additional 1.95 g of Malonate resin
(I) from example 2 was charged to the vial and 1.58 g of DTMPTA was
added next. The materials in the vial were mixed by hand using a
spatula to achieve homogeneity. After this, 0.41 g of butylacetate
(BA) was mixed in as well. The vial was sealed and vigorously
shaken until homogenous. Test panels to be coated were placed into
position at this point. Bird Bars (3 & 6 mil) for coating
application were made ready. The glass vial was unsealed and 0.41 g
of the methanol based catalyst of example 1 was added. The lid was
placed back on the vial. The complete mixture was vigorously shaken
for 1-3 minutes to make it homogenous. Once mixing was completed,
the mixture was promptly cast as films using the Bird Bars on
4''.times.6'' polycarbonate panels. Tack free time was recorded and
coating surface wrinkling was observed as the films cured. Nail
enamel coatings typically are about 1.0-1.5 mil thick, sometimes up
to 2 mil thick per coating layer when applied by brush on finger-
and/or toe nails although even thicker coatings are applied by
consumers that are less experienced.
[0074] Various dyes were thus evaluated and compared to a dye free
(uncolored) control and results are shown in Table 1.
[0075] The uncolored nail coating used as a reference film exhibits
slight surface wrinkling without any dye present. The amount of
surface wrinkling is inherent in the resin/formula combination used
for this evaluation. Any worsening of this surface wrinkling is
considered less desirable.
[0076] The films prepared at 3% dye concentration and 3 mil film
wet applied film thickness, were additionally evaluated by color
spectrophotometry to monitor color change upon aging. Once the
applied coating became tack free, a timer was started. Color
measurements were carried out for each film. Each coated panel was
measured at 3 different points during the aging process: (1) 1 hr.;
(2) overnight (>16 hours); and (3) after 1 week. Color analyses
were performed using a calibrated DataColor 800 Spectrophotometer
to measure the coated panels. The panels sat in ambient laboratory
conditions during the period of aging. The color measurement
changes (CIELAB system, L*(0=Black,100=White), a*(+Red,-Green),
b*(+Yellow,-Blue), total color change .DELTA.E,) for overnight and
1 week of aging, were determined using the 1 hr. color measurement
as the reference point from which the instrument's software
calculated the delta values. Whether a color change is noticeable
to the eye is a matter of personal opinion for end users of nail
color cosmetics. For purposes of this example, color changes of
.DELTA.E of <=1.0 were interpreted as Good. Color change of
.DELTA.E>1.0 but<=2.0 were interpreted as Fair yet still
considered acceptable as being viewed that such a color change
would be likely detected by a trained eye only. Color changes of
.DELTA.E>2.0 were less desirable as this color change is likely
to be readily noticeable even to an untrained eye. A color change
.DELTA.E>4.0 is significant, while a color change of
.DELTA.E>5 is an entirely different color. The results are shown
in Table 2.
TABLE-US-00001 TABLE 1 Films - 3 Films - 6 mils applied Thickness
mils applied Thickness Tack free Coating Tack free Coating Dye
used, time, Surface time, Surface Dye name Wt. % [min] Wrinkling
[min] Wrinkling Blank no dye 1.7 slight 2.0 slight Control FD&C
3% 5.3 slight 22.0 moderate Yellow 5 D&C 3% 4.5 none 5.3 none
Red 30
TABLE-US-00002 TABLE 2 3 mil Wet Film Same Day Color Overnight
Cured Analysis Color Change ~7 Day Color DYE (Reference Point)
Analysis Change Analysis Name L* a* b* .DELTA.L* .DELTA.a*
.DELTA.b* .DELTA.E* .DELTA.L* .DELTA.a* .DELTA.b* .DELTA.E*
FD&C 59.18 4.14 58.68 0.12 -0.5 -1.78 1.86 -1.94 2.70 -0.82
3.44 Yellow 5 D&C 33.83 31.45 13.40 0.29 0.02 1.07 1.11 0.40
0.23 1.28 1.36 Red 30
Example 4
General Synthesis of Carbonate Catalyst by Reacting Base and Carbon
Dioxide.
[0077] Tributylmethylammonium chloride (TBMA Cl), (10 g) was
dissolved in ethanol (8.7 g) and mixed with a 20 wt. % solution of
potassium ethoxide in ethanol (17.8 g) in 1:1 molar ratio.
Anhydrous ethanol was used. The mixture was allowed to mix under
agitation for 30 min, and was then centrifuged at 5000 rpm for 15
min to remove potassium chloride precipitate. The concentration of
tributylmethylammonium ethoxide was determined potentiometrically
by titrating it against 0.1 N HCl solution. Dry carbon dioxide gas
was passed through the tributylmethylammonium ethoxide solution
with stirring for 1 hour as to obtain the desired initiator. The
tributylmethylammonium ethylcarbonate (TBMA EC) solution in ethanol
is light yellow in color and is characterized by means of acid and
base titrations (potentiometric and with indicator) and NMR.
[0078] A tributylmethylammonium isopropylcarbonate (TBMA IPC)
catalyst solution was prepared in a similar manner.
Tributylmethylammonium chloride was reacted with potassium
tert-butoxide in essentially water free isopropanol followed by
centrifugation prior to passing carbon dioxide through the
solution. NMR analysis confirmed isopropylcarbonate as the anionic
species.
Example 5
Malonate Resin (II) Synthesis
[0079] A 3 L reactor was charged with 700.0 g of diethyl malonate,
619.8 g of 1,6-hexanediol (HDO) and 227.5 g of ethyl acetoacetate
(EAA). The reactor was equipped with a Dean-Stark apparatus,
overhead mechanical stirrer, nitrogen flow and heating equipment.
The mixture was heated to about 120.degree. C. with stirring under
nitrogen and then 0.62 g of phosphoric acid was added. Temperature
was then increased to 145.degree. C. and ethanol started to distill
at this temperature. Temperature was then stepwise increased to
180.degree. C. and continued until ethanol distillation stopped. In
total, 588 ml of ethanol was collected. The reaction was then
cooled to 120.degree. C. and vacuum was applied for 4 hours while
driving molecular weight. The final product is clear with less than
0.1% of residual monomer. GPC analysis showed Mw/Mn (PD) of
4143/1792 (2.31) in g/mole.
Example 6
Malonate Resin (III) Synthesis
[0080] A 5 L reactor was charged with 2075.0 g (8.12 moles) of
diethyl malonate (DEM), 1182.9 g (9.74 moles) of 1,3-propanediol
(PD) and 674.4 g (3.25 moles) of ethyl acetoacetate (EAA). The
reactor was equipped with a Dean-Stark apparatus, overhead
mechanical stirrer, nitrogen flow and heating equipment. The
mixture was heated to about 120.degree. C. with stirring under
nitrogen and then 1.57 g of phosphoric acid was added. Temperature
was then increased to 145.degree. C. and ethanol started to distill
at this temperature. Temperature was then stepwise increased to
180.degree. C. and continued until ethanol distillation stopped. In
total, 1396 g of ethanol was collected. The reaction was then
cooled to 120.degree. C. and vacuum was applied for 4 hours while
driving the molecular weight. The final product was very light
yellow in color with less than 0.5% of residual monomer. GPC
analysis showed Mw/Mn (PD) of 2337/1507 (1.55) in g/mole and
malonate methylene equivalent molecular weight of 169 g/mole.
Example 7
Basic Clear Nail Polish Formulation
[0081] The TBMA EC solution of Example 4 was tested as an initiator
catalyst. In a vial, 2.0 g of the malonate resin II of Example 5
was mixed with 2.68 g of DTMPTA, 0.4 g of BA and 0.80 g of the TBMA
EC solution was added. The complete formulation was mixed well
prior to observing gel time and applying a 3 mil test film on a
polycarbonate substrate to test coating curing behavior. The
ambient relative humidity was low at 15%, while the temperature was
21.degree. C. The absolute humidity was 2.8 [g/m.sup.3]. A similar
test was carried out with the TBMA IPC catalyst using 0.90 g of the
TBMA IPC solution to keep molar amounts of catalyst constant versus
the resin. Data in Table 3 shows that a notably shorter gel time
for the isopropanol based catalyst was observed in comparison to
the ethanol based catalyst.
TABLE-US-00003 TABLE 3 Tack free Gel time Catalyst Solvent time
[m:s] [min] TBMA EC Ethanol 1:30 50 TBMA IPC 2-Propanol 2:00 25
Example 8
[0082] The procedure as per Example 7 was repeated except that
varying amounts of dimethylammonium dimethylcarbamate (DMADMC) were
added to the TBMA EC solution prior to adding said solution to the
resin/DTMPTA solvent mix. The DMADMC was obtained from commercial
sources and purity was checked via NMR. DMADMC is the reaction
product between dimethylamine and carbon dioxide in a 2:1 molar
ratio, albeit small deviations from this stoichiometry are possible
in commercially available DMADMC materials. Such commercial
materials may also contain ammonium carbonates depending on source
purity. All ingredient amounts were kept the same and the DMADMC
amount is thus on top of the formulation. Only in experiment #4,
was DMADMC added to the resin/DTMPTA solvent mix rather than to the
catalyst solution. The complete formulation was mixed well prior to
observing gel time and applying a 3 mil test film on a
polycarbonate substrate to test coating curing behavior. The
ambient relative humidity was 48% while the temperature was
21.degree. C. The absolute humidity was 8.8 [g/m3]. Results in
Table 4 shows that addition of DMADMC greatly increases gel time
while the tack free time only marginally increases unless
significant amounts of DMADMC in excess to the catalyst are added.
No significant effect of DMADMC addition on film properties were
noted after cure.
TABLE-US-00004 TABLE 4 DMADMC/carbonate Tack free # catalyst (molar
ratio) time [m:s] Gel time 1 0 2:30 1 hr 2 0.5 2:20 12 hr 3 1 2:30
2 days 4 1 2:45 2 days 5 2 2:55 4 days 6 5 4:00 >4 days
Example 9
Red Nail Polish Formulation
[0083] A basic nail color formulation was prepared and evaluated
per the general procedures as outlined in example 3, however,
malonate resin II of example 5 was used to prepare a D&C Red 7
dye dispersion. The final overall formulation contained 0.167 g
D&C Red 7 dye, 0.948 g resin II of example 5, 0.632 g resin III
of example 6, 0.837 g ethanol and 2.449 g DTMPTA. 1.1604 g of TBMA
EC catalyst solution of example 4 was used to cure the formulation.
Another such formulation was prepared except that 4 wt % water
(relative to the total weight of the formulation) was added to this
second formulation. All formulations were mixed well and then a 3
mil test film was applied on a polycarbonate substrate to test the
curing behavior and coating final color. The relative humidity and
temperature was kept constant as the films cured and the absolute
humidity was 9.4 [g/m.sup.3]. Data in Table 5 shows that
significant and undesirable color change occurs as water is added
to the formulation.
TABLE-US-00005 TABLE 5 Water Tack free content, time, # wt. % [m:s]
L* a* b* .DELTA.E* Color 1 0 2:15 42.7 51.1 32.2 -- Red/Orange 2 4
2:30 51.5 46.1 47.6 18.5 Orange/Yellow
Example 10
Red Nail Polish Formulation
[0084] The procedure as per Experiment 9 was repeated except that a
D&C Red 33 was used as pigment to color the coating
formulation. Data in Table 6 shows that color does not change as
water is added to the formulation.
TABLE-US-00006 TABLE 6 Water Tack free content, time, # wt. % [m:s]
L* a* b* .DELTA.E* Color 1 0 1:45 44.28 47.44 19.19 -- Red 2 4 2:15
44.17 47.22 19.25 0.3 Red
Example 11
Red Nail Polish Formulation
[0085] The procedure as per Experiment 9 was repeated except that a
D&C Red 7 Calcium Lake was used as pigment. No additional water
was added and 0.967 g of the TBMA EC catalyst solution of Example 4
was used. However, two different rooms with controlled humidity and
temperatures were utilized to explore influence of low-to-medium
and high relative humidity levels coupled with temperatures at
about 20 and 25.degree. C. respectively. This represents nail
polish application use under normal and high humidity conditions.
The complete formulation was mixed well, split in two and then 3
mil test films were applied on polycarbonate substrates to test
curing behavior and coating final color. Results in Table 7 show
drastic color changes for this D&C Red 7 Calcium Lake system as
the nail coating cures at high humidity conditions--the color
changes notably as the film cures. The color displayed by the film
cured under low humidity conditions is considered the normal
D&C Red 7 Calcium Lake color and no color change is observed
during cure.
TABLE-US-00007 TABLE 7 Absolute Tack free humidity, time, # [g/m3]
[m:s] L* a* b* .DELTA.E* Color 1a 2.9 <2:30 37.39 46.14 18.23 --
Dark Red 1b 10.5 <2:30 62.31 36.09 62.28 51.6 Yellow
Example 12
Red Nail Polish Formulation
[0086] The procedure as per experiment 11 was repeated exploring a
variety of D&C and FD&C dyes. Data is presented in Table 8.
D&C Red No. 17 and D&C Red No. 36 are incompatible with the
nail polish chemistry as significant color changes are observed
during the curing process at both humidity levels. D&C Red No.
7 and D&C Red No. 33 show observable and undesirable color
changes during cure at higher humidity levels. D&C Red No. 6
does show a measurable color difference for the cured films but the
color change during cure is less apparent. The other dyes show
minor color differences when the cured films are compared but no
visible color change during the cure is observed. Since the
formulation is split in two and brought into a higher temperature
and humidity environment during the experiment, it is speculated
that condensation of water at high humidity levels on the colder
film may potentially have affected film surface and therewith moved
the color CIELAB results slightly yet systematically. Since only a
minor color change was observed for these dyes, the panels prepared
under high humidity conditions were re-measured one week later to
assess dye color stability. Results shown in Table 9 show minor
color changes for the cured films and these dyes are assessed as
stable.
TABLE-US-00008 TABLE 8 Tack Absolute free Dye humidity, time, # Dye
class [g/m3] [m:s] L* a* b* .DELTA.E* Color 1a D&C Red Monoazo
7.0 1.5 51.96 51.52 39.82 -- Red/Orange No. 6 1b D&C Red
Monoazo 19.5 2.5 52.24 48.51 47.04 7.8 Red/Orange No. 6 2a D&C
Red Monoazo 7.2 1.5 38.93 46.25 23.28 -- Red No. 7 2b D&C Red
Monoazo 20.0 7 55.05 42.22 53.41 34.4 Yellow No. 7 3a D&C Red
Diazo 8.8 1.5 Significant and immediate color change/dye No. 17
breakdown to brown 3b D&C Red Diazo 19.6 2 Significant and
immediate color change/dye No. 17 breakdown to brown 4a D&C Red
Xanthene 9.0 2.5 61.06 55.69 35.84 -- Red/Orange No. 21 4b D&C
Red Xanthene 19.3 3.5 61.76 56.05 31.57 4.3 Red/Orange No. 21 5a
D&C Red Xanthene 9.0 2 63.58 56.03 24.02 -- Red/Orange No. 22
5b D&C Red Xanthene 19.5 5 63.42 56.51 28.57 4.6 Red/Orange No.
22 6a D&C Red Xanthene 8.5 1.5 58.76 70.41 -5.17 -- Bright No.
28 Red/Pink 6b D&C Red Xanthene 20.8 4 55.99 71.61 -2.15 4.3
Bright No. 28 Red/Pink 7a D&C Red Indigoid 9 1.5 51.41 43.81
13.45 -- Red No. 30 7b D&C Red Indigoid 20.8 2.5 53.61 39.86
12.71 4.6 Red No. 30 8a D&C Red Monoazo 8.7 1.5 34.31 42.79
-3.88 -- Dark Red No. 33 8b D&C Red Monoazo 21 4 40.23 39.3
-11.74 10.4 Dark Red No. 33 9a D&C Red Monoazo 9.0 1.5
Significant and immediate color change/dye No. 36 breakdown to
black 9b D&C Red Monoazo 20.9 2.0 Significant and immediate
color change/dye No. 36 breakdown to black 10a FD&C Monoazo 8.6
1.5 46.19 50.28 30.66 -- Red Red No. 40 10b FD&C Monoazo 19.6
2.5 47.79 49.64 28.03 3.1 Red Red No. 40
TABLE-US-00009 TABLE 9 # Dye Dye class L* a* b* .DELTA.E* Color 1b
D&C Red Monoazo 52.24 48.51 47.04 Red/ No. 6 Orange 1c D&C
Red Monoazo 52.44 49.48 48.02 1.4 Red/ No. 6 Orange 4b D&C Red
Xanthene 61.76 56.05 31.57 Red/ No. 21 Orange 4c D&C Red 2
Xanthene 63.02 57.09 31.37 1.6 Red/ No. 1 Orange 5b D&C Red
Xanthene 63.42 56.51 28.57 Red/ No. 22 Orange 5c D&C Red
Xanthene 64.30 56.14 27.50 1.4 Red/ No. 22 Orange 6b D&C Red
Xanthene 55.99 71.61 -2.15 Bright No. 28 Red/ Pink 6c D&C Red
Xanthene 56.77 71.71 0.57 2.83 Bright No. 28 Red/ Pink 7b D&C
Red Indigoid 53.61 39.86 12.71 Red No. 30 7c D&C Red Indigoid
53.6 40.51 13.07 0.74 Red No. 30 8b D&C Red Monoazo 40.23 39.3
-11.74 -- Dark No. 33 Red 8c D&C Red Monoazo 39.65 40.02 -10.70
1.4 No. 33 10b FD&C Red Monoazo 47.79 49.64 28.03 -- Red No. 40
10c FD&C Red Monoazo 45.45 47.84 25.86 3.7 Red No. 40
List of Chemical Acronyms Used in the Examples
TABLE-US-00010 [0087] BA butyl acetate DEM diethyl malonate DEtC
diethyl carbonate DMADMC dimethylammonium dimethylcarbamate DTMPTA
di-trimethylolpropane tetraacrylate EAA ethyl acetoacetate HDO
1,6-hexanediol PD 1,3-propanediol PEG 300 polyethylene glycol, Mw =
300 TBA OH tetrabutylammonium hydroxide TBMA Cl
tributylmethylammonium chloride TBMA EC tributylmethylammonium
ethylcarbonate TBMA IPC tributylmethylammonium isopropylcarbonate
TMPTA trimethylolpropane triacrylate
[0088] The present disclosure may be embodied in other specific
forms without departing from the spirit or essential attributes of
the invention. Accordingly, reference should be made to the
appended claims, rather than the foregoing specification, as
indicating the scope of the disclosure. Although the foregoing
description is directed to the preferred embodiments of the
disclosure, it is noted that other variations and modification will
be apparent to those skilled in the art, and may be made without
departing from the spirit or scope of the disclosure.
* * * * *