U.S. patent application number 10/383826 was filed with the patent office on 2004-09-09 for covalently bonding nail primer.
Invention is credited to Duff, James, Hong, Andry, Moore, Daniel, Schoon, Douglas, Vu, Thong.
Application Number | 20040176507 10/383826 |
Document ID | / |
Family ID | 32927134 |
Filed Date | 2004-09-09 |
United States Patent
Application |
20040176507 |
Kind Code |
A1 |
Schoon, Douglas ; et
al. |
September 9, 2004 |
Covalently bonding nail primer
Abstract
The present invention relates generally to the field of primers
and adhesion promoters. More specifically, the primer of the
present invention is comprised of one or more multi-carbonylated
methacrylates. In a preferred embodiment, a non-ketone polar
solvent is also employed. The resulting composition eliminates
primer related discoloration of artificial nail enhancements,
eliminates the potential for corrosion of skin and nails, and
eliminates risk of chemical burn injury, while providing stronger
adhesion than currently available primers.
Inventors: |
Schoon, Douglas; (Dana
Point, CA) ; Duff, James; (Escondido, CA) ;
Vu, Thong; (Vista, CA) ; Hong, Andry;
(Monterey Park, CA) ; Moore, Daniel; (Escondido,
CA) |
Correspondence
Address: |
Ward & Olivo
708 Third Avenue
New York
NY
10017
US
|
Family ID: |
32927134 |
Appl. No.: |
10/383826 |
Filed: |
March 7, 2003 |
Current U.S.
Class: |
524/315 |
Current CPC
Class: |
C08F 290/06 20130101;
A61K 8/37 20130101; A61Q 3/02 20130101; C09D 133/10 20130101; C08L
2205/05 20130101; C08L 71/02 20130101; A61K 8/41 20130101; C08G
2650/50 20130101; C08L 71/02 20130101; C08L 2666/04 20130101; C09D
133/10 20130101; C08L 2666/20 20130101 |
Class at
Publication: |
524/315 |
International
Class: |
C08K 005/10 |
Claims
We claim:
1. A primer comprising: an amine; a multi-carbonylated
methacrylate; and a solvent.
2. A primer according to claim 1, wherein said solvent comprises a
polar non-ketone solvent.
3. A primer according to claim 1, wherein said solvent comprises a
non-polar non-ketone solvent.
4. A primer according to claim 1, wherein said amine is a
polyethyleneglycolamine, polyoxypropyleneamine,
polyethyleneglycol-polyox- ypropyleneamine,
polyoxypropylenediamine, polyethyleneglycol-polyoxypropyl-
enediamine, polyethyleneglycoltriamine, or
polyethyleneglycol-polyoxypropy- lenetriamine.
5. A primer according to claim 1, wherein the amine concentration
ranges between 0.5 and 20 percent inclusively.
6. A primer according to claim 1, wherein said multi-carbonylated
methacrylate is acetoacetoxy ethyl methacrylate.
7. An adhesive primer comprising: an amine; an acetoacetoxy ethyl
methacrylate; and a solvent.
8. A primer according to claim 7, wherein said solvent comprises a
polar non-ketone solvent.
9. A primer according to claim 7, wherein said solvent comprises a
non-polar non-ketone solvent.
10. A primer according to claim 7, wherein said amine is a
polyethyleneglycolamine, polyoxypropyleneamine,
polyethyleneglycol-polyox- ypropyleneamine,
polyoxypropylenediamine, polyethyleneglycol-polyoxypropyl-
enediamine, polyethyleneglycoltriamine, or
polyethyleneglycol-polyoxypropy- lenetriamine.
11. A primer according to claim 7, wherein said amine concentration
ranges between 0.5 and 20 percent inclusively.
12. An improved nail primer comprising: an amine; a
multi-carbonylated methacrylate; and a solvent.
13. A primer according to claim 12, wherein said solvent comprises
a polar non-ketone solvent.
14. A primer according to claim 12, wherein said solvent comprises
a non-polar non-ketone solvent.
15. A primer in accordance with claim 12, wherein said amine has a
hydrophilic backbone.
16. A primer in accordance with claim 12, wherein said amine is a
polyethyleneglycolamine, polyoxypropyleneamine,
polyethyleneglycol-polyox- ypropyleneamine,
polyoxypropylenediamine, polyethyleneglycol-polyoxypropyl-
enediamine, polyethyleneglycoltriamine, or
polyethyleneglycol-polyoxypropy- lenetriamine.
17. A primer according to claim 12, wherein said amine
concentration ranges between 0.5 and 20 percent inclusively.
18. A primer according to claim 12, wherein said multi-carbonylated
methacrylate is acetoacetoxy ethyl methacrylate.
19. An essentially non-yellowing nail primer comprising: an amine;
a multi-carbonylated methacrylate; and a solvent.
20. A primer according to claim 19, wherein said solvent comprises
a polar non-ketone solvent.
21. A primer according to claim 19, wherein said solvent comprises
a non-polar non-ketone solvent.
22. A primer in accordance with claim 19, wherein said amine has a
hydrophilic backbone.
23. A primer in accordance with claim 19, wherein said amine is a
polyethyleneglycolamine, polyoxypropyleneamine,
polyethyleneglycol-polyox- ypropyleneamine,
polyoxypropylenediamine, polyethyleneglycol-polyoxypropyl-
enediamine, polyethyleneglycoltriamine, or
polyethyleneglycol-polyoxypropy- lenetriamine.
24. A primer according to claim 19, wherein said amine
concentration ranges between 0.5 and 20 percent inclusively.
25. A primer according to claim 19, wherein said multi-carbonylated
methacrylate is acetoacetoxy ethyl methacrylate.
Description
FIELD OF THE INVENTION
[0001] The present invention relates generally to the field of
primers and adhesion promoters. More specifically, the primer of
the present invention is comprised of one or more
multi-carbonylated methacrylates. In a preferred embodiment, a
non-ketone polar solvent is also employed.
[0002] The disclosed primer has particular utility as a primer for
nails and other proteinaceous substrates. For a number of years,
nail technicians have searched for acceptable substitutes for
extremely corrosive primers that cause yellowing of nail
enhancements. These (meth)acrylic acid-based primers (and all other
current nail primers) rely on relatively weak hydrogen bonding to
achieve interfacial bonding. In contrast, the present invention is
a significant advance in the art--a non-corrosive, non-yellowing
primer that covalently bonds to the nail plate. In other words, the
disclosed primer will not corrode or irritate the surrounding
tissue or nail plate, nor will it discolor the artificial nail
enhancement, while simultaneously bonding the enhancement to the
keratin substrate far more strongly than currently available
products.
BACKGROUND OF THE INVENTION
[0003] The nail plate (i.e., the natural nail) is primarily
composed of keratin, a water-insoluble, fibrous protein that is a
major structural component of skin, hair, wool, silk, feathers,
scales, nails and hooves. While keratins can obviously differ
greatly in their amino acid makeup, hard keratins may all be
generally characterized as cross-linked polypeptides.
Alpha-keratins such as nails and hooves may be further
characterized by their relatively higher percentages of the amino
acid cysteine. Typically, the alpha-helix coils of the polypeptides
are cross-linked with disulphide bonds between adjacent cysteines.
The resulting plate-like cells are cemented to each other with a
sticky substance and held together by rivet-like structures called
desmosomes. Many cell layers adhere to each other to form the nail
plate--a structure that resembles a brick and mortar wall.
[0004] Primers are adhesion promoters that improve adhesion by
increasing interfacial compatibility between surfaces, e.g., the
nail plate and an applied coating. For example, a coating of nail
polish will resist chipping and peeling if a good base coat is
used. Base coats are more compatible with the nail plate than the
nail polish. Base coats act as the "go-between" or "anchor", to
improve adhesion.
[0005] Primers are also frequently used with artificial nail
enhancements since acrylic nail products normally have poor
adhesion to nail plates. In general, nail plate primers can be
thought of as double-sided sticky tape, joining the nail plate to
the nail enhancement. The nail plate surface is made up of chemical
groups possessing specific structures. Primer molecules must match
the chemical and structural characteristics of the nail plate. More
particularly, one end of the primer is reactive with the
methacrylate monomers. With these types of primers, physical
abrasion of the nail plate is required to achieve proper levels of
adhesion to the keratin substrate. Moreover, these acids are
corrosive, and if used improperly they can cause damage to the nail
plate and surrounding tissue. These acids can also cause
discoloration of the nail enhancement and are a leading cause of
nail product discoloration. This invention eliminates a large
percentage of discoloration problems for professional nail
technicians. But even more importantly, in response to a number of
chemical burn injuries, primarily to children, the Consumer Product
Safety Commission recently issued a regulation requiring
child-resistant packaging for all household products containing
more than 5% methacrylic acid. However, child-resistant caps
increase the risk of spills in the salon as Nail Professionals
struggle to remove the cap. This invention solves both the burn
injury and child-resistant cap issues because it utilizes a
non-corrosive solvent, while still providing the desired adhesion
properties.
[0006] Commercially available nail primers rely solely on hydrogen
bonding. Hydrogen bonding on organic substrates such as keratin
typically depends on the interaction between an oxygen or nitrogen
atom that is covalently bonded to the upper surface of the nail
plate and a hydrogen atom, covalently bonded to methacrylic acid,
which is covalently linked to the polymer. A special type of
interaction called a hydrogen bond exists between the interfaces of
these dissimilar surfaces. Hydrogen bonds are types of attractive,
intermolecular bonds that are characteristic of atoms with high
electonegativity, i.e. fluorine, oxygen, sulfur, and nitrogen. They
are many times weaker than the weakest covalent bond, which is
found between a carbon and acidic hydrogens such as C--H as found
in chloroform and acetylene. This weakness accounts for the
attraction between the acidic hydrogen and a nearby organic, acidic
hydroxyl group of acrylic or methacrylic acid primer, as well as
the inherent relative weakness of hydrogen bonds. The overall
strength of the hydrogen bond is determined by the strength of this
relatively weak carbon/hydrogen bond. It is a controlling factor in
hydrogen bond strength. Therefore, when acidic primers are used,
the weakest adhesive link will exist between an oxygen molecule on
the keratin surface and the acidic hydrogen of (meth)acrylic acid.
Since covalent bonds are many times stronger than hydrogen bonding,
improvements in adhesive bond strength can be achieved by
eliminating the hydrogen bond and replacing it with a stronger,
more permanent, organic covalent bond.
[0007] It is clear from the foregoing that there are three
fundamental problems with currently available methacrylic primers
and acrylic acid adhesion promoters. First is the corrosive nature
of their primary component, methacrylic acid. Second, they create
temporary hydrogen bonds that are inherently weaker than covalent
bonds, leading to a weaker interfacial adhesive bond between the
natural nail plate and the primer molecule, with a stronger
adhesive bond between the primer molecule and the polymer chain of
the nail enhancement. Third, acid-based primers are a primary cause
of nail enhancement discoloration. Fourth, acid-based primers can
result in chemical burn injuries.
SUMMARY OF THE INVENTION
[0008] The present invention solves the discoloration and
corrosiveness problems associated with currently available primers
by providing the first truly non-corrosive, non-yellowing
covalently bonding primer. To date, nail primers and adhesion
promoters have been corrosive due to their use of methacrylic or
acrylic acid as the primary component. The present invention does
not rely on these problematic components. Previous nail primers
relied on relatively weak hydrogen bonding between nail and primer.
The present invention employs components that are capable of
creating continuous covalent bonds from the nail plate to the
artificial nail enhancement, providing much improved adhesion.
Additionally, previous nail primers were a prevalent cause of
yellowing during "fills" when the primer came into direct contact
with existing nail enhancement product on the natural nail. When
using traditional primers, Nail Professionals must take great care
to avoid the acid-based primer coming into contact with the
artificial nail. Every two weeks when the artificial nail is
"filled in" in the areas of new growth, dark yellow bands appear
across the width of the nail enhancement when the (meth)acrylic
acid primer comes into contact with the existing enhancement
polymer.
[0009] These and other advantages are accomplished by the present
invention, which relates to a primer comprised of one or more
multi-carbonylated methacrylates. In a preferred embodiment,
acetoacetoxy ethyl methacrylate ("AAEMA") is reacted with
polyoxypropylenetriamine to produce an imine, or Schiff base, in an
equilibrium reaction. In alternative embodiments,
triethyleneglycoldiamine or other primary amines can be used
instead of triethyleneglycoldiamine to achieve similar results.
Simultaneous with this imine reaction, an amine group of the
polyoxypropylenetriamine may also react with a carbonyl ester group
of AAEMA to form an amide. Finally, the Schiff base undergoes a
further electron rearrangement reaction in which an electron shifts
to the beta carbon of the acetoacetoxy group (as shown below).
[0010] The resulting composition does not exhibit undesirable
corrosive properties and is not based on (meth)acrylic acid and, in
fact, contains no acidic functionality. Moreover, the disclosed
primer provides stronger adhesion than any commercially available
nail primer because it allows certain amino acid functional groups
on the surface of the nail plate to covalently bond with carbonyl
groups in the primer, creating much stronger linkages than can be
achieved with hydrogen bonding of traditional primers.
[0011] Other objects, features, and characteristics of the present
invention, as well as the methods of operation and functions of the
related elements of the structure, and the combination of parts and
economies of manufacture, will become more apparent upon
consideration of the following detailed description, which forms
part of this specification.
DETAILED DESCRIPTION OF THE INVENTION
[0012] As required, a detailed illustrative embodiment of the
present invention is disclosed herein. However, techniques,
systems, and operating structures in accordance with the present
invention may be embodied in a wide variety of forms and modes,
some of which may be quite different from those in the disclosed
embodiment. Consequently, the specific structural and functional
details disclosed herein are merely representative, yet in that
regard, they are deemed to afford the best embodiment for purposes
of disclosure and to provide a basis for the claims herein, which
define the scope of the present invention. The following presents a
detailed description of a preferred embodiment (as well as some
alternative embodiments) of the present invention.
[0013] The present invention is a dramatically improved primer that
is particularly appropriate for use with nails. Herein, "nail"
refers to not only human nails, but also nails and hooves of
animals, and any other hard surface proteinaceous materials. The
nail primer of the present invention is principally comprised of
multi-carbonylated methacrylates dissolved in a suitable solvent or
other delivery system. In a preferred embodiment of the present
invention, the aforementioned components may be diluted in polar
non-ketone solvents, however, non-polar solvents will work as
well.
[0014] Various formulas have been tested by the applicant. One
preferred embodiment comprises a polyether amine having a
hydrophilic backbone, an acetoacetoxy methacrylate, and a polar
non-ketone solvent. Of course, other components can be substituted
as described below. One preferred polyether amine is
triethyleneglycoldiamine. Again, other similar components (such as
polyoxypropylenetriamine) can be utilized to achieve the results of
this invention.
[0015] The preferred amines contain two or three primary amine
functional groups, respectively. The primary amine functional
groups are located on secondary carbon atoms at the ends of
aliphatic polyether chains. Other primary amines, including
monofunctional, difunctional and trifunctional amines, may be used
in the present invention to achieve the desired results. Such
primary amines include all polyetheramines, including but not
limited to polyethyleneglycolamine, polyoxypropyleneamine,
polyethyleneglycol-polyoxypropyleneamine, polyoxypropylenediamine,
polyethyleneglycol-polyoxypropylenediamine,
polyethyleneglycoltriamine,
polyethyleneglycol-polyoxypropylenetriamine. Some examples of the
above-mentioned components include, but are not limited to
melamine, N,N-dimethylformamide, 1,5-diaminopentane and
dibutylamine.
[0016] One particularly preferred multi-carbonylated methacrylate
is acetoacetoxy ethyl methacrylate (referred to herein as
"AAEMA").
[0017] The preferred solvent of the present invention is a
non-ketone solvent. This ensures that the solvent will not react
with the carbonyl group in the methacrylate, nor compete with the
AAEMA carbonyl reaction. In nail applications, this helps prevent
yellowing of the nail enhancement. However, in alternative
embodiments of the invention where perhaps a slight coloration to
the solvent blend would not be objectionable, a ketone solvent can
be utilized if appropriate conditions are used during the bulk
chemical reaction.
[0018] The solvent utilized in the present invention is also
preferably a polar solvent to minimize the amount of discoloration
which is observed when a non-polar solvent is utilized. However, in
alternative embodiments of the present invention, a non-polar
solvent can be utilized without compromising the integrity of the
primer, which retains its adhesive and non-corrosive properties.
Particularly preferred polar non-ketone solvents include ethanol
and isopropanol. Other useful solvents include, but are not limited
to, ethers, esters, glycol ethers, chlorinated solvents, siloxanes,
tetrahydrofuran, methanol and other higher molecular weight
alcohols, and suitable combinations thereof.
[0019] The weight percentages of the epoxy amine component in the
tested formulas ranged from 0.75 to 2.5 percent, while the molar
ratios of AAEMA to amine ranged from 1 to 5. Upon mixing, the
carbonyl group of the acetoacetoxy group of AAEMA reacts with the
primary amine group to form an imine, or Schiff base. In a
preferred embodiment, the primary amine is
triethyleneglycoldiamine. This reaction proceeds as follows: 1
[0020] wherein R represents the remainder of the amine. Other amine
groups may also react with AAEMA. This reaction is followed by
electron re-arrangement favoring the beta carbon of the
acetoacetoxy group: 2
[0021] It should also be appreciated that the amine groups can also
react with AAEMA ester groups to form an amide: 3
[0022] Analytical testing using a Liquid Chromatography Mass
Spectrometer (LC-MS) demonstrates that the imine formation reaction
takes place more readily than the amide formation reaction. Further
analytical testing using a Gas Chromatograph Mass Spectrometer
(GC-MS) indicates that less than 10 percent of the AAEMA reacted in
the amide formation reaction. Additional testing confirms that
increasing the molar ratio of AAEMA to amine increases the number
of amine functional groups that react with AAEMA.
[0023] While the preferred embodiment of the present invention has
been illustrated with the reaction of an AAEMA and a polyether
amine (such as polyoxypropylenetriamine), other multi-carbonyl
methacrylate chemicals, and other amines may also be used. By using
chemicals with slightly different properties, the resulting primer
can effectively adhere to a wide variety of surfaces, such as
glass, metal, sheetrock, etc., to act as a primer for other
applications.
[0024] Comparative testing on the adhesion promoting activity of
the improved primer of the present invention was performed both in
a laboratory (with an instrument that tests adhesion) and in the
field by professional nail technicians. Laboratory testing showed
that the primer functioned better than its ingredients (amine,
AAEMA, and ethanol) individually. More importantly, the nail primer
of this invention worked better than all other commercially
available nail primers tested.
[0025] The following procedure was used in the laboratory testing.
First, a clean keratin substrate (hoof) was coated with the tested
primer. A system utilizing ethyl methacrylate monomer liquid and a
methacrylate copolymer powder was applied to the top of the primed
hoofs. After the monomer and copolymer completely polymerized,
adhesion testing apparatus utilizing a computer controlled
assembly, including a sharp blade held at a precise angle to the
surface of the hoof, was used to peel or delaminate the
methacrylate polymer from the coated keratin substrate at a
predetermined speed. The force needed to delaminate the polymer was
detected and recorded by the computerized control system. The
greater the force needed to peel or delaminate the polymer from the
keratin substrate, the stronger the adhesive bond was to the
keratin substrate. Table 1 illustrates the results of the
laboratory tests:
1 TABLE 1 Adhesion Standard Strength Deviation N N Main Ingredients
Company Advanced 300 65 Methacrylic acid, Pinnacle Formula Isobutyl
Methacry- Primer late X- 340 60 Methacrylic acid, Star Nail
Strength Isobutyl Methacry- Primer late Original 400 65 Methacrylic
acid, International Non- Isobutyl Methacry- Nail Lifting late
Manufacturers No Lift 490 105 100% Methacrylic No Lift Nails Primer
acid Bondex 500 80 Methacryloyloxy- O.P.I ethyl maleate, ethyl
acetate Coval- 570 140 Polyoxypropylene- Creative Nail ently
triamine, AAEMA, Design Bonding Ethanol Primer
[0026] The improved nail primer of the present invention shows
average adhesion strength of 570 N. The strongest commercially
available primer had adhesion strength of only 500 N.
[0027] The significant increase in strength achieved by the
disclosed primer can be largely attributed to its ability to
covalently bond to the nail plate. As was previously discussed,
presently available primers, including those identified in Table 1
(other than the present invention) are bonded to the nail plate via
hydrogen bonding. In contrast, applicant's primer takes advantage
of the greatly increased bond strengths attained through covalent
bonding.
[0028] Obviously, with individual differences in both keratins and
nail surfaces, a number of covalent reaction mechanisms are
possible. It is anticipated, however, that two reactions will
dominate. Because of the surprisingly high level of adhesion, we
believe our data shows that the dominant reaction involves a
direct, continuous series of covalent bonds between the keratin and
the enhancement polymer. In the first, ester groups in the primer
react with amines in keratin: 4
[0029] where R is the rest of the primer. In the alternative
reaction, amines in the primer react with carboxylic groups in
keratin: 5
[0030] where R' is the rest of the primer.
[0031] In any given case, one reaction might dominate over the
other, or both reactions may proceed simultaneously. Those of skill
in the art will appreciate that it is not the precise reaction
mechanism that is important, but rather the fact that covalent
bonding, via one or more mechanisms, is occurring. This is the
advance that arguably will make all previous nail primers
obsolete.
[0032] Confirmatory data was also collected in field tests. In a
two month study, 18 nail technicians performed tests on a total of
429 clients. The tests showed that the client's nail enhancements
were less likely to lift when using the primer of the present
invention. Moreover, while discoloration of nail enhancements is
inevitable when using a primer that contains methacrylic acid, use
of the primer of the present invention eliminated such
discoloration. To date, the improved primer of the present
invention has been field tested on 4,582 people yielding equally
successful results.
[0033] While the present invention has been described with
reference to one or more preferred embodiments, which embodiments
have been set forth in considerable detail for the purposes of
making a complete disclosure of the invention, such embodiments are
merely exemplary and are not intended to be limiting or represent
an exhaustive enumeration of all aspects of the invention. The
scope of the invention, therefore, shall be defined solely by the
following claims. Further, it will be apparent to those of skill in
the art that numerous changes may be made in such details without
departing from the spirit and the principles of the invention.
* * * * *