U.S. patent application number 11/579274 was filed with the patent office on 2009-05-21 for nail polish film with optical effect.
This patent application is currently assigned to L'OREAL. Invention is credited to Doris Hiam Galvez, Philippe Ilekti.
Application Number | 20090126316 11/579274 |
Document ID | / |
Family ID | 34952372 |
Filed Date | 2009-05-21 |
United States Patent
Application |
20090126316 |
Kind Code |
A1 |
Ilekti; Philippe ; et
al. |
May 21, 2009 |
NAIL POLISH FILM WITH OPTICAL EFFECT
Abstract
The present invention provides a flexible article with an
optical, relief, and/or olfactory effect for making up and/or
caring for the nails, comprising: at least one adhesive layer for
fixing the article to the nail; at least one organic film; and at
least one material with an optical, relief, or olfactory
effect.
Inventors: |
Ilekti; Philippe; (Maison
Alfort, FR) ; Hiam Galvez; Doris; (Burlington,
CA) |
Correspondence
Address: |
OLIFF & BERRIDGE, PLC
P.O. BOX 320850
ALEXANDRIA
VA
22320-4850
US
|
Assignee: |
L'OREAL
Paris
FR
|
Family ID: |
34952372 |
Appl. No.: |
11/579274 |
Filed: |
May 17, 2005 |
PCT Filed: |
May 17, 2005 |
PCT NO: |
PCT/FR2005/050335 |
371 Date: |
January 15, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60583492 |
Jun 29, 2004 |
|
|
|
Current U.S.
Class: |
53/111R ; 132/73;
156/313; 156/60 |
Current CPC
Class: |
A45D 31/00 20130101;
A61Q 3/02 20130101; A61Q 3/00 20130101; A61K 8/87 20130101; A45D
29/001 20130101; A61K 8/0208 20130101; Y10T 156/10 20150115 |
Class at
Publication: |
53/111.R ;
132/73; 156/60; 156/313 |
International
Class: |
A45D 29/00 20060101
A45D029/00; B65B 9/00 20060101 B65B009/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 19, 2004 |
FR |
0451004 |
Claims
1-52. (canceled)
53. A flexible article with an optical, relief, and/or olfactory
effect for making up and/or caring for the nails and/or nails,
comprising: at least one adhesive layer for fixing the article to
the nail; at least one organic film; and at least one material with
an optical, relief, and/or olfactory effect.
54. An article according to claim 53, wherein said material is
present within said film.
55. An article according to claim 53, wherein it comprises at least
two films with distinct compositions, superposed on the adhesive
layer.
56. An article according to claim 55, wherein each of the films
contains at least one material with an optical, relief, and/or
olfactory effect.
57. An article according to claim 55, wherein at least one of the
organic films is free of material with an optical, relief, and/or
olfactory effect.
58. An article according to claim 57, wherein said film is
transparent.
59. An article according to claim 57, wherein it is a film which is
not contiguous with the adhesive layer.
60. An article according to claim 53, wherein it has a dry matter
content of more than 80% by weight or more.
61. An article according to claim 53, wherein it has a water
take-up at 25.degree. C. of 20% or less.
62. An article according to claim 53, wherein it has a storage
modulus E' of 1 MPa or more, at a temperature of 30.degree. C. and
a frequency of 0.1 Hz.
63. An article according to claim 53, wherein it has a deformation
at break, .di-elect cons..sub.r, of 5% or more, and/or an energy at
break per unit volume, W.sub.r, of 0.2 J/cm.sup.3 or more.
64. An article according to claim 53, wherein said organic film
derives from cross-linking a cross-linkable composition and/or from
evaporating off the organic or aqueous solvent phase from a
solution or dispersion of at least one film-forming polymer.
65. An article according to claim 64, wherein it comprises at least
one polymeric film deriving from thermally, photochemically and/or
chemically cross-linking a cross-linkable composition.
66. An article according to claim 65, wherein said composition
comprises at least one reactive system formed by: at least one
first compound (A) comprising at least two functions (X); at least
one second compound (B) comprising at least two functions (Y),
reactive towards the X functions, said reactive systems having a
mean functionality (total number of X and Y functions/total number
of molecules of compounds (A) and (B)) of more than 2.
67. An article according to claim 64, wherein said cross-linking is
of the polyaddition and/or polycondensation type, of compounds
comprising at least two isocyanate and/or epoxy functions with
compounds having at least two labile hydrogen functions.
68. An article according to claim 67, wherein the compounds
carrying reactive isocyanate type functions are selected from
aliphatic, cycloaliphatic or aromatic diisocyanates, triisocyanates
and polyisocyanates, with a molecular mass of less than 10000.
69. An article according to claim 64, wherein said cross-linking is
carried out photochemically and employs at least two types of
compounds respectively carrying at least one unsaturated double
bond, in the presence of a photoinitiator.
70. An article according to claim 53, wherein it comprises at least
one polymeric film obtained by evaporating off the organic or
aqueous solvent phase from a solution or dispersion of at least one
film-forming polymer.
71. An article according to claim 70, wherein said polymeric film
derives from evaporating off the organic solvent phase of a
solution or dispersion of at least one film-forming polymer.
72. An article according to claim 71, wherein said polymer is
selected from homo- and copolymers of (meth) acrylic acid esters
and/or amides, homo- and copolymers of vinyl esters or amides,
celluloses and cellulose derivatives, polyurethanes, acrylic
polyurethanes, polyureas, polyurea polyurethanes, polyester
polyurethanes, polyether polyurethanes, polyesters, polyester
amides, fatty chain polyesters, epoxy compounds and arylsulfonamide
condensates.
73. An article according to claim 70, wherein said polymeric film
derives from evaporating off the aqueous phase of an aqueous
dispersion of film-forming polymeric particles and wherein the
aqueous dispersion of film-forming polymer particles is a latex,
pseudolatex or a mixture thereof.
74. An article according to claim 73, wherein said polymer is
selected from polycondensates, anionic, cationic, non ionic or
amphoteric polyurethanes, polyurethane-acrylics,
polyurethane-polyvinylpyrrolidones, polyester-polyurethanes,
polyether-polyurethanes, polyureas, polyurea polyurethanes,
polyesters, polyester amides, fatty chain polyesters, polyamides
and epoxy ester resins, acrylic and/or vinyl polymers or
copolymers, acrylic/silicone or nitrocellulose/acrylic copolymers,
polymers resulting from radical polymerization of one or more
radical monomers, inside and/or partially on the surface of
pre-existing particles of at least one polymer selected from the
group constituted by polyurethanes, polyureas, polyesters and
polyesteramides and/or alkyds.
75. An article according to claim 53, wherein it comprises at least
one material with an optical effect in a quantity sufficient to
produce a specific optical effect perceptible to the naked eye,
said specific optical effect being chosen from a metallic effect
and in particular a mirror effect, a goniochromatic effect, a
rainbow effect and a thermochromic effect.
76. An article according to claim 53, wherein it comprises at least
one material with a relief effect present in a quantity sufficient
to produce, on the surface of said art, a specific relief effect
which is perceptible to the touch, said specific relief effect
being chosen from a rough effect, a grained effect and a hammered
effect.
77. An article according to claim 53, wherein it comprises at least
one material with an olfactory effect in a quantity sufficient to
produce a specific odorizing effect which is perceptible by the
user, which is a fragrancing substance.
78. An article according to claim 53, wherein said adhesive layer
comprises at least one adhesive material.
79. An article according to claim 53, wherein said adhesive
material is such that said article cannot be removed by peeling
when it is applied to the surface of a synthetic or natural nail
after leaving for at least 24 hours.
80. An article according to claim 78, wherein said adhesive
material is selected from copolymers deriving from copolymerizing
vinyl monomers with polymeric entities, copolymers having a
polymeric skeleton with a Tg of 0.degree. C. to 45.degree. C.
grafted with chains deriving from acrylic and/or methacrylic
monomers and, in contrast, having a Tg of 50.degree. C. to
200.degree. C., and polyisobutylenes having a relative molar mass,
Mv, of 10000 or more and 150000 or less.
81. An article according to claim 53, wherein the surface of said
adhesive layer is coated with a removable support constituted by a
plastic film modified by a surface treatment with silicone or with
salts of C.sub.12 to C.sub.22 fatty acids.
82. An article according to claim 53, wherein said removable
support is constituted by a plastic film modified by a surface
treatment with silicone or with salts of C.sub.12 to C.sub.22 fatty
acids.
83. A substance for making up and/or for caring for nails and/or
false nails comprising, in packaging, which is substantially
airtight, at least one article according to claim 53, the packaging
being such that said article is preserved in a partially dry
form.
84. A substance according to claim 83, wherein said article has a
dry matter content of less than 80% by weight relative to the total
weight of said article.
85. A substance according to claim 83, wherein the packaging
comprises a reservoir which may contain said article in a sealed
manner.
86. A method of preparing a flexible article for making up and/or
caring for the nails, comprising at least the following steps
consisting of superposing on a removable support: a) at least one
layer of a composition based on at least one adhesive material; and
b) at least one layer of at least one composition which can form,
by cross-linking and/or evaporation of its organic or aqueous
solvent phase, an organic film containing at least one material
with an optical, relief, and/or olfactory effect, said film being
formed consecutively to deposition of said composition.
87. A method according to claim 86, wherein it comprises in step b)
deposition of a first composition and its transformation into an
organic film, and depositing, onto the film formed, a second
composition which differs from the first composition and
transforming it into a second organic film.
88. A method according to claim 87, wherein each of the films
contains a material with an optical, relief, and/or olfactory
effect.
89. A method according to claim 86, wherein the second film is free
of material with an optical, relief, and/or olfactory effect.
90. A method according to claim 86, wherein the article is a
flexible article with an optical, relief, and/or olfactory effect
for making up and/or caring for the nails and/or false nails,
comprising: at least one adhesive layer for fixing the article to
the nail; at least one organic film; and at least one material with
an optical, relief, and/or olfactory effect.
91. A method of preparing a substance according to claim 86,
comprising the following steps consisting of superposing on a
removable support: a) at least one layer of a composition based on
at least one adhesive material; and b) at least one layer of at
least one composition which can form, by cross-linking and/or
evaporation of its organic or aqueous solvent phase, an organic
film containing at least one material with an optical, relief,
and/or olfactory effect, said film being formed consecutively to
deposition of said composition; c) if necessary, partially drying
said article obtained; and d) packaging said article in a partially
dry condition within a substantially airtight packaging.
92. A method of making up the nails using an article, comprising
applying the adhesive face of an article as defined in claim 53 to
a natural or synthetic nail.
93. An article according to claim 79, wherein said adhesive
material is selected from copolymers deriving from copolymerizing
vinyl monomers with polymeric entities, copolymers having a
polymeric skeleton with a Tg of 0.degree. C. to 45.degree. C.
grafted with chains deriving from acrylic and/or methacrylic
monomers and, in contrast, having a Tg of 50.degree. C. to
200.degree. C., and polyisobutylenes having a relative molar mass,
Mv, of 10000 or more and 150000 or less.
94. A substance according to claim 84, wherein the packaging
comprises a reservoir which may contain said article in a sealed
manner.
95. A method according to claim 87, wherein the second film is free
of material with an optical, relief, and/or olfactory effect.
Description
[0001] The present invention relates to a flexible article with an
optical, relief, and/or olfactory effect for application to the
nails to make them up and/or to care for them.
[0002] Conventionally, nails or false nails are made up using
liquid makeup compositions, still generally known as nail polish.
Such nail polish is generally applied to the surface of the nail to
be made up in the form of superposed layers, allowing an
intermediate drying step between each application of nail polish.
In reality, such a makeup method is not entirely satisfactory.
[0003] Firstly, applying it requires a certain amount of time.
[0004] Further, that type of makeup has to be re-applied within a
short period because it does not stay on sufficiently well. In
three to five days in general, polish which has been applied flakes
and loses its gloss. It must then be removed and fresh makeup needs
to be re-applied.
[0005] Finally, conventional nail polish formulations generally
involve the use of volatile solvents which generate a disagreeable
odor during application.
[0006] The aim of the present invention is to propose a method of
making up and/or caring for nails or false nails which, in contrast
to conventional liquid type nail polish formulations, is easy and
rapid to apply stays on significantly longer, has a significantly
reduced organic solvent(s) content and also can provide an optical,
relief, and/or olfactory cosmetic effect.
[0007] More precisely, in a first aspect, the present invention
provides a flexible article for making up and/or caring for nails
and/or false nails, comprising: [0008] at least one adhesive layer
for fixing the article to the nail; [0009] at least one organic
film; and [0010] at least one material with an optical, relief,
and/or olfactory effect.
[0011] In a variation, the article may comprise at least two
different organic films superposed on the adhesive layer.
[0012] In particular, each of said films may contain at least one
material with an optical, relief, and/or olfactory effect.
[0013] More particularly, one of them is free of said material. In
that implementation, it is generally the film which is not
contiguous with the adhesive layer.
[0014] In this variation of the invention, the film which is free
of material with an optical, relief, and/or olfactory effect is
preferably transparent.
[0015] As used here, the term "transparent" means that the
cross-linked coating has a HAZEBYK index of less than 5 as measured
with a KYKHAZEGLOSS type gloss meter.
[0016] In a second aspect, the present invention provides a method
of preparing a flexible article for making up and/or caring for the
nails comprising at least the following steps consisting of
superposing, on a removable support:
[0017] a) at least one layer of a composition based on at least one
adhesive material; and
[0018] b) at least one layer of at least one composition which can
form, by cross-linking and/or evaporation of its organic or aqueous
solvent phase, an organic film containing at least one material
with an optical, relief, and/or olfactory effect, said film being
formed consecutively to deposition of said composition.
[0019] In a variation of the invention, the method comprises a step
b) of depositing a first composition and transforming it into an
organic film and depositing, onto the film thus formed, a second
composition which differs from the first composition, and then
transforming it into a second organic film.
[0020] In a further variation, said method comprises, at the end of
step b), a step of drying said article which step is stopped before
a completely dry condition is obtained for said article. The
article obtained is termed "partially dry".
[0021] In a third aspect, the present invention provides a
substance for making up and/or caring for the nails and/or false
nails comprising, in packaging which is substantially airtight, at
least one article in accordance with the invention, the packaging
being such that the article is preserved in a partially dry
form.
[0022] Within the context of the present invention, the term
"partly dry" is intended to mean that the article obtained after
forming an organic film, i.e. after evaporating off the organic or
aqueous solvent phase from a solution or dispersion of at least one
film-forming polymer or by cross-linking a cross-linkable
composition, is not entirely free of residual solvent. In
particular, it has a dry matter content of less than 80%, in
particular less than 75% and more particularly less than 70% by
weight relative to its total weight.
[0023] In accordance with a particular implementation, said
packaging comprises a reservoir, such as a pouch, which may or may
not be flexible, and which is suitable for containing a substance
in airtight manner. In particular, it is impermeable to air and/or
solvents. Said packaging can preserve said article from prematurely
drying out completely before it is used.
[0024] In a fourth aspect, the present invention provides a method
of preparing a substance as defined above, comprising the following
steps consisting of superposing, on a removable support:
[0025] a) at least one layer of a composition based on at least one
adhesive material; and
[0026] b) at least one layer of at least one composition which can
form an organic film by cross-linking and/or evaporation of its
organic or aqueous solvent phase, containing at least one material
with an optical, relief, and/or olfactory effect, said film being
formed consecutively to deposition of said composition;
[0027] c) if necessary, partially drying the article obtained;
and
[0028] d) packaging said article in a partially dry condition
within a substantially airtight packaging.
[0029] In this implementation, the article only becomes completely
dry, and thus only achieves its definitive form, after application
to the nail, simply by exposure to the ambient air.
[0030] In a fifth aspect, the present invention provides a method
of making up and/or caring for the nails, the method comprising
applying the adhesive face of an article in accordance with the
invention to a natural or synthetic nail.
[0031] Within the context of the present invention, the term
"organic" also encompasses composite type materials, i.e.
associating an organic component with an inorganic component. As an
example, the organic film may behave as an organic matrix into
which at least one inorganic material is incorporated, and which
may contribute per se to the production of the film.
[0032] Within the context of the present invention, the term
"flexible" means sufficient flexibility for the article of the
invention. More precisely, that article is in the form of a film
which can accommodate stretch-type mechanical deformations to
adjust to the surface of a nail. This deformability is
characterized in particular by the deformation at break parameter
.di-elect cons..sub.r discussed below.
[0033] The article of the invention differs from a false nail type
article, which is characterized by a stiffness which is
incompatible with such mechanical deformation.
[0034] A further difference between the article of the invention
and a false nail lies in the fact that this article is sensitive to
polar organic solvents of the acetone, ester and/or lower alcohol
type. The organic film on the outer face of the article of the
invention, i.e. the face which does not adhere to the nail, can
swell, which results in an increase in its weight when it is
brought into contact with one of said solvents. A false nail is
completely free of such sensitivity. This ability of the article of
the invention to swell is advantageous since it can be eliminated
when it is applied to the surface of a nail or a false nail. The
article of the invention can readily be removed simply by using a
conventional remover, as opposed to a false nail which has to be
taken off. More precisely, it may be removed by organic solvents,
in particular alkyl acetates and mixtures thereof.
[0035] It also stays on for a significant period on the scale of at
least one week. It turns out to be resistant to water, friction and
shocks and does not wear or flake significantly within that
period.
[0036] Finally, as indicated above, the article of the invention is
of particular advantage on the make-up front since it can produce a
large variety of original effects which go beyond conventional
colored effects. The inventors have shown that the film structure
of the article is particularly advantageous in producing effects
which are other than simple conventional static colored effects, in
particular by packaging therewith materials with an optical,
relief, and/or olfactory effect, of a wide variety of natures. Said
materials may in particular be organic, inorganic and/or composite
in nature.
[0037] Clearly, certain materials may produce a plurality of
simultaneous effects on the articles of the invention. As an
example, particles with an optical effect may, in addition to the
expected optical effect, provide a colored or even a relief effect
if their particle size is sufficiently large.
[0038] For obvious reasons, the quantities of these materials which
may be used can vary significantly as a function of the desired
effect and as a function of the nature of the materials and/or
their size and/or their form when in the form of particles and/or
fibers.
[0039] The skilled person will be capable of making that adjustment
as a function of the material under consideration.
[0040] Optical Effect Material
[0041] The flexible article of the invention may contain at least
one material with a specific optical effect, in particular present
in its organic film.
[0042] As described above, this effect differs from a simple
conventional hue effect, i.e. uniform and stabilized such as that
produced by conventional coloring materials, for example
monochromatic pigments. Within the context of the invention, the
term "stabilized" means free of color variability with angle of
observation or in response to a temperature change.
[0043] Said material is present in a quantity sufficient to produce
an optical effect which is visible to the naked eye.
Advantageously, it is an effect selected from goniochromatic,
metallic especially mirror, soft-focus, rainbow and/or
thermochromic effects.
[0044] As an example, said material may be selected from particles
with a metallic glint, goniochromatic coloring agents, diffractive
pigments, thermochromic agents, optical whitening agents, as well
as fibers, in particular interferential fibers. Clearly, said
various materials may be combined to simultaneously produce two
effects or even a novel effect within the context of the
invention.
[0045] Particles with a Metallic Glint
[0046] The term "particles with a metallic glint" denotes particles
of nature, size, structure, and surface condition that allows them
to reflect incident light, in particular in a non iridescent
manner.
[0047] Particles with a substantially planar outer surface are also
suitable since they can readily produce intense specular reflection
which may be qualified as a mirror effect if their size, structure
and surface condition allow.
[0048] The particles with a metallic glint of the invention may,
for example, reflect light in all of its visible components without
significantly absorbing one or more wavelengths. The spectral
reflectance of said particles may, for example, be more than 70% in
the 400 nm [nanometers] to 700 nm range, preferably at least 80% or
even 90% or 95%.
[0049] Said particles are generally 1 .mu.m [micrometer] or less in
thickness, in particular 0.7 .mu.m or less in thickness, and in
particular 0.5 .mu.m or less in thickness.
[0050] In particular, the total proportion of particles with a
metallic glint is 20% by weight or less, in particular 10% by
weight or less relative to the total weight of the article.
[0051] In particular, the particles with a metallic glint which are
used in accordance with the invention are selected from: [0052]
particles of at least one metal and/or at least one metallic
derivative; [0053] particles comprising a substrate, which may be
organic or mineral, a mono-material or a multi-material, at least
partially covered with at least one layer with a metallic glint
comprising at least one metal and/or at least one metallic
derivative; and [0054] mixtures of said particles.
[0055] Examples of metals which may be present in said particles
which may be mentioned are Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti,
Zr, Pt, Va, Rb, w, Zn, Ge, Te, Se and mixtures or alloys thereof.
Ag, Au, Cu, Al, Zn, Ni, Mo, Cr and their mixtures or alloys (for
example bronzes and brasses) are preferred metals.
[0056] The term "metallic derivatives" means compounds derived from
metals, in particular oxides, fluorides, chlorides and
sulfides.
[0057] Examples that can be mentioned of metallic derivatives which
may be present in said particles are metallic oxides such as oxides
of titanium, in particular TiO.sub.2, of iron, in particular
Fe.sub.2O.sub.3, of tin, of chromium, barium sulfate and the
following compounds: MgF.sub.2, CrF.sub.3, ZnS, ZnSe, SiO.sub.2,
Al.sub.2O.sub.3, MgO, Y.sub.2O.sub.3, SeO.sub.3, SiO, HfO.sub.2,
ZrO.sub.2, CeO.sub.2, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, MoS.sub.2
and their mixtures or alloys.
[0058] In a first variation, the particles with a metallic glint
may be composed of at least one metal as defined above, at least
one metallic derivative as defined above or a mixture thereof.
[0059] Said particles may be at least partially covered with a
layer of another material, for example a transparent material such
as colophany, silica, stearates, polysiloxanes, polyester resins,
epoxy resins, polyurethane resins or acrylic resins.
[0060] Illustrative examples of such particles which may be
mentioned are particles of aluminum, such as those sold under the
trade names STARBRITE 1200 EAC.RTM. by SIBERLINE and METALURE.RTM.
by ECKART.
[0061] It is also possible to mention copper powders or alloy
mixtures such as reference 2844 sold by RADIUM BRONZE, metallic
pigments such as aluminum or bronze, such as those sold under the
trade name ROTOSAFE 700 by ECKART, particles of aluminum coated
with silica sold under the trade name VISIONAIRE BRIGHT SILVER by
ECKART and particles of metal alloy such as bronze powders (copper
and zinc alloy) coated with silica sold as VISIONAIRE BRIGHT
NATURAL GOLD by ECKART.
[0062] In a second variation, said particles may be particles
comprising a substrate and which thus present a structure that is
multilayered, for example two-layered. Said substrate may be
organic or inorganic, natural or synthetic, a mono- or
multi-material, solid or hollow. When the substrate is synthetic,
it may be produced in a form encouraging the formation of a
reflective surface after coating, in particular after depositing a
layer of material with a metallic glint. The substrate may, for
example, have a planar surface and the layer of materials with a
metallic glint may have substantially uniform thickness.
[0063] In particular, the substrate may be selected from the metals
and metallic derivatives mentioned above, and also from glasses,
ceramics, aluminas, silicas, silicates and in particular
aluminosilicates and borosilicates, synthetic mica such as
fluorophlogopite, and mixtures thereof, this list not being
limiting.
[0064] The layer with a metallic effect may completely or partially
coat the substrate and said layer may be at least partially coated
with a layer of another material, for example a transparent
material as mentioned above. In a particular implementation, said
layer with a metallic glint completely coats the substrate directly
or indirectly, i.e. with the interposition of at least one metallic
or non metallic intermediate layer.
[0065] The metals or metallic derivatives which may be used in the
reflective layer are as defined above. As an example, it may be
formed by at least one metal selected from silver, aluminum,
chromium, nickel, molybdenum, gold, copper, tin, magnesium and
mixtures (alloys) thereof. More particularly, sliver, chromium,
nickel, molybdenum and mixtures thereof may be used.
[0066] An illustrative example of said second type of particle
which may be mentioned is as follows: [0067] particles of glass
coated with a metallic layer, in particular those described in
Japanese patent documents JP-A-09188830, JP-A-10158450,
JP-A-10158541; JP-A-07258460 and JP-A-05017710.
[0068] Illustrative examples of such particles comprising a glass
substrate which may be mentioned are those coated respectively with
silver, gold or titanium in the form of flakes sold by NIPPON SHEET
GLASS under the MICROGLASS METASHINE trade names. Particles with a
glass substrate coated with silver in the form of flakes are sold
under the trade name MICROGLASS METASHINE REFSX 2025 PS by TOYAL.
Particles with a glass substrate coated with
nickel/chromium/molybdenum alloy are sold under the trade name
CRYSTAL STAR GF 550, GF 2525 by the same firm. Those coated with
either brown iron oxide or titanium oxide, tin oxide or a mixture
thereof such as those sold under the trade name REFLECKS.RTM. by
ENGELHARD or those sold under the trade name METASHINE MC 2080GP by
NIPPON SHEET GLASS are also known.
[0069] Said glass particles coated with metals may be coated with
silica, such as those sold under the trade name METASHINE series
PSS1 or GPS1 by NIPPON SHEET GLASS. [0070] Particles with a
spherical glass substrate which may or may not be coated with a
metal, in particular those sold under the trade name PRIZMALITE
MICROSPHERE by PRIZMALITE industries. [0071] Pigments from the
METASHINE 1080R range sold by NIPPON SHEET GLASS Co. LTD are also
suitable. Said pigments, more particularly those described in
Japanese patent JP 2001-11340, are C-GLASS glass flakes comprising
65% to 72% of SiO.sub.2 coated with a layer of rutile (TiO.sub.2)
type titanium oxide. Said glass flakes have a mean thickness of 1
.mu.m and a mean size of 80 .mu.m, giving a mean size/mean
thickness ratio of 80. They have blue, green, yellow or silver
glints depending on the thickness of the TiO.sub.2 layer. [0072]
Particles comprising a borosilicate substrate coated with silver,
also known as "white nacres". [0073] Particles with a metallic
substrate such as aluminum, copper, bronze, in the form of flakes,
are sold under the trade name STARBRITE by SILBERLINE and under the
trade name VISIONAIR by ECKART. [0074] Particles comprising a
synthetic mica substrate coated with titanium dioxide, for example
particles with a dimension in the range 80 .mu.m to 100 .mu.m
comprising a synthetic mica (fluorophlogopite) substrate coated
with titanium dioxide representing 12% of the total weight of the
particle are sold under the trade name PROMINENCE by NIHON KOKEN.
[0075] The particles with a metallic glint may also be selected
from particles formed by a stack of at least two layers with
different refractive indices. Said layers may be polymeric or
metallic in nature and in particular may include at least one
polymeric layer.
[0076] Thus, the particles with a metallic effect may be particles
deriving from a multi-layered polymeric film.
[0077] The choice of materials intended to constitute the various
layers of the multi-layered structure is clearly made so as to
provide the particles formed with the desired metallic effect.
[0078] Such particles have in particular been described in
International patent application WO-A-99/36477 and United States
patents U.S. Pat. No. 6,299,979 and U.S. Pat. No. 6,387,498 and are
more particularly identified in the section on goniochromatic
effects.
[0079] Diffractive Pigments
[0080] The term "diffractive pigment" as used in the present
invention means a pigment which is capable of producing a variation
in color depending on the angle of observation when illuminated
with white light, due to the presence of a structure which
diffracts light.
[0081] A diffractive pigment may comprise a diffraction grating
capable, for example, of diffractive an incident ray of
monochromatic light in predefined directions.
[0082] The diffraction grating may comprise a periodic motif, in
particular a line, the distance between two adjacent motifs being
of the same order of magnitude as the wavelength of the incident
light.
[0083] When the incident light is polychromatic, the diffraction
grating will separate the various spectral components of the light
and produce a rainbow effect.
[0084] Reference concerning the structure of diffractive pigments
can usefully be made to the article "Pigments exhibiting
diffractive effects" by Alberto Argoitia and Matt Witzman, 2002,
Society of Vacuum Coaters, 45.sup.th Annual Technical Conference
Proceedings, 2002.
[0085] The diffractive pigment may be produced from motifs having
different profiles, in particular triangular, symmetrical or
otherwise, crenellated, with a constant or non constant width, or
sinusoidal.
[0086] The spatial frequency of the grating and the depth of the
motifs will be selected as a function of the degree of separation
of the various desired orders. The frequency may, for example, vary
from 500 lines per mm [millimeter] to 3000 lines per mm.
[0087] Preferably, the particles of diffractive pigment each have a
flattened form, in particular the form of a flake.
[0088] A single pigment particle may comprise two diffractive
gratings which cross, perpendicularly or otherwise.
[0089] One possible structure for the diffractive pigment may
comprise a layer of a reflective material, covered on at least one
side with a layer of a dielectric material. This layer may provide
the diffractive pigment with better rigidity and durability. The
dielectric material may thus, for example, be selected from the
following materials: MgF.sub.2, SiO.sub.2, Al.sub.2O.sub.3,
AlF.sub.3, CeF.sub.3, LaF.sub.3, NdF.sub.3, SmF.sub.2, BaF.sub.2,
CaF.sub.2, LiF and combinations thereof. The reflective material
may, for example, be selected from metals and their alloys and also
from non metallic reflective materials. Some metals which may be
used which may be mentioned are Al, Ag, Cu, Au, Pt, Sn, Ti, Pd, Ni,
Co, Rd, Nb, Cr and compounds, combinations and alloys thereof. Such
a reflective material may alone constitute the diffractive pigment
which will then be a monolayer.
[0090] In a variation, the diffractive pigment may comprise a
multi-layered structure comprising a core of a dielectric material
covered on at least one side with a reflective layer, or it may
completely encapsulate the core. A layer of a dielectric material
may also cover the reflective layer or layers. The dielectric
material used is thus preferably inorganic and may, for example, be
selected from metallic fluorides, metallic oxides, metallic
sulfides, metallic nitrides, metallic carbides and combinations
thereof. The dielectric material may be in the crystalline, semi
crystalline or amorphous state. In this configuration, the
dielectric material may, for example, be selected from the
following materials: MgF.sub.2, SiO, SiO.sub.2, Al.sub.2O.sub.3,
TiO.sub.2, WO, AlN, BN, B.sub.4C, WC, TiC, TiN, N.sub.4Si.sub.3,
ZnS, glass particles, diamond type carbon and combinations
thereof.
[0091] The diffractive pigment used may in particular be selected
from those described in United States patent application US
2003/0031870 published on Feb. 13, 2003.
[0092] A diffractive pigment may, for example, comprise the
following structure: MgF.sub.2/Al/MgF.sub.2; a diffractive pigment
with that structure is sold under the trade name SPECTRAFLAIR 1400
Pigment Silver by FLEX PRODUCTS, or SPECTRAFLAIR 1400 Pigment
Silver FG. The proportion by weight of MgF.sub.2 may be in the
range 80% to 95% of the total pigment weight.
[0093] Goniochromatic Coloring Agents
[0094] Within the context of the invention, a goniochromatic
coloring agent allows a color change, also termed a "color flop",
to be observed as a function of the angle of observation, which is
higher than that which may be obtained with nacres. One or more
goniochromatic coloring agents may be used simultaneously.
[0095] The goniochromatic coloring agent may be selected to present
a relatively large color change with the angle of observation.
[0096] The goniochromatic coloring agent may thus be selected so
that for a variation in the angle of observation in the range
0.degree. to 80.degree., illuminated at 450, a variation .DELTA.E
of at least 2 is observed in the color of the cosmetic composition,
measured in the CIE 1976 colorimetric space.
[0097] The goniochromatic coloring agent may also be selected so
that for an illumination at 45.degree. and a variation in the angle
of observation in the range 0.degree. to 80.degree., a variation Dh
of at least 30.degree. or even at least 40.degree. or at least
60.degree. or even at least 100.degree. is observed in the angle of
the hue of the cosmetic composition, using the CIE 1976
colorimetric space.
[0098] The goniochromatic coloring agent may, for example, be
selected from interferential multi-layered structures and liquid
crystal coloring agents.
[0099] In the case of a multi-layered structure, this may, for
example, comprise at least two layers, each layer, independently or
otherwise of the other layer(s) being produced, for example, from
at least one material selected from the group constituted by the
following materials: MgF.sub.2, CeF.sub.3, ZnS, ZnSe, Si,
SiO.sub.2, Ge, Te, Fe.sub.2O.sub.3, Pt, Va, Al.sub.2O.sub.3, MgO,
Y.sub.2O.sub.3, S.sub.2O.sub.3, SiO, HfO.sub.2, ZrO.sub.2,
CeO.sub.2, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, TiO.sub.2, Ag, Al, Au,
Cu, Rb, Ti, Ta, W, Zn, MoS.sub.2, cryolite, alloys, polymers and
combinations thereof.
[0100] The multi-layered structure may or may not be symmetrical
relative to a central layer as regards the chemical nature of the
stacked layers.
[0101] Examples of symmetrical interferential multi-layered
structures which may be used in compositions produced in accordance
with the invention are as follows: Al/SiO.sub.2/Al/SiO.sub.2/Al,
pigments with this structure being sold by DUPONT DE NEMOURS;
Cr/MgF.sub.2/Al/MgF.sub.2/Cr, pigments with this structure being
sold under the trade name CHROMAFLAIR by FLEX;
MoS.sub.2/SiO.sub.2/Al/SiO.sub.2/MoS.sub.2;
Fe.sub.2O.sub.3/SiO.sub.2/Al/SiO.sub.2/Fe.sub.2O.sub.3, and
Fe.sub.2O.sub.3/SiO.sub.2/Fe.sub.2O.sub.3/SiO.sub.2/Fe.sub.2O.sub.3,
pigments having these structures being sold under the trade name
SICOPEARL by BASF;
MoS.sub.2/SiO.sub.2/mica-oxide/SiO.sub.2/MoS.sub.2;
Fe.sub.2O.sub.3/SiO.sub.2/mica-oxide/SiO.sub.2/Fe.sub.2O.sub.3;
TiO.sub.2/SiO.sub.2/TiO.sub.2 and
TiO.sub.2/Al.sub.2O.sub.3/TiO.sub.2;
SnO/TiO.sub.2/SiO.sub.2/TiO.sub.2/SnO;
Fe.sub.2O.sub.3/SiO.sub.2/Fe.sub.2O.sub.3;
SnO/mica/TiO.sub.2/SiO.sub.2/TiO.sub.2/mica/SnO, pigments having
these structures being sold under the trade name XIRONA by MERCK
(Darmstadt). By way of example, said pigments may be pigments with
a silica/titanium oxide/tin oxide structure sold under the trade
name XIRONA MAGIC by MERCK, pigments with a silica/brown iron oxide
structure sold under the trade name XIRONA INDIAN SUMMER by MERCK
and pigments with a silica/titanium oxide/mica/tin oxide structure
sold under the trade name XIRONA CARIBBEAN BLUE by MERCK. INFINITE
COLORS pigments by SHISEIDO may also be mentioned. Depending on the
nature of the various layers, different effects are obtained. Thus,
with the Fe.sub.2O.sub.3/SiO.sub.2/Al/SiO.sub.2/Fe.sub.2O.sub.3
structure, the color passes from golden green to red-gray for
SiO.sub.2 layers from 320 nm to 350 nm; from red to golden for
SiO.sub.2 layers from 380 nm to 400 nm; from violet to green for
SiO.sub.2 layers from 410 nm to 420 nm; from copper to red for
SiO.sub.2 layers from 430 nm to 440 nm.
[0102] It is also possible to use goniochromatic coloring agents
with a multi-layered structure comprising alternating polymeric
layers.
[0103] A non-limiting list of illustrative materials which may
constitute the various layers of the multi-layered structure which
may be mentioned is as follows: polyethylene naphthalate (PEN) and
its isomers, for example 2,6-, 1,4-, 1,5-, 2,7- and 2,3-PEN,
polyalkylene terephthalates, polyimides, polyetherimides, atactic
polystyrenes, polycarbonates, polymethacrylates and alkyl
polyacrylates, syndiotactic polystyrene (sPS), syndiotactic
poly-alpha-methylstyrenes, syndiotactic polydichlorostyrene,
copolymers and mixtures of said polystyrenes, cellulose
derivatives, polyalkylene polymers, fluorinated polymers,
chlorinated polymers, polysulfones, polyethersulfones,
polyacrylonitriles, polyamides, silicone resins, epoxy resins,
polyvinyl acetate, polyether-amides, ionomeric resins, elastomers
and polyurethanes. Copolymers are also suitable, for example
copolymers of PEN (for example, copolymers of 2,6-, 1,4-, 1,5-,
2,7-, and/or 2,3-naphthalene dicarboxylic acid or its esters with
(a) acid terephthalic or its esters; (b) isophthalic acid or its
esters; (c) phthalic acid or its esters; (d) alkane glycols; (e)
cycloalkane glycols (for example cyclohexane dimethanol diol); (f)
alkane dicarboxylic acids; and/or (g) cycloalkane dicarboxylic
acids, copolymers of polyalkylene terephthalates and styrene
copolymers. Further, each individual layer may include mixtures of
two or more of the preceding polymers or copolymers. The choice of
materials intended to constitute the various layers of the
multi-layered structure is clearly made so as to endow the
particles formed with the desired optical effect.
[0104] Examples of pigments with a polymeric multi-layered
structure which may be mentioned are those sold by 3M under the
trade name COLOR GLITTER.
[0105] Liquid crystal coloring agents comprise, for example,
silicones or cellulose ethers onto which mesomorphous groups are
grafted.
[0106] Liquid crystal goniochromatic particles which may, for
example, be used are those sold by Chenix as well as those sold
under the trade name HELICONE.RTM. HC by WACKER.
[0107] Said agents may also be in the form of dispersed
goniochromatic fibers. Said fibers may, for example, be of a size
in the range 50 .mu.m to 700 .mu.m, for example about 300
.mu.m.
[0108] In particular, it is possible to use interferential fibers
with a multi-layered structure. Fibers with a multi-layered polymer
structure have in particular been described in European patent
documents EP-A-0 921 217 and EP-A-0 686 858 and in U.S. Pat. No.
5,472,798. The multi-layered structure may comprise at least two
layers, each layer, independently or not of the other layer(s),
being produced from at least one synthesized polymer. The polymers
present in the fibers may have a refractive index of 1.30 to 1.82
and preferably 1.35 to 1.75. Preferred polymers for constituting
the fibers are polyesters such as polyethylene terephthalate,
polyethylene naphthalate, polycarbonate; acrylic polymers such as
polymethyl methacrylate; polyamides.
[0109] Goniochromatic fibers with a two layered polyethylene
terephthalate/nylon-6 structure are sold under the trade name
TEIJIN under the trade name MORPHOTEX.
[0110] In a variation, said goniochromatic coloring agent may be
associated with at least one diffractive pigment.
[0111] The combination of these two materials results in an article
with an enhanced color variability, and thus which is capable of
allowing an observer to perceive a color change or even color
movement under a number of observation and illumination
conditions.
[0112] The weight ratio of the diffractive pigment relative to the
goniochromatic coloring agent is preferably in the range 85/15 to
15/85, more preferably in the range 80/20 to 20/80, still more
preferably in the range 60/40 to 40/60, for example of the order of
50/50. Such a ratio is favorable to the production of a sustained
rainbow effect and goniochromatic effect.
[0113] Optical Whitening Agents
[0114] Optical whitening agents are compounds which are well known
to the skilled person. Such compounds have been described in
"Fluorescent whitening agents, Encyclopedia of Chemical Technology,
Kirk-Othmer", vol 11, p. 227-241, 4.sup.eme edition, 1994,
Wiley.
[0115] More particularly, they can be defined as compounds which
absorb essentially in the UVA region between 300 nm and 390 nm and
emit essentially between 400 nm and 525 nm.
[0116] Optical whitening agents which may in particular be
mentioned include stilbene derivatives, in particular
polystyrylstilbenes and triazinstilbenes, coumarin derivatives, in
particular hydroxycoumarins and aminocoumarins, oxazole,
benzoxazole, imidazole, triazole, pyrazoline derivatives, pyrene
derivatives and porphyrin derivatives and mixtures thereof.
[0117] Said compounds are readily available commercially. Examples
which may be mentioned are as follows: [0118] the stilbene
derivative of naphtho-triazole sold under the trade name "Tinopal
GS", 4,4'-di-styryl-biphenyl sulfonate di-sodium salt (CTFA name:
disodium distyrylbiphenyl disulfonate) sold under the trade name
"Tinopal CBS-X", the cationic derivative of aminocoumarin sold
under the trade name "Tinopal SWN CONC.", sodium
4,4'-bis[(4,6-dianilino-1,3,5-triazin-2-yl)amino]stilbene-2,2'-disulfonat-
e sold under the trade name "Tinopal SOP",
4,4'-bis-[(4-anilino-6-bis(2-dihydroxyethyl)amino-1,3,5-triazin-2-yl)amin-
o]stilbene-2,2'-disulfonic acid sold under the trade name "Tinopal
UNPA-GX",
4,4'-bis-[anilino-6-morpholine-1,3,5-triazin-2-yl)amino]stilben- e
sold under the trade name "Tinopal AMS-GX",
4,4'-bis-[(4-anilino-6-(2-hydroxyethyl)methyl
amino-1,3,5-triazin-2-yl)amino]stilbene-2,2'-disodium sulfonate
sold under the trade name "Tinopal 5BM-GX", all from CIBA
Specialites Chimiques;
[0119] 2,5-thiophene di-yl bis(5-ter-butyl-1,3-benzoxazole) sold
under the trade name "Uvitex OB" by CIBA; [0120] the anionic
derivative of di-aminostilbene in dispersion in water, sold under
the trade name "Leucophor BSB liquide" by CLARIANT; [0121] optical
whitening lakes sold under the trade name "COVAZUR" by
WACKHERR.
[0122] The optical whitening agents which may be used in the
present invention may also be in the form of copolymers, for
example of acrylates and/or methacrylates, grafted with optical
whitening agent groups as described in French patent application FR
99 10942.
[0123] They may be used as is or introduced into the film in the
form of particles and/or fibers coated with said whitening agents,
such as those described below.
[0124] In particular, it is possible to use fibers coated with
optical whitening agents as sold by LCW under the trade name
Fiberlon 54 ZO3, with a length of about 0.4 mm and a weight of 0.5
deniers.
[0125] Material with Relief Effect
[0126] As described above, this relief effect may or may not be
associated with an optical effect. A material of this type is
generally present in a quantity sufficient to produce a relief
effect which is perceptible to the touch or even to the naked eye.
It may also be a rough, grained and/or hammered effect.
[0127] Material Producing a Rough Effect
[0128] The article of the invention is particularly advantageous as
regards binding solid particles or fibers in its film, thus
producing an original make-up relief effect. Further, particles
with a substantially spherical or ovoid form may produce a soft
make-up touch effect.
[0129] Advantageously, the solid particles have a substantially
spherical form to allow them to be properly distributed during
application onto the first layer.
[0130] The solid particles used in accordance with the invention
may have a mean size of 2.5 .mu.m to 5 mm, preferably 50 .mu.m to 2
mm. The smaller the particles, the better the staying power of the
particles. Using particles is also compatible with producing
motifs.
[0131] The solid particles may be formed from any material
satisfying the density properties defined above. As an example, the
solid particles may be formed from a material selected from glass,
zirconium oxide, tungsten carbide, plastics such as polyurethanes,
polyamides, polytetrafluoroethylene, polypropylene, metals such as
steel, copper, brass, chromium, wood, marble, onyx, jade, natural
nacre, precious stones (diamond, emerald, ruby, sapphire),
amethyst, aquamarine. Preferably, glass beads are used, such as
those sold under the trade name "SILIBEADS.RTM." by SIGMUND
LINDNER; said beads have the further advantage of also producing a
glossy and scintillating cosmetic effect.
[0132] The solid particles, which may or may not be deformable, may
be solid or hollow, colorless or colored, coated or otherwise.
[0133] Regarding the fibers used in the invention, they may be
fibers of synthetic or natural, mineral or organic origin.
[0134] The term "fiber" means an object with a length L and a
diameter D such that L is much greater than D, D being the diameter
of the circle in which the section of the fiber is inscribed. In
particular, the ratio L/D (or form factor) is selected so as to be
in the range 3.5 to 2500, preferably in the range 5 to 500, more
preferably in the range 5 to 150.
[0135] They may be fibers used in the fabrication of textiles, in
particular fibers of silk, cotton, wool, linen, cellulose fibers,
especially those derived from wood, vegetable or algae, rayon,
polyamide (Nylon.RTM.), viscose, acetate, in particular rayon
acetate, poly-(p-phenylene-terephthalamide) (or aramide) especially
Kevlar.RTM., acrylic polymer, especially polymethyl methacrylate or
poly 2-hydroxyethyl methacrylate, polyolefin and especially
polyethylene or polypropylene, glass, silica, carbon in particular
in the form of graphite, polytetrafluoroethylene (such as
Teflon.RTM.), insoluble collagen, polyesters, polyvinyl or
polyvinylidene chloride, polyvinyl alcohol, polyacrylonitrile,
chitosan, polyurethane, polyethylene phthalate and fibers formed by
a mixture of polymers such as those mentioned above, such as
polyamide/polyester fibers.
[0136] More particularly, the fibers are fibers of polyamide
(Nylon.RTM.).
[0137] In particular, it is possible to use polyamide fibers sold
by P Bonte under the trade name "Polyamide 0.9 Dtex 3 mm" having a
mean diameter of 6 .mu.m, a titer of about 0.9 dtex and a length of
0.3 mm to 5 mm. It is also possible to use cellulose (or rayon)
fibers having a mean diameter of 50 .mu.m and a length of 0.5 mm to
6 mm, such as those sold under the trade name "Natural rayon flock
fiber RC1BE-N003-M04" by Claremont Flock. It is also possible to
use polyethylene fibers such as those sold under the trade name
"Shurt Stuff 13 099F" by Mini Fibers.
[0138] Material Producing a Crepe Effect
[0139] The flexible article of the invention is also suitable for
containing a material which is capable of producing a grained or
crepe effect on the article surface.
[0140] Said material with a grained effect may be fragments of a
polymer film, which may or may not be colored, having two
substantially planar faces, with a thickness of 40 .mu.m to 200
.mu.m with the largest dimension being from 0.1 mm to 4 mm, the
fragments being insoluble in the medium of the composition intended
to form the organic film.
[0141] When the composition intended to form the film is applied to
the adhesive layer or to a support, the fragments of films are
readily distributed in the deposited layer and are disposed in a
random manner through its thickness. Cross-linking and/or drying
said composition then produces a film having portions which are
thicker than the mean thickness of the film, distributed in a
random manner on the film surface. The film surface then has a
discontinuous relief which is resistant to friction. An original
cosmetic relief effect is thus obtained, both to the touch and
visually, which adheres well to the made up support and has good
staying power.
[0142] The colored polymer film fragment may be obtained from
radical polymers, in particular vinyl polymers such as acrylic
polymers or polymers based on polyvinyl acetate, styrene-acrylic,
vinyl/versatate, vinyl/ethylene copolymers,
vinyl/versatate/acrylate or vinyl/ethylene/chloride terpolymers.
Preferably, styrene/acrylic copolymers are used. Such fragments
have in particular been described in European patent application
EP-A-1 036 554.
[0143] Advantageously, the thickness of the film fragment may be
from 70 .mu.m to about 130 .mu.m, preferably from about 90 .mu.m to
about 110 .mu.m.
[0144] Colored film fragments used in accordance with the invention
are sold under the trade name MONOCOLOR by QUADRA INDUSTRIES.
[0145] Material Producing a Hammered Effect
[0146] The inventors have also established that it is possible for
the film of the article of the invention to contain a material
comprising a pyrogenated silica mixture, a metallic pigment and an
organopolysiloxane compound to produce therein a hammered
appearance.
[0147] Such a mixture has been described in European patent
application EP-A-1 040 813. [0148] The organopolysiloxane may be
selected from polydimethylsiloxanes, polymethylethylsiloxanes,
copolymers of dimethylsiloxane and methylvinylsiloxane, copolymers
of dimethylsiloxane and up to 50 mole percent of
phenylmethylsiloxane.
[0149] The organopolysiloxanes may in particular be those sold in
solution in xylene under the trade name "Dow Corning 61 additive"
by Dow Corning, or those sold under the trade name "Rhodorsil SIL
AID 16" by Rhone-Poulenc.
[0150] The organopolysiloxane may be present in the organic film in
an effective amount so as to produce the hammered effect (formation
of a crater) and in particular in an amount of 0.01% to 10% by
weight relative to the total weight of said film, preferably 0.1%
to 5% by weight. [0151] The metallic pigments which may be used are
aluminum powders sold under the trade names "STAPA Non leafing
grade", "STAPA Metallic", "METALURE L55350" by ECKART, "Aluminum
Super 800" by WOLSTENHOLME International, "SILVET and 1630" by
SILBERLINE; bronze powders sold under the trade names "STAPA Golden
Bronze" by ECKART, "Pastel Standard" by WOLSTENHOLME
International.
[0152] Preferably, the organopolysiloxane and the metallic pigment
may be present in the organic film in an
organopolysiloxane/metallic pigment weight ratio of 0.1/100 to
5/100, preferably 0.5/100 to 1.5/100. In this weight ratio, a film
with a good hammered effect is obtained. [0153] The pyrogenized
silica present in the organic film may be in the form of
hydrophilic or hydrophobic pyrogenized silica film. Preferably,
hydrophilic pyrogenized silica is used.
[0154] The pyrogenized silicas may be obtained by high temperature
hydrolysis of a volatile silicon compound in a hydrogen-oxygen
flame, producing a finely divided silica. Such hydrophilic silicas
are, for example, sold under the trade names "AEROSIL 130.RTM.",
"AEROSIL 200.RTM.", "AEROSIL 255.RTM.", "AEROSIL 300.RTM.",
"AEROSIL 380.RTM." by DEGUSSA, "CAB-O-SIL HS-5.RTM.", "CAB-O-SIL
EH-5.RTM.", "CAB-O-SIL LM-130.RTM.", "CAB-O-SIL MS-55.RTM. ",
"CAB-O-SIL M-5.RTM." by CABOT.
[0155] Material with an Olfactory Effect
[0156] Advantageously, the articles of the invention may also be
provided with olfactory properties, especially by incorporating
into their organic film at least one odorifying material or a
fragrancing substance.
[0157] The fragrancing substance may be selected from any
odorifying substance which is well known to the skilled person, in
particular from essential oils and/or essences.
[0158] Said material olfactory may, if appropriate, be introduced
via a solvent-plasticizer.
[0159] The term "solvent-plasticizer" means a compound which at
least partially dissolves the olfactory material and which is
capable of evaporating off slowly.
[0160] The solvent-plasticizer may be selected from glycols such as
dipropylene glycol, ethyldiglycol, n-propylglycol, n-butylglycol,
methyldiglycol, n-butyldiglycol, alcohols such as cyclohexanol,
2-ethyl butanol, 3-methoxy butanol, 2-ethyl hexanol,
phenoxyethanol, esters such as glycol monoacetate, ethylglycol
acetate, n-butylglycol acetate, ethyldiglycol acetate,
n-butyldiglycol acetate, methyl abietate, isopropyl myristate,
propylene glycol diacetate, the acetate of propylene glycol methyl
ether, glycol ethers such as dipropylene glycol-methyl ether or
-butyl ether, used alone or as a mixture.
ARTICLE IN ACCORDANCE WITH THE INVENTION
[0161] The article of the invention may be characterized by a high
dry extract. In the dry state, it may have a quantity of dry
material of more than 80%, in particular more than 85%, in
particular more than 90% by weight relative to its total weight. In
other words, the quantity of volatile solvent is less than 20%, in
particular less than 15% and more particularly less than 10% by
weight relative to the total article weight.
[0162] However, in a further advantageous implementation, the
article of the invention may advantageously be in the partially dry
form. In this particular case, the article is advantageously
packaged in a reservoir such as a pouch, for example, which may or
may not be flexible, which is sufficiently airtight to preserve
this partially dry aspect. Only when used, and as a result when it
is brought into contact with air, will the article dry slowly to
acquire the dry matter content defined above.
[0163] In one substance in accordance with the invention, the
article of the invention advantageously has a dry matter content of
less than 80%, in particular less than 75%, in particular less than
70% relative to its total weight. Said article may also have a dry
matter content of more than 60%, especially more than 65% by weight
relative to the total weight.
[0164] Such an article, when removed from the packaging of the
substance of the invention, becomes dry as defined above within 24
hours following exposure to ambient air.
[0165] Preferably, the quantity of dry matter, usually termed the
"dry extract" of the films of the invention, is measured by heating
a sample using infrared radiation with a wavelength of 2 .mu.m to
3.5 .mu.m. Substances contained in said films which have a high
vapor pressure evaporate off under the effect of this radiation.
Measuring the loss of mass of the sample allows the "dry extract"
of the film to be determined. Said measurements are made using a
commercial LP16 infrared dessicator from Mettler. That technique is
fully described in the documentation furnished by Mettler
accompanying the apparatus.
[0166] The following measurement protocol is followed.
[0167] About 10 g [grams] of sample is placed in a metal cup. After
introduction into a dessicator, it is subjected to a temperature of
120.degree. C. for one hour. The moist mass of the sample,
corresponding to the initial mass and the dry mass of the sample,
corresponding to the mass after exposure to radiation, are measured
using a precision balance.
[0168] The dry matter content is calculated as follows:
Dry extract=100.times.(dry mass/moist mass).
[0169] Water Take-Up
[0170] The article of the invention is characterized in the dry
state by a water take-up at 25.degree. C. of 20% or less, in
particular 16% or less, and more particularly less than 10%.
[0171] In the present application, the term "water take-up of a
film" denotes the percentage of water absorbed by the article after
immersion in water for 60 minutes at 25.degree. C. (ambient
temperature). The water take-up is measured using pieces of about 1
cm.sup.2 cut from the dry article and weighed (measurement of mass
M1) then immersed in water for 60 minutes; after immersion, the
piece of the article is wiped to eliminate excess surface water
then weighed (measuring mass M2). The difference, M2-M1,
corresponds to the quantity of water absorbed by the article.
[0172] The water take-up is equal to [(M2-M1)/M1].times.100 and is
expressed as the percentage by weight relative to the weight of the
article.
[0173] Storage Modulus E'
[0174] Further, the article of the invention is advantageously a
film having a storage modulus E' of 1 MPa [megapascals] or more, in
particular 1 MPa to 5000 MPa, more particularly 5 MPa or more, in
particular 5 to 1000 MPa and still more particularly 10 MPa or
more, for example 10 MPa to 500 MPa at a temperature of 30.degree.
C. and a frequency of 0.1 Hz [Hertz].
[0175] The storage modulus is measured by DMTA (dynamic and
mechanical temperature analysis).
[0176] The viscoelastic tests are carried out with a DMTA apparatus
from Polymer TA Instruments (DMA2980 model) on a sample of the
article. Specimens are cut out (for example using a punch). They
have a typical thickness of about 150 .mu.m, a width of 5 mm to 10
mm and a useful length of about 10 mm to 15 mm.
[0177] The measurements are carried out at a constant temperature
of 30.degree. C.
[0178] The sample is placed under tension and subjected to small
deformations (for example a sinusoidal displacement of .+-.8 .mu.m)
during a frequency scan, the frequency being from 0.1 Hz to 20 Hz.
Thus, the working region is linear, with small deformations.
[0179] Said measurements allow the complex modulus E*=E'+iE'' of
the test composition film to be determined, E' being the storage
modulus and E'' the "lossy" modulus.
[0180] Deformation and/or Energy at Break
[0181] Advantageously, in the dry state the articles of the
invention have a deformation at break .di-elect cons..sub.r of 5%
or more, in particular 5% to 500%, more preferably 15% or more,
especially 15% to 400%, and/or an energy at break per unit volume
W.sub.r of 2 J/cm.sup.3 [joules/cubic centimeter] or more, in
particular 0.2 J/cm.sup.3 to 100 J/cm.sup.3, preferably more than 1
J/cm.sup.3, in particular 1 J/cm.sup.3 to 50 J/cm.sup.3.
[0182] The deformation at break and the energy at break per unit
volume are determined by tensile tests carried out on an article
about 200 .mu.m thick.
[0183] To carry out these tests, the article is cut into dumb-bell
shaped test specimens with a useful length of 33.+-.1 mm and a
useful width of 6 mm. The section (S) of the specimen is thus
defined as: S=width.times.thickness (cm.sup.2); this section is
used for the stress calculation.
[0184] The tests are carried out, for example, using a commercial
tensile apparatus sold under the trade name Lloyd.RTM. LR5K. The
measurements are carried out at ambient temperature (20.degree.
C.).
[0185] The specimens are stretched at a displacement rate of 33
mm/min, corresponding to a 100% extension per minute.
[0186] Thus, a displacement rate is imposed and the extension
.DELTA.L of the specimen and the force F necessary to impose said
extension are measured simultaneously. These data .DELTA.L and F
are used to determine the stress .sigma. and deformation .di-elect
cons. parameters.
[0187] A stress curve of .sigma.=(F/S) is obtained as a function of
the deformation .di-elect cons.=(.DELTA.L/L.sub.0).times.100, the
test being carried out until the sample breaks, L.sub.0 being the
initial length of the sample.
[0188] The deformation at break .di-elect cons..sub.r is the
maximum deformation of the sample before the break point (as a
%).
[0189] The energy at break per unit volume, W.sub.r in J/cm.sup.2,
is defined as the area beneath the stress/deformation curve,
i.e.:
W r = .intg. 0 r .sigma. ##EQU00001##
[0190] The organic film of the article of the invention may be
obtained by cross-linking a cross-linkable composition and/or by
evaporating off the organic or aqueous solvent phase of a solution
or dispersion of at least one film-forming polymer.
[0191] Cross-Linked Polymer
[0192] Within the context of the present invention, a
"cross-linked" film may be completely or partially cross-linked. In
the case of partial cross-linking, this is clearly sufficient to
form the expected film.
[0193] Clearly, the compounds used are selected, in particular
depending on the nature of the functions they respectively possess,
to be capable of interacting under the cross-linking reaction
conditions under consideration.
[0194] Said cross-linking can thus be achieved by a thermal,
photochemical and/or chemical route, in the presence or absence of
a catalyst. The skilled person is capable of carrying out said
cross-linking.
[0195] In a first variation, the cross-linking reaction is a
polyaddition or polycondensation reaction carried out in the
presence or absence of a catalyst.
[0196] In this first variation, the organic film may in particular
derive from cross-linking a reactive system formed by: [0197] at
least one first compound (A) comprising at least two functions (X);
and [0198] at least one second compound (B) comprising at least two
functions (Y), reactive towards the X functions.
[0199] Advantageously, the reactive system has a mean functionality
(total number of X and Y functions/total number of molecules of
compounds (A) and (B)) of more than 2 to produce a
three-dimensional network.
[0200] More particularly, to obtain a satisfactory cross-linking
effect, the mean functionality of the reactive system may be at
least 2.2 and more particularly may be from 2.5 to 100.
[0201] Compounds (A) and (B) may be organic in origin and in
particular of the monomer, oligomer, polymer and/or copolymer type,
or they may be inorganic in nature, for example, like a mineral
particle, in which case they have the two required functions (X) or
(Y) on the surface.
[0202] Reactive functions X and Y are selected from "reactive"
functions and functions comprising at least one labile
hydrogen.
[0203] More precisely, the reactive functions are selected from
isocyanates, epoxy compounds and ethylenically unsaturated double
bonds and the functions with labile hydrogen(s) are of the
carboxylic, alcohol (in particular phenol), primary or secondary
amine, amide, aminoalcohol and/or thiol type.
[0204] In this variation, compounds (A) and (B) respectively have
at least two reactive epoxy and/or isocyanate type functions and at
least two functions with (a) labile hydrogen(s), in particular of
the amine or aminoalcohol type, and may especially be selected from
the compounds mentioned above.
[0205] As an example, X may be an epoxy and/or isocyanate function
and Y may be selected from a carboxylic acid function and/or an
anhydride function and/or an amine function and/or a thiol function
and/or a hydroxyl function, in particular phenolic.
[0206] In this variation of the invention, cross-linking may be
carried out by bringing compounds (A) and/or (B) having functions
(X) and/or (Y) functions into contact in a blocked form which can
be unblocked in advance or under the reaction conditions used for
cross-linking. This alternative is well known to the skilled person
and will not be described in detail.
[0207] Compounds with Isocyanate Functions
[0208] Compounds comprising at least two free isocyanate functions
are known in the art. They may be polyisocyanates, including
diisocyanates or triisocyanates, which may have a molecular mass of
less than 500000, or even less than 10000. Said polyisocyanates are
generally obtained by polyaddition, polycondensation and/or
grafting, carrying at least two isocyanate functions, either at the
chain extremities or on the lateral groups.
[0209] The poly isocyanates may be linear, branched, aliphatic,
cycloaliphatic or aromatic.
[0210] Particular polyisocyanates which may be mentioned are
DESMODUR.RTM. N from BAYER and TOLONATE.RTM. HDB-LV from
RHODIA.
[0211] Compounds with Epoxy Functions
[0212] Compounds comprising at least two epoxy functions are also
known in the art. They may have any chemical nature. They may be
diepoxy compounds or polyepoxy compounds with low masses (5000 or
less), or oligomers or polymers of any chemical nature, obtained by
polyaddition, polycondensation and/or grafting, carrying at least
two free epoxy functions either at the chain extremities or on the
lateral groups.
[0213] Polymers with an epoxy function are sold under the trade
names CYRACURE.RTM. UVR-6110, CYRACURE.RTM. UVR-6105, CYRACURE.RTM.
ERL-4221E, CYRACURE.RTM. ERL-4206, CYRACURE.RTM. UVR 6128,
CYRACURE.RTM. UVR 6216 by UNION CARBIDE, DER.RTM. 439 by DOW
CHEMICAL, EPIKATES.RTM. 828, 1001, 1004, 1007 from SHELL,
ARALDITE.RTM. ECN1299 from CIBA-GEIGY, EPOXYNOVOLACS.RTM. from DOW
CHEMICAL.
[0214] Compounds with Ethylenically Unsaturated Double Bonds
[0215] Compounds carrying ethylenically unsaturated double bonds
may have any chemical nature. In particular, they may be selected
from:
[0216] a) polyesters with lateral and/or terminal (meth)acrylate
groups:
[0217] Said polyesters are, for example, sold by UCB under the
EBECRYL.RTM. (EBECRYL.RTM. 450: molar mass 1600, a mean of 6
acrylate functions per molecule, EBECRYL.RTM. 652: molar mass 1500,
a mean of 6 acrylate functions per molecule, EBECRYL.RTM. 800:
molar mass 780, a mean of 4 acrylate functions per molecule,
EBECRYL.RTM. 810: molar mass 1000, a mean of 4 acrylate functions
per molecule, EBECRYL.RTM. 50 000: molar mass 1500, a mean of 6
acrylate functions per molecule).
[0218] b) polyurethanes and/or polyureas with (meth)acrylate groups
obtained by polycondensation: [0219] said polyurethanes/polyureas
with acrylate groups are, for example, sold under the trade name SR
368 (tris(2-hydroxyethyl)isocyanurate-triacrylate) or CRAYNOR.RTM.
435 by CRAY VALLEY, or under the trade name EBECRYL.RTM. by UCB
(EBECRYL.RTM. 210: molar mass 1500, 2 acrylate functions per
molecule, EBECRYL.RTM. 230: molar mass 5000, 2 acrylate functions
per molecule, EBECRYL.RTM. 270: molar mass 1500, 2 acrylate
functions per molecule, EBECRYL.RTM. 8402: molar mass 1000, 2
acrylate functions per molecule, EBECRYL.RTM. 8804: molar mass
1300, 2 acrylate functions per molecule, EBECRYL.RTM. 220: molar
mass 1000, 6 acrylate functions per molecule, EBECRYL.RTM. 2220:
molar mass 1200, 6 acrylate functions per molecule, EBECRYL.RTM.
1290: molar mass 1000, 6 acrylate functions per molecule,
EBECRYL.RTM. 800: molar mass 800, 6 acrylate functions per
molecule).
[0220] Hydrosoluble diacrylate aliphatic polyurethanes sold under
the trade names EBECRYL.RTM. 2000, EBECRYL.RTM. 2001 and
EBECRYL.RTM. 2002 can also be mentioned, along with diacrylate
polyurethanes in aqueous dispersion sold by UCB under the trade
names IRR.RTM. 390, IRR.RTM. 400, IRR.RTM. 422 IRR.RTM. 424.
[0221] c) Polyethers with (meth)acrylate groups obtained by
esterification, by (meth)acrylic acid, of the terminal hydroxyl
groups of homopolymers or copolymers of C.sub.1-C.sub.4 alkylene
glycols, such as polyethylene glycol, polypropylene glycol,
copolymers of ethylene oxide and propylene oxide preferably having
a mass average molecular mass of less than 10000, and
polyethoxylated or polypropoxylated trimethylolpropane.
[0222] Di(meth)acrylate polyoxyethylenes with a suitable molar mass
are, for example, sold under the trade names SR 259, SR 344, SR
610, SR 210, SR 603 and SR 252 by CRAY VALLEY or under the trade
name EBECRYL.RTM. 11 by UCB. Polyethoxylated trimethylolpropane
triacrylates are sold, for example, under the trade names SR 454,
SR 498, SR 502, SR 9035, SR 415 by CRAY VALLEY or under the trade
name EBECRYL.RTM. 160 by UCB. Polypropoxylated trimethylolpropane
triacrylates are, for example, sold under the trade names SR 492
and SR 501 by CRAY VALLEY.
[0223] d) Epoxyacrylates obtained by reaction between:
[0224] Such polymers are, for example, sold under the trade names
SR 349, SR 601, CD 541, SR 602, SR 9036, SR 348, CD 540, SR 480, CD
9038 by CRAY VALLEY, under the trade names EBECRYL.RTM. 600 and
EBECRYL.RTM. 609, EBECRYL.RTM. 150, EBECRYL.RTM. 860, EBECRYL.RTM.
3702 by UCB and under the trade names PHOTOMER.RTM. 3005 and
PHOTOMER.RTM. 3082 by HENKEL.
[0225] e) C.sub.1-C.sub.50 alkyl poly(meth)acrylates comprising at
least two ethylenically unsaturated double bonds carried by the
lateral and/or terminal hydrocarbon chains.
[0226] Such copolymers are, for example, sold under the trade names
IRR.RTM. 375, OTA.RTM. 480 and EBECRYL.RTM.2047 by UCB.
[0227] f) Polyorganosiloxanes with (meth)acrylate or
(meth)acrylamide groups.
[0228] .alpha.,.omega.-diacrylate polydimethylsiloxanes are
available from SHIN-ETSU under the trade names X-22-164 B and
X-22-164C.
[0229] g) Hyper-branched dendrimers and polymers carrying
(meth)acrylate or (meth)acrylamide terminal groups respectively
obtained by esterification or amidification of dendrimers and
hyper-branched polymers with hydroxyl or amino functions by
(meth)acrylic acid.
[0230] Dendrimers (from the Greek dendron=tree) are "arborescent"
polymer molecules, i.e. highly branched, invented by D A Tomalia
and his team at the beginning of the 1990s (Donald A Tomalia et al,
Angewandte Chemie, Int. Engl Ed, vol 29, n.sup.o 2, pages 138-175).
They are structures constructed around a generally polyvalent
central motif. Linked around this central motif in a predetermined
structure are branched chain extension motifs giving rise to
mono-dispersed symmetrical macromolecules with a well defined
chemical or stereochemical structure. Polyamidoamine type
dendrimers are, for example, sold under the trade name
STARBUST.RTM. by DENDRITECH.
[0231] Hyper-branched polymers are polycondensates, generally of
the polyester, polyamide or polyethyleneamine type, obtained from
multi-functional monomers which have an arborescent structure
similar to that of dendrimers but much less regular (see, for
example, WO-A-93/17060 and WO-A-96/12754).
[0232] PERSTORP sells hyper-branched polyesters under the trade
name BOLTORN.RTM.. Hyper-branched polyethylene amines sold under
the trade name COMBURST.RTM. can be obtained from DENDRITECH.
Hyper-branched poly(esteramide)s with hydroxyl extremities are sold
by DSM under the trade name HYBRANE.RTM..
[0233] Said hyper-branched dendrimers and polymers esterified or
amidified by acrylic acid and/or methacrylic acid are distinguished
from polymers described in points a) to h) above by the very large
number of ethylenically unsaturated double bonds present.
[0234] This high functionality, usually more than 5, renders them
particularly useful, allowing them to act as a "cross-linking
node", i.e. a multiple cross-linking site.
[0235] In a preferred implementation of the invention, dendritic
and hyper-branched polymers will as a result be used in association
with one or more of the polymers and/or oligomers a) to h)
above.
[0236] Compounds Carrying at Least Two Functions with Labile
Hydrogen(s)
[0237] Compounds carrying at least two functions with a labile
hydrogen which can be used in the present invention are also known.
They may be organic compounds with a low molecular mass or
oligomers or synthetic polymers obtained by polyaddition,
polycondensation and/or grafting, or natural chemically modified
polymers.
[0238] In accordance with the present invention, the functions with
a labile hydrogen are preferably selected from primary amine
(--NH.sub.2), secondary amine (>NH), hydroxyl (--OH), carboxylic
acid (--COOH) or thiol (--SH) functions. [0239] when the function
with a labile function is a hydroxyl function, aliphatic diols and
polyols may be mentioned as categories of compounds; [0240] when
the function with a labile hydrogen is an amine function
(NH.sub.2), it may be a diamine, a polyamine, an aminoalcohol, an
oligomer or a polymer with amine groups.
[0241] Particular examples of compounds carrying functions with
labile hydrogen functions are: C.sub.1-C.sub.4 alkyleneglycols,
glycerol, trimethylolpropane, pentaerythritol, poly C.sub.1-C.sub.4
alkylene glycols such as polyethylene glycol or polypropylene
glycol or copolymers thereof, the condensation product of propylene
glycol and trimethylolpropane, castor oil, phytantriol, sugars and
carbohydrates such as saccharose or cellulose, ethylenediamine,
1,3-diaminopropane, lysine, 2-amino-2-methyl-propan-1ol,
poly(alkyleneoxy)diamines such as JEFFAMINE.RTM. products sold by
TEXACO, nitrocellulose, cellulose esters, especially those with a
degree of substitution of less than 3 such as cellulose
acetobutyrate or cellulose acetopropionate, cellulose ethers such
as hydroxyethylcellulose, carboxymethylcellulose,
hydroxypropylcellulose or ethylcellulose, polyester resins,
silicones, perfluoropolyethers, alkyds and polyketones with
hydroxylated ends, polyvinyl alcohol and copolymers based on vinyl
alcohol, allyl alcohol copolymers, copolymers based on
C.sub.2-C.sub.10 hydroxyalkyl(meth)acrylate such as 2-hydroxyethyl
or 2-hydroxypropyl(meth)acrylate sold under the trade name
JONCRYL.RTM. SCX 910 by JOHNSON POLYMER or under the trade name
CRODOPLAST.RTM. AC 5725 by CRODA, copolymers based on vinylamine or
allylamine, silicones and perfluoroethers with primary or secondary
amine extremities, hyper-branched dendrimers or polymers with
hydroxyl or primary amine extremities such as hyper-branched
polyesters with hydroxyl extremities sold by PERSTORP under the
trade names BOLTORN.RTM. H40 TMP CORE and HBP POLYOL.RTM. 3G
(described in International patent applications WO 93/17060 and WO
96/12754), or dendrimers of the polyamido-amine type with primary
amine extremities described in the article by Tomalia, Angewandte
Chemie, Int. Engl. Ed., vol. 29, n.sup.o 2, pages 138-175.
[0242] In a second variation of the invention, cross-linking is
carried out photochemically and employs at least two types of
compounds, (A) and (B) respectively having at least one unsaturated
double bond in the presence of a photoinitiator.
[0243] In this variation, A and B are selected so as to form a
reactive system the mean valency of which is more than 2. The
"valency" of a compound is the number of covalent bonds it may
establish with the compounds with which it is associated. The mean
valency is defined as being equal to the ratio of the sum of the
valencies of all of compounds A and B divided by the total number
of compounds A and B.
V m = nivi ni ##EQU00002##
[0244] In this variation of the invention, compounds A or B may be
a compound comprising a function of the unsaturated double bond
type and in particular as defined above, and/or a monomer with an
ethylenically unsaturated bond.
[0245] One particular group of advantageous photoinitiators for use
in the invention is that of copolymerizable photoinitiators. These
are molecules comprising both a photoinitiator group capable of
photoinduced radical scission and at least one ethylenically
unsaturated double bond.
[0246] To obtain properties with satisfactory behavior, a total
quantity of photoinitiator(s) of at least 0.1% by weight is
generally used, at most 10% by weight, preferably in the range 0.2%
to 5% by weight, compared with the total weight of compounds
comprising ethylenically unsaturated double bonds.
[0247] In this variation, cross-linking may be carried out in the
presence of a co-film-forming agent such as nitrocellulose or
cellulose esters.
[0248] Film-Forming Polymer Particles
[0249] In a second variation of the invention, the article
comprises at least one polymeric film obtained by evaporating off
the organic or aqueous solvent phase from a solution or dispersion
of at least one film-forming polymer.
[0250] The term "film-forming polymer" designates a polymer which
can by itself form, or form in the presence of an auxiliary
film-forming agent, an isolatable film, in particular a continuous
film on a support, especially on keratinous substances.
[0251] To prepare a polymeric film in accordance with the
invention, a single film-forming polymer or a mixture of
film-forming polymers may be used. Said film-forming polymer may be
selected from the group constituted by radical polymers,
polycondensates and polymers of natural origin.
[0252] Film-Forming Polymers which are Soluble or Dispersible in an
Organic Solvent
[0253] In a first variation of the invention, said polymeric film
derives from evaporation of the organic solvent phase of a solution
or dispersion of at least one film-forming polymer. In this
implementation, the organic film-forming polymer is at least one
polymer selected from the group comprising: film-forming polymers
which are soluble or dispersible in at least one class of organic
solvent such as ketones, alcohols, glycols or propylene glycol
ethers, short chain esters, alkanes and their aqueous or non
aqueous mixtures.
[0254] The corresponding polymers may have any chemical nature. In
particular, they may result either from homo- or co-polymerization
of unsaturated monomers, or from polycondensation, or from
modification of natural polymers, in particular polysaccharides.
The mass average molecular masses (Mp) of these polymers may be
from 3000 to 1000000, in particular 5000 to 800000, in particular
10000 to 500000.
[0255] Particularly suitable polymers which are soluble or
dispersible in organic solvents include the following:
[0256] a) (meth)acrylic acid ester and/or amide homo- and
co-polymers, in particular polymers resulting from the
polymerization or copolymerization of methyl, ethyl, propyl, butyl,
isobutyl, tertiobutyl, pentyl, hexyl, cyclohexyl, 2-ethylhexyl,
heptyl, octyl, isobornyl, norbornyl, adamantyl acrylates and/or
methacrylates or the corresponding (meth)acrylamides. Said polymers
preferably comprise 0 to 20% of a polar co-monomer such as
(meth)acrylic acid, (meth)acrylamide, hydroxyethyl (meth)acrylate,
2-hydroxypropyl(meth)acrylate and (meth)acrylonitrile. They may
also result from copolymerization with styrene or a substituted
styrene.
[0257] b) Vinyl ester or amide homo- and copolymers, in particular
homo- and co polymers resulting from the polymerization of vinyl
acetate, vinyl propionate, vinyl versatate, with or without the
presence of a polar co-monomer such as crotonic acid,
allyloxyacetic acid, maleic anhydride or acid, itaconic anhydride
or acid, vinyl acetamide or vinyl formamide. Similarly, they may
result from copolymerizing at least one of the monomers mentioned
above with styrene or with a substituted styrene.
[0258] c) Celluloses and cellulose derivatives, such as
nitrocelluloses and/or cellulose esters such as cellulose acetates,
cellulose propionates, cellulose butyrates, cellulose
acetopropionates or cellulose acetobutyrates.
[0259] d) Polycondensates which are soluble or dispersible in said
solvents. They are generally used as a principal film-forming agent
or as a co-film-forming agent with one of the polymer classes
mentioned above (a to c), in particular if they have a low
molecular weight (Mp<20000). They may be selected from the
following polymers or copolymers: polyurethanes, acrylic
polyurethanes, polyureas, polyurea polyurethanes, les polyester
polyurethanes, polyether polyurethanes, polyesters,
polyester-amides, fatty chain polyesters, epoxy compounds, and
arylsulfonamide condensates, in particular
tosylamide/formaldehydes.
[0260] Of these polycondensates, in particular if they are used as
a film-forming agent or a co film-forming agent with one or more
nitrocelluloses and/or a cellulose ester (class c), the following
may in particular be mentioned: [0261] polyesters, in particular
fatty chain polyesters and more particularly copolymers with the
CTFA name: "copolymer of glycidyl phthalic/glycerol/decanoate
anhydride" and "adipic acid/neopentylglycol/trimellitic anhydride
copolymer"; [0262] alkyds; [0263] tosyl amide/formaldehyde
condensates; [0264] polyurethanes and polyurea-urethanes; [0265]
acrylic resins; [0266] silicone resins (non volatile or partially
volatile).
[0267] Aqueous Dispersions of Polymer Particles or Film-Forming
Latexes
[0268] In a second variation of the invention, said polymeric film
derives from evaporating off the aqueous phase of an aqueous
dispersion of film-forming polymer particles. In this case, the
film-forming polymer may be selected from aqueous dispersions of
polymer particles or film-forming latexes, and in this case the
composition of the invention comprises at least one aqueous
phase.
[0269] The aqueous dispersion comprising one or more film-forming
polymers may be prepared by the skilled person using general
knowledge, in particular by emulsion polymerization or by
dispersing the formed polymer.
[0270] Film-forming polymers of this type which may be used in the
composition of the present invention which may be mentioned are
synthetic polymers of the polycondensate or radical type, polymers
of natural origin, and mixtures thereof.
[0271] In particular, it is possible to use, in the form of a
latex, polymers (homo and copolymers) which are mentioned above as
polymers which are soluble or dispersible in an organic solvent
medium, more particularly polymers of classes a, b and c.
[0272] Polycondensates which can thus be mentioned include anionic,
cationic, non ionic or amphoteric polyurethanes,
polyurethane-acrylics, polyurethane-polyvinylpyrrolidones,
polyester-polyurethanes, polyether-polyurethanes, polyureas,
polyurea polyurethanes and mixtures thereof.
[0273] It is also possible to mention polyesters, polyester amides,
fatty chain polyesters, polyamides and epoxy ester resins.
[0274] The polyesters may be obtained in known manner by
polycondensation of aliphatic or aromatic dibasic acids with
aliphatic or aromatic diols or polyols. Aliphatic dibasic acids
which may be used are succinic acid, glutaric acid, adipic acid,
pimelic acid, suberic acid or sebacic acid. Aromatic dibasic acids
which may be used are terephthalic acid or isophthalic acid, or a
derivative such as phthalic anhydride. Aliphatic diols which may be
used are ethylene glycol, propylene glycol, diethylene glycol,
neopentyl glycol, dimethanol cyclohexane and
4,41-(1-methylpropylidene)bisphenol. Polyols which may be used are
glycerol, pentaerythritol, sorbitol and trimethylol propane.
[0275] Radical type polymers may in particular be acrylic and/or
vinylic polymers or copolymers. Preferably, anionic radical
polymers are used. Monomers carrying an anionic group which may be
used during radical polymerization which may be mentioned are
acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and
2-acrylamido-2-methylpropanesulfonic acid.
[0276] The acrylic polymers may result from copolymerization of
monomers selected from esters and/or amides of acrylic acid or
methacrylic acid. Examples of ester type monomers which may be
mentioned are methyl methacrylate, ethyl methacrylate, butyl
methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and
lauryl methacrylate. Examples of amide type monomers which may be
mentioned are N-t-butyl acrylamide and N-t-octyl acrylamide.
[0277] The vinyl polymers may result from the homopolymerization or
copolymerization of monomers selected from vinyl esters, styrene
and butadiene. Examples of vinyl esters which may be mentioned are
vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate
and vinyl t-butyl benzoate.
[0278] It is also possible to use acrylic/silicone copolymers or
nitrocellulose/acrylic copolymers.
[0279] It is also possible to mention polymers resulting from
radical polymerization of one or more radical monomers inside
and/or partially on the surface of pre-existing particles of at
least one polymer selected from the group constituted by
polyurethanes, polyureas, polyesters, polyester amides and/or
alkyds. Said polymers are generally termed hybrid polymers.
[0280] The dispersion may also comprise an associative polyurethane
type polymer or a natural gum such as xanthan gum.
[0281] Polymers in aqueous dispersion which may be mentioned are
dispersions of acrylic polymers sold under the trade names NEOCRYL
XK-90.RTM., NEOCRYL A-1070.RTM., NEOCRYL A-1090.RTM., NEOCRYL
BT-62.RTM., NEOCRYL A-1079.RTM., NEOCRYL A-523.RTM. by ZENECA and
DOW LATEX 432.RTM., by DOW CHEMICAL. It is also possible to use
aqueous dispersion of polyurethane, in particular
polyester-polyurethanes sold under the trade names "AVALURE
UR-405.RTM.", "AVALURE UR-410.RTM.", "AVALURE UR-425.RTM.",
"SANCURE 2060.RTM." by GOODRICH and polyether-polyurethanes sold
under the trade names "SANCURE 878.RTM." by GOODRICH, "NEOREZ
R-970.RTM." by AVECIA.
[0282] The group of film-forming polymers mentioned above may be
associated with at least one auxiliary film-forming and/or
coalescing agent.
[0283] The auxiliary film-forming agent may be selected from any of
the compounds known to the skilled person as being susceptible of
fulfilling the desired function, and in particular may be selected
from plasticizers and coalescence agents for the film-forming
polymer.
[0284] In particular, it is possible to use, alone or as a mixture,
the usual plasticizers or coalescence agents such as: [0285]
glycols and their derivatives such as diethylene glycol ethyl
ether, diethylene glycol methyl ether, diethylene glycol butyl
ether or diethylene glycol hexyl ether, ethylene glycol ethyl
ether, ethylene glycol butyl ether, ethylene glycol hexyl ether;
[0286] glycol esters; [0287] propylene glycol derivatives, in
particular propylene glycol phenyl ether, propylene glycol
diacetate, dipropylene glycol butyl ether, tripropylene glycol
butyl ether, propylene glycol methyl ether, dipropylene glycol
ethyl ether, tripropylene glycol methyl ether and diethylene glycol
methyl ether, propylene glycol butyl ether; [0288] esters, in
particular of carboxylic acids such as citrates, in particular
triethyl citrate, tributyl citrate, triethyl acetyl citrate,
tributyl acetyl citrate, 2-triethylhexyl acetyl citrate;
phthalates, in particular diethyl phthalate, dibutyl phthalate,
dioctyl phthalate, dipentyl phthalate, dimethoxyethyl phthalate;
phosphates, in particular tricresyl phosphate, tributyl phosphate,
triphenyl phosphate, tributoxyethyl phosphate; tartrates, in
particular dibutyl tartrate; adipates; carbonates; sebacates;
benzyl benzoate, butyl acetylricinoleate, glyceryl
acetylricinoleate, butyl glycolate, camphor, glycerol triacetate,
N-ethyl-o,p-toluenesulfonamide; [0289] oxyethylenated derivatives
such as oxyethylenated oils, in particular vegetable oils such as
castor oil; silicone oils; [0290] mixtures thereof.
[0291] The type and quantity of plasticizing and/or coalescence
agent may be selected by the skilled person on the basis of general
knowledge.
[0292] As an example, the amount of plasticizing and/or coalescence
agent may be from 0.01% to 10%, in particular from 1% to 3% by
weight relative to the total composition weight.
[0293] Adhesive Material
[0294] The article of the invention has an adhesive outer face.
Said adhesive face is generally obtained by dint of the presence of
at least one layer of at least one adhesive material.
[0295] The term "material" as used in the context of the present
invention means a polymer or a polymeric system which may comprise
one or more polymers of different natures. Said adhesive material
may be in the form of a solution of polymer or a dispersion of
polymer particles in a solvent. Said adhesive material may also
contain a plasticizer as defined above. Said adhesive material may
have a certain adhesive power as defined by its viscoelastic
properties.
[0296] The viscoelastic properties of a material are conventionally
defined by two characteristic values which are as follows: [0297]
the elastic modulus, which represents the elastic behavior of the
material for a given frequency and which is conventionally denoted
G'; [0298] the viscous modulus, which represents the viscous
behavior of the material for a given frequency which is
conventionally denoted G''.
[0299] These magnitudes have been defined in the "Handbook of
Pressure Sensitive Adhesive Technology" 3.sup.rd edition, D. Satas,
chap. 9, p. 155 a 157.
[0300] Adhesive materials which can be used in the context of the
present invention have viscoelastic properties which are measured
at a reference temperature of 35.degree. C. and in a certain
frequency range.
[0301] In the case of adhesive materials in the form of a solution
or dispersion of polymer in a volatile solvent (such as water, a
short chain ester, a short chain alcohol, acetone, etc), the
viscoelastic properties of the material are measured under
conditions under which it has a volatile solvent content of less
than 30%, in particular a volatile solvent content of less than
20%.
[0302] In particular, the elastic modulus of the material is
measured at three different frequencies: [0303] at low frequency,
i.e. 2.times.10.sup.-2 Hz; [0304] at an intermediate frequency,
i.e. 0.2 Hz; [0305] at high frequency, i.e. at 2 Hz; [0306] and the
viscous modulus at the frequency of 0.2 Hz.
[0307] These measurements allow the change of adhesive power of the
adhesive material over time to be measured.
[0308] These viscoelastic properties are measured during dynamic
tests under low amplitude sinusoidal stresses (small deformations)
carried out at 35.degree. C. over a frequency range of
2.times.10.sup.-2 to 20 Hz using a "Haake RS50.RTM." type rheometer
under tension/shear stress, for example in cone/plane geometry (for
example with a cone angle of 1.degree.).
[0309] Advantageously, said adhesive material satisfies the
following conditions:
G'(2 Hz,35.degree. C.).gtoreq.10.sup.3 Pa; and
G'(35.degree. C.).ltoreq.10.sup.8 Pa, in particular G'(35.degree.
C.).ltoreq.10.sup.7 Pa;
G'(2.times.10.sup.-2 Hz,35.degree. C.).ltoreq.310.sup.5 Pa;
[0310] in which: [0311] G' (2 Hz, 35.degree. C.) is the elastic
shear modulus of said adhesive material, measured at a frequency of
2 Hz and at a temperature of 35.degree. C.; [0312] G' (35.degree.
C.) is the elastic shear modulus of said adhesive material measured
at a temperature of 35.degree. C., for any frequency in the range
2.times.10.sup.-2 to 2 Hz; [0313] G'(2.times.10.sup.-2 Hz,
35.degree. C.) is the elastic shear modulus of said adhesive
material, measured at a frequency of 2.times.10.sup.-2 Hz and at a
temperature of 35.degree. C.
[0314] In a particular form of the invention, the adhesive material
also satisfies the following condition:
G''/G'(0.2 Hz,35.degree. C.).gtoreq.0.35.
[0315] in which: [0316] G'' (0.2 Hz, 35.degree. C.) is the viscous
shear modulus of said adhesive material, measured at a frequency of
0.2 Hz and at a temperature of 35.degree. C.; [0317] G' (0.2 Hz,
35.degree. C.) is the elastic shear modulus of said adhesive
material, measured at a frequency of 0.2 Hz and at a temperature of
35.degree. C.
[0318] In a particular form of the invention, we have:
G'(2 Hz,35.degree. C.).gtoreq.5.times.10.sup.3 Pa, and in
particular, G'(2 Hz,35.degree. C.).gtoreq.10.sup.4 Pa.
[0319] In a further particular form of the invention, we have:
G'(2.times.10.sup.-2 Hz,35.degree. C.).ltoreq.5.times.10.sup.4
Pa.
[0320] In particular, the adhesive materials of the invention
satisfy the following four conditions:
G'(2 Hz,35.degree. C.).gtoreq.10.sup.4 Pa; and
G'(35.degree. C.).ltoreq.10.sup.8 Pa, in particular G'(35.degree.
C.).ltoreq.10.sup.7 Pa;
G'(2.times.10.sup.-2 Hz,35.degree. C.).ltoreq.5.times.10.sup.4 Pa;
and
G''/G'(0.2 Hz,35.degree. C.).gtoreq.0.35.
[0321] In general, the adhesive is such that said article cannot be
removed by peeling when it is applied to the surface of a synthetic
or natural nail after leaving for at least 24 hours.
[0322] More particularly, the adhesive materials of the invention
may be selected from adhesives of the "Pressure sensitive
adhesives" type, for example those mentioned in the "Handbook of
pressure sensitive adhesive technology", 3.sup.rd edition, D
Satas.
[0323] The adhesive materials of the invention are polymers
selected from block or random copolymers comprising at least one
monomer or an association of monomers, the resulting polymer having
a low glass transition temperature at ambient temperature
(25.degree. C.), said monomers or associations of polymers possibly
being selected from butadiene, ethylene, propylene, isoprene,
isbutylene, a silicone, and mixtures thereof. Examples of such
materials are styrene-butadiene-styrene,
styrene-(ethylene-butylene)-styrene, styrene-isoprene-styrene type
block copolymers such as those sold under the trade name
"Kraton.RTM." by SHELL CHEMICAL Co. or "Vector.RTM." from
EXXON.
[0324] The adhesive materials of the invention are in particular
adhesive polymers selected from: [0325] polyurethanes, [0326]
acrylic polymers, [0327] silicones, [0328] butyl gums, in
particular polyisobutylenes, [0329] ethylene-vinyl acetate
polymers, [0330] polyamides, optionally modified by fatty chains,
[0331] natural gums, [0332] and mixtures thereof.
[0333] In particular, they may be adhesive copolymers deriving from
the copolymerization of vinyl monomers with polymeric entities such
as those described in U.S. Pat. No. 6,136,296, for example. The
invention also encompasses the adhesive copolymers described in
U.S. Pat. No. 5,929,173 having a polymeric skeleton, with a Tg of
0.degree. C. to 45.degree. C., grafted by chains deriving from
acrylic and/or methacrylic monomers and, in contrast, having a Tg
of 50.degree. C. to 200.degree. C.
[0334] The adhesive materials are, for example, selected from
polyisobutylenes having a relative molar mass Mv of 10000 or more
and 150000 or less. In particular, said relative molar mass is
18000 or more and 150000 or less.
[0335] Commercially available products which are of particular
service to the present invention which may be mentioned are
polyisobutylenes with a relative molar mass Mv of 40000, 55000 and
85000 sold respectively under the trade names "Oppanol B 10.RTM.",
"Oppanol B 12.RTM." and "Oppanol B 15.RTM." by BASF, and mixtures
thereof.
[0336] Advantageously, the adhesive material and the film are
compatible because of their chemical nature and composition. In one
particular implementation, the solvent for the adhesive can result
in an increase in the mass of the film in contact therewith, in
particular by at least 10% by weight relative to the initial weight
of the film. In other words, this increase results in the film
increasing in mass.
[0337] The adhesive material in the article of the invention is
generally in the form of a layer with a thickness of 1 .mu.m to 100
.mu.m, in particular 1 .mu.m to 50 .mu.m, preferably 1 .mu.m to 25
.mu.m.
[0338] Other Additives
[0339] The organic film of the article may also comprise at least
one coloring material, which may be organic or inorganic, in
particular of the pigment or nacre type conventionally used in
cosmetic compositions.
[0340] The term "pigments" means white or colored particles,
mineral or organic, insoluble in an aqueous solution, intended to
color and/or opacify the resulting film.
[0341] The pigments may be present in an amount of 0.01% to 15% by
weight, in particular 0.01% to 10% by weight, more particularly
0.02% to 5% by weight, relative to the total article weight.
Mineral pigments which are suitable in the context of the invention
which may be mentioned are oxides of titanium, zirconium or cerium
and oxides of zinc, iron or chromium, ferric blue, manganese
violet, ultramarine blue and chromium hydrate.
[0342] It may also be a pigment with a structure which may, for
example, be of the sericite/brown iron oxide/titanium
dioxide/silica type. Such a pigment is, for example, sold under the
reference COVERLEAF NS or JS by CHEMICALS AND CATALYSTS and has a
contrast ratio of close to 30.
[0343] The coloring material may also comprise a pigment having a
structure which may, for example, be of the silica microsphere type
containing iron oxide. An example of a pigment having that
structure is sold by MIYOSHI with reference number PC BALL
PC-LL-100 P, said pigment being constituted by silica microspheres
containing yellow iron oxide.
[0344] Organic pigments which may be used in the context of the
invention which may be mentioned are carbon black, D&C type
pigments, lakes based on cochineal carmine, barium, strontium,
calcium, aluminum or the diketo pyrrolopyrroles (DPP) described in
EP-A-0 542 669, EP-A-0 787 730, EP-A-0 787 731 and
WO-A-96/08537.
[0345] The term "nacres" means colored particles of any form,
iridescent or otherwise, produced in the shells of certain mollusks
or synthesized, the color effect in which is produced by optical
interference.
[0346] The nacres may be selected from nacreous pigments such as
mica titanium covered with chromium oxide, mica covered with
bismuth oxychloride, mica titanium covered with chromium oxide,
mica titanium covered with an organic colorant and nacreous
pigments based on bismuth oxychloride. It may also concern mica
particles on the surface of which at least two successive layers of
metallic oxides and/or organic coloring materials is
superposed.
[0347] Examples of nacres which may be mentioned are natural mica
covered with titanium oxide, iron oxide, natural pigment and
bismuth oxychloride.
[0348] Commercially available nacres which may be mentioned are
TIMICA, FLAMENCO and DUOCHROME (mica based) sold by ENGELHARD,
TIMIRON nacres sold by MERCK, PRESTIGE mica based nacres sold by
ECKART and SUNSHINE synthetic mica based nacres sold by SUN
CHEMICAL.
[0349] More particularly, the nacres may have a color or a yellow,
pink, red, bronze, orangey, brown, gold and/or coppery glint.
[0350] Illustrative examples of nacres which may be employed in the
context of the present invention which may be mentioned are gold
colored nacres, in particular those sold by ENGELHARD denoted
Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold
(Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne);
bronze nacres sold by MERCK under the trade name Bronze fine
(17384) (Colorona) and Bronze (17353) (Colorona) and by ENGELHARD
under the trade name Super bronze (Cloisonne); orange nacres sold
by ENGELHARD under the trade name Orange 363C (Cloisonne) and
Orange MCR 101 (Cosmica) and by MERCK under the trade name Passion
orange (Colorona) and Matte orange (17449) (Microna); nacres with a
brown tint sold by ENGELHARD under the trade name Nu-antique copper
340XB (Cloisonne) and Brown CL4509 (Chromalite); nacres with a
copper glint sold by ENGELHARD under the trade name Copper 340A
(Timica); nacres with a red tint sold by MERCK under the trade name
Sienna fine (17386) (Colorona); nacres with a yellow tint sold by
ENGELHARD under the trade name Yellow (4502) (Chromalite); red
tinted nacres with a gold tint sold by ENGELHARD under the trade
name Sunstone G012 (Gemtone); pink nacres sold by ENGELHARD under
the trade name Tan opale G005 (Gemtone); black nacres with a gold
glint sold by ENGELHARD under the trade name Nu antique bronze 240
AB (Timica), blue nacres sold by MERCK under the trade name Matte
blue (17433) (Microna), white nacres with a silver glint sold by
MERCK under the trade name Xirona Silver and green-gold pink orange
nacres sold by MERCK under the trade name Indian summer
(Xirona).
[0351] The article of the invention may also comprise hydrosoluble
or liposoluble colorants in an amount of 0.01% to 10% by weight, in
particular 0.01% to 5% by weight relative to the total article
weight. Examples of liposoluble colorants are Sudan red DC Red 17,
DC Green 6, .beta.-carotene, soya oil, Sudan brown, DC Yellow 11,
DC Violet 2, DC orange 5 and quinoline yellow. Examples of
hydrosoluble colorants are beetroot juice and methylene blue.
[0352] It may also contain one or more additives with a formulation
currently used in cosmetics, and more especially in the field of
cosmetics and/or nail care. They may also be selected from
vitamins, oligo-elements, softeners, sequestrating agents,
alkalinizing agents or acidifying agents, wetting agents,
thickening agents, dispersing agents, anti-foaming agents,
spreading agents, co-resins, film-forming agents, plasticizing
agents, coalescence agents, preservatives, UV filters, active
ingredients, moisturizing agents, neutralizing agents, stabilizing
agents, antioxidants and mixtures thereof.
[0353] Thus, it is possible to incorporate, as active ingredients,
hardening agents for keratinous materials and/or active ingredients
to treat various diseases affecting the nails, such as
onychomycosis.
[0354] The quantities of these various ingredients are those
conventionally used in this field, for example 0.01% to 20% by
weight, in particular 0.01% to 10% by weight relative to the total
article weight.
[0355] The article of the invention generally has a thickness of 1
.mu.m to 500 .mu.m, in particular 1 .mu.m to 300 .mu.m, more
particularly 1 .mu.m to 200 .mu.m.
[0356] As mentioned before, the article of the invention is coated
at least on its outer adhesive face with a removable support.
[0357] Said support may have any nature compatible with the fact
that while it is in contact with an adhesive material, it may also
be separated therefrom.
[0358] The removable support defined above may be in the form of a
protective layer consisting, for example, of a film, in particular
a plastic or paper film or a paper or a sheet type textile
structure.
[0359] Advantageously, said support is constituted by a transparent
material to prevent any error in the choice of color. It may be
constituted by one or more layers which may be of different
natures. As an example, it may be a sheet of paper coated with one
of the plastics mentioned above.
[0360] Suitable plastic films which may, for example, be used in
the article of the invention which may be mentioned are films
formed from polyesters, for example polyethylene terephthalates,
polybutylene terephthalates or polyethylene sebacates or made from
polyethylene, polypropylene or polyamides, such as
polyhexamethylene adipate, polycaprolactame or
poly(omega-.omega.-undecanoic acid amide). Because of their surface
characteristics, said plastics are clearly not removable per se. To
provide this characteristic, it is necessary to carry out a surface
treatment using appropriate substances such as a treatment with
silicones or, particularly advantageously, by a treatment with
salts of long chain fatty acids such as C.sub.12 to C.sub.22, for
example, said acids being saturated or possibly containing up to
three olefinic bonds, and at least some divalent metals, in
particular salts of heavy transition metals of this type and more
particularly chromium salts.
[0361] The sheet type textile structure may be woven or
non-woven.
[0362] In a particular implementation, both faces of the article of
the invention are coated with identical or different removable
support.
[0363] The article of the present invention may be in various forms
such as a star, square, roundel, etc.
[0364] As described above, the present invention also encompasses a
product suitable for packaging an article of the present invention
in a partially dry form.
[0365] This means that once applied, the article of the present
invention is dried and then adopts its definitive structure by
contact with the ambient air.
[0366] An article of the invention may be obtained with a device as
described in U.S. Pat. No. 4,903,840.
[0367] As indicated above, the present invention also provides a
method of preparing a flexible nail cosmetic and/or nail care
article.
[0368] The adhesive material is generally deposited in the form of
a layer of material with a thickness of 0.5 .mu.m to 200 .mu.m, in
particular 1 .mu.m to 100 .mu.m.
[0369] An article of the invention the organic film of which is
obtained by evaporation of the organic or aqueous solvent phase
from a solution or dispersion of film-forming polymer(s) may, for
example, be obtained by transposing the method described in U.S.
Pat. No. 5,415,903. The material with an optical, relief, and/or
olfactory effect is in this case introduced into the solvent phase
under consideration.
[0370] The article obtained, in particular excess film, is then
generally cut out, before or after application thereof, to the
desired shape and form with small scissors, nail clippers or by
scratching the film.
[0371] The present invention also provides a method of making up
the nails in which the article as defined above is applied.
* * * * *