U.S. patent application number 11/664003 was filed with the patent office on 2008-05-29 for method of applying makeup by means of a magnetic composition incorporating at least one coloring agent having optical properties that are sensitive to an external stimulus.
This patent application is currently assigned to L"oreal. Invention is credited to Ludovic Thevenet.
Application Number | 20080124288 11/664003 |
Document ID | / |
Family ID | 34949907 |
Filed Date | 2008-05-29 |
United States Patent
Application |
20080124288 |
Kind Code |
A1 |
Thevenet; Ludovic |
May 29, 2008 |
Method of Applying Makeup by Means of a Magnetic Composition
Incorporating at Least one Coloring Agent Having Optical Properties
that are Sensitive to an External Stimulus
Abstract
The present invention relates to method of applying makeup to
keratinous substances, in particular the skin, the nails, hair, or
the lips, the method comprising the following steps: depositing at
least one cosmetic composition on the surface, the cosmetic
composition comprising: bodies that present magnetic susceptibility
that is non-zero; and at least one coloring agent having optical
properties that are sensitive to an external stimulus; and exposing
at least part of the composition to a magnetic field to modify the
orientation and/or to displace at least some of the magnetic
bodies.
Inventors: |
Thevenet; Ludovic; (Bourg La
Reine, FR) |
Correspondence
Address: |
OLIFF & BERRIDGE, PLC
P.O. BOX 320850
ALEXANDRIA
VA
22320-4850
US
|
Assignee: |
L"oreal
Paris
FR
|
Family ID: |
34949907 |
Appl. No.: |
11/664003 |
Filed: |
July 8, 2005 |
PCT Filed: |
July 8, 2005 |
PCT NO: |
PCT/FR05/50560 |
371 Date: |
August 16, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60619928 |
Oct 20, 2004 |
|
|
|
Current U.S.
Class: |
424/63 ; 424/64;
424/70.6 |
Current CPC
Class: |
A45D 29/004 20130101;
A61K 2800/47 20130101; A61Q 1/00 20130101; A61K 2800/42 20130101;
A61K 2800/88 20130101; A61Q 3/02 20130101; A61Q 1/06 20130101; A61Q
1/02 20130101; A45D 33/00 20130101; A61K 8/19 20130101; A45D 34/00
20130101 |
Class at
Publication: |
424/63 ; 424/64;
424/70.6 |
International
Class: |
A61K 8/00 20060101
A61K008/00; A61Q 19/00 20060101 A61Q019/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 5, 2004 |
FR |
0410501 |
Claims
1. A method of applying makeup to keratinous substances,
comprising: depositing at least one cosmetic composition on the
surface, the cosmetic composition comprising: bodies that present
magnetic susceptibility that is non-zero; and at least one coloring
agent having optical properties that are sensitive to an external
stimulus; and exposing at least part of the composition to a
magnetic field to modify the orientation and/or to displace at
least some of the magnetic bodies.
2. A method according to claim 1, in which the coloring agent that
is sensitive to an external stimulus changes chemical form in
response to the external stimulus.
3. A method according to claim 1, in which the coloring agent
passes into an excited state without changing its chemical form in
response to an external stimulus.
4. A method according to claim 1, in which the coloring agent
comprises at least one thermochromic agent.
5. A method according to claim 1, in which the coloring agent
comprises at least one photochromic agent.
6. A method according to claim 1, in which the coloring agent
comprises at least one tribochromic or piezochromic agent.
7. A method according to claim 1, in which the coloring agent
comprises at least one solvatochromic agent.
8. A method according to claim 1, in which the coloring agent is
luminescent.
9. A method according to claim 8, in which the coloring agent is
mechanoluminescent.
10. A method according to claim 8, in which the coloring agent is
phosphorescent.
11. A method according to claim 8, in which the coloring agent is
fluorescent.
12. A method according to claim 1, in which the coloring agent
having optical properties that are sensitive to an external
stimulus comprises at least some of the magnetic bodies.
13. A method according to claim 1, in which the coloring agent
having optical properties that are sensitive to an external
stimulus is non-magnetic.
14. A method according to claim 1, in which the magnetic field is
applied to form at least one pattern on the composition.
15. A method according to claim 1, in which the magnetic field is
exerted by a permanent magnet.
16. A method according to claim 1, in which the magnetic field is
exerted by an electromagnet.
17. A method according to claim 14, in which the magnet or
electromagnet is driven in rotation.
18. A method according to claim 15, in which the electromagnet is
powered by at least one optionally rechargeable battery.
19. A method according to claim 15, in which the electromagnet is
powered intermittently during formation of a pattern.
20. A method according to claim 1, in which the magnetic field is
applied until the composition attains a frozen appearance.
21. A method according to claim 1, in which the magnetic field is
applied for a period which is shorter than that causing all of the
magnetic bodies of the exposed region to be definitively displaced
and/or oriented.
22. A method according to claim 1, in which the magnetic field is
exerted in succession over different regions of the surface coated
with the composition.
23. A method according to claim 1, wherein the magnetic field is
exerted in succession over disconnected regions of the surface.
24. A method according to claim 1, in which at least one region of
the surface coated with the composition is not exposed to the
magnetic field.
25. A method according to claim 1, in which the composition is
applied using a cosmetic applicator.
26. A method according to claim 25, in which the applicator
comprises a brush, a cotton bud, or a foam.
27. A method according to claim 24, in which the applicator is
non-magnetic.
28. A method according to claim 1, wherein the magnetic bodies
comprise a pigment.
29. A method according to claim 1, wherein the magnetic bodies
comprise fibers or chains of particles.
30. A method according to claim 1, in which the composition
includes at least one volatile solvent.
31. A method according to claim 1, in which the composition
includes at least one film-forming polymer.
32. A kit for making-up keratinous substances, the kit comprising:
a magnetic device enabling a magnetic field to be generated; and a
cosmetic composition including: magnetic bodies that present
non-zero magnetic susceptibility and that are movable under the
effect of a magnetic field; and at least one coloring agent having
optical properties that are sensitive to an external stimulus; the
magnetic device being capable of creating a magnetic field that is
capable, when the keratinous substance covered in a deposit of said
composition is inserted in said magnetic field, of modifying the
orientation and/or the position of the magnetic bodies inside the
deposit.
33. A kit according to claim 32, in which the composition is a nail
polish.
34. A kit according to claim 32, in which the composition is a
foundation.
35. A kit according to claim 32, in which the composition is a
product to be applied to the lips.
36. A kit according to claim 32, in which the composition is a
product to be applied to the keratinous fibers.
37. A kit according to claim 32, in which the magnetic device
comprises a magnet or an electromagnet.
38. A kit according to claim 32, in which the coloring agent having
optical properties that are sensitive to an external stimulus
comprises a photochromic agent.
39. A kit according to claim 32, in which the coloring agent having
optical properties that are sensitive to an external stimulus
comprises a thermochromic agent.
40. A kit according to any claim 32, in which the coloring agent
having optical properties that are sensitive to an external
stimulus comprises a piezochromic or tribochromic agent.
41. A kit according to claim 32, in which the coloring agent having
optical properties that are sensitive to an external stimulus
comprises at least one solvatochromic agent.
42. A kit according to claim 32, in which the coloring agent having
optical properties that are sensitive to an external stimulus
comprises at least one luminescent agent.
43. A kit according to claim 32, comprising magnetic bodies
comprising metallic iron, especially soft iron.
44. Cosmetic composition comprising: magnetic bodies that present
non-zero magnetic susceptibility and that are movable under the
effect of a magnetic field; and at least one coloring agent having
optical properties that are sensitive to an external stimulus; the
magnetic bodies comprising metallic iron.
Description
[0001] The present invention relates to a method of applying makeup
to a natural surface, such as the skin, the nails, hair, or the
lips, or to an artificial surface, such as false nails, and it also
relates to a kit for implementing such a method.
[0002] A need exists to benefit from novel appearance effects in
the field of makeup and the invention seeks to satisfy that
need.
A METHOD OF APPLYING MAKEUP
[0003] According to one of its aspects, the invention provides a
method of applying makeup to keratinous substances, in particular
the skin, the lips, the nails, or hair, the method comprising the
following steps: [0004] depositing at least one cosmetic
composition on the surface, the cosmetic composition comprising:
[0005] bodies that present magnetic susceptibility that is
non-zero; and [0006] at least one coloring agent having optical
properties that are sensitive to an external stimulus; and [0007]
exposing at least part of the composition to a magnetic field to
modify the orientation and/or to displace at least some of the
magnetic bodies.
[0008] The invention allows novel esthetic effects to be created,
for example by combining effects linked to orientation and/or a
displacement of the magnetic bodies and to the coloring agent that
is sensitive to an external stimulus.
[0009] The coloring agent that is sensitive to an external stimulus
may change form chemically in response to the external stimulus.
The coloring agent may also keep the same chemical form and pass
into an excited state in response to the external stimulus.
[0010] The external stimulus may be light radiation, a temperature
variation, or a mechanical or chemical action.
[0011] The bodies with non-zero magnetic susceptibility, also
termed magnetic bodies, may be composed at least in part by the
coloring agent that is sensitive to an external stimulus, or they
may be different therefrom.
[0012] When the magnetic bodies contribute color, a change in their
orientation under the effect of the magnetic field may lead to a
change in the appearance of the composition.
[0013] When the magnetic bodies are displaced, the shape of the
deposit of composition may be affected, thereby enabling a portion
in relief to be created, for example.
[0014] The composition need not be exposed to the magnetic field
while the composition is being applied. The magnetic field may be
exerted after the composition has been applied.
[0015] The magnetic field may be applied so as to form at least one
pattern on the composition, said pattern being linked to the shape
of the field lines, for example.
[0016] The invention makes it possible to create novel makeup
effects with a cosmetic composition, enabling patterns in relief to
be produced, for example, or imparting an impression of relief or
various other possibly geometrical patterns.
[0017] Said pattern may be permanently visible or may appear only
under certain conditions connected with the coloring agent having
optical properties that are sensitive to an external stimulus.
[0018] As an example, under certain environmental conditions, the
pattern may be more visible. The coloring agent that is sensitive
to an external stimulus may, for example, have a highly saturated
color under certain conditions, which renders a pattern connected
with a particular orientation of at least one magnetic pigment
difficult to see. Under other environmental conditions, the color
of the coloring agent is less saturated or even non-existent, and
the pattern becomes clear or easier to see.
[0019] When the coloring agent that is sensitive to an external
stimulus is a thermochromic or photochromic agent, the pattern may,
for example, appear or disappear as a function of the temperature
or intensity of UV radiation.
[0020] The coloring agent may also be luminescent, for example
mechanoluminescent, phosphorescent, or fluorescent.
[0021] At least one coloring agent that is sensitive to an external
stimulus may be fixed to a magnetic body. Said coloring agent may,
for example, coat a magnetic body at least in part, it may be mixed
with or form a matrix loaded with magnetic particles, or it may be
grafted to a magnetic body.
[0022] The magnetic field may also be applied so as to model the
clarity and/or the color of at least a region of the face or of the
body to which the composition has been applied.
[0023] For example, when the cosmetic composition is a foundation,
orienting the magnetic bodies under the effect of the magnetic
field makes it possible to modify the clarity of the composition
and thus to model the appearance of the face in the regions exposed
to the magnetic field, in particular so as to apply makeup of cameo
type, without sharp transitions between the light regions and the
dark regions if so desired. By way of example, the magnetic field
may be applied so as to darken the sides of the face, so as to make
it appear thinner than it really is.
[0024] In an implementation of the invention, a layer of a second
cosmetic composition is applied to the first containing the
magnetic bodies with a view to obtaining a depth, gloss,
smoothness, or other effect, for example. The second composition
may be transparent and may optionally be colored. By way of
example, the second composition may be for application to the lips
or to the nails. The second composition may also be applied to the
surface before the first composition, so as to create a colored
base, or so as to improve the retention and/or the comfort of the
first composition, for example.
[0025] The magnetic field may be applied until the composition
containing the magnetic bodies obtains a fixed appearance, i.e. the
appearance of said composition ceases to vary even if the magnetic
field continues to exist. In a variant, the magnetic field may be
applied for a period of time that is shorter than the period of
time that causes all of the magnetic bodies in the exposed region
to be permanently displaced and/or oriented.
[0026] Since the clarity and/or the color of the first composition
change progressively under the effect of the magnetic field, the
user can stop subjecting the magnetic bodies to the field when the
first composition presents the desired appearance.
[0027] The magnetic field may be exerted successively on different
regions of the surface that are coated with the composition.
[0028] The magnetic field may be exerted on regions of the surface
that are disjoint, so as to create separate patterns, for
example.
[0029] A region of the surface coated with the composition need not
be exposed to the magnetic field, so as not to modify the
appearance of the composition in said region after it has been
deposited. Two regions of the surface may be exposed unequally to
the magnetic field.
[0030] The composition may be applied in various ways, e.g. by
means of a cosmetics applicator that is preferably non-magnetic and
that is selected from brushes, flocked endpieces, foams, woven
fabrics, non-woven fabrics, brushes, or combs, for example, or it
may be applied without using an applicator, with the composition
being spread on with the fingers, or sprayed on, for example.
[0031] In an implementation of the invention, the composition is
applied to the surface through a perforated mask. This makes it
possible to produce a predetermined pattern corresponding to the
shape of the perforation, for example. At least one region of the
surface covered in the first composition may then be exposed to the
magnetic field.
[0032] After a given drying time, the composition may take on a
state that prevents the magnetic bodies from further changing their
orientation under the effect of a magnetic field. This applies to a
nail varnish, for example. In some circumstances, the orientation
of the magnetic particles may also be modified at any time, in
particular when the first composition does not dry, or presents a
very long drying time. This may apply to a foundation, for
example.
[0033] The magnetic bodies may be presented in various forms.
Magnetic Bodies
[0034] The expression "magnetic bodies" must not be understood in
limiting manner and covers particles, fibers, or clumps of
particles and/or fibers, of any shape, presenting non-zero magnetic
susceptibility.
[0035] The concentration of magnetic bodies in the composition lies
in the range about 0.05% to about 50% by weight, for example, in
particular in the range about 0.1% to about 40% by weight, better
in the range 1% to about 30% by weight.
[0036] The applied composition may include magnetic fibers or other
aspherical bodies, such as chains of particles or of fibers.
[0037] In the absence of a magnetic field, the magnetic bodies
preferably do not present any remanent magnetism.
[0038] The magnetic bodies may comprise any magnetic material that
presents sensitivity to the lines of a magnetic field, regardless
of whether the field is produced by a permanent magnet or is the
result of induction, the material being selected from nickel,
cobalt, iron, and alloys and oxides thereof, in particular
Fe.sub.3O.sub.4, and also from gadolinium, terbium, dysprosium,
erbium, and alloys and oxides thereof, for example. The magnetic
material may be of the "soft" or of the "hard" type. In particular,
the magnetic material may be soft iron.
[0039] The magnetic bodies may optionally present a multilayer
structure including at least one layer of a magnetic material such
as iron, nickel, cobalt, and alloys and oxides thereof, in
particular Fe.sub.3O.sub.4, for example.
[0040] The magnetic bodies are preferably aspherical, presenting an
elongate shape, for example. Thus, when the particles are subjected
to the magnetic field, they tend to become oriented with their
longitudinal axes in alignment with the field lines, and they are
subjected to a change in orientation which results in the first
composition changing in appearance.
[0041] When the magnetic bodies are substantially spherical
particles, their appearance is preferably non-uniform, so that a
change in orientation results in a change in appearance.
[0042] Regardless of their form, the size of the bodies may be in
the range 1 nanometers (nm) to 10 millimeters (mm), for example,
preferably in the range 10 nm to 5 mm, and more preferably in the
range 100 nm to 1 mm, e.g. in the range 0.5 micrometers (.mu.m) to
300 .mu.m or 1 .mu.m to 150 .mu.m. The size is the size given by
the statistical grain size distribution at half the population,
referred to as "D50".
[0043] When the bodies are particles that do not have an elongate
shape, or that have an elongate shape with a relatively small form
factor, the size of the particles is less than 1 mm, for
example.
[0044] The magnetic bodies are magnetic pigments, for example.
Magnetic Pigments
[0045] Particularly suitable pigments are nacres comprising iron
oxide Fe.sub.3O.sub.4. By way of example, pigments presenting
magnetic properties are those sold under the trade names COLORBNA
BLACKSTAR BLUE, COLORONA BLACKSTAR GREEN, COLORONA BLACKSTAR GOLD,
COLORONA BLACKSTAR RED, CLOISONNE NU ANTIQUE SUPER GREEN, MICRONA
MATTE BLACK (17437), MICA BLACK (17260), COLORONA PATINA SILVER
(17289), and COLORONA PATINA GOLD (117288) by MERCK, or indeed
FLAMENCO TWILIGHT RED, FLAMENCO TWILIGHT GREEN, FLAMENCO TWILIGHT
GOLD, FLAMENCO TWILIGHT BLUE, TIMICA NU ANTIQUE SILVER 110 AB,
TIMICA NU ANTIQUE GOLD 212 GB, TIMICA NU-ANTIQUE COPPER 340 AB,
TIMICA NU ANTIQUE BRONZE 240 AB, CLOISONNE NU ANTIQUE GREEN 828 CB,
CLOISONNE NU ANTIQUE BLUE 626 CB, GEMTONE MOONSTONE G 004,
CLOISONNE NU ANTIQUE RED 424 CHROMA-LITE, BLACK (4498), CLOISONNE
NU ANTIQUE ROUGE FLAMBE (code 440 XB), CLOISONNE NU ANTIQUE BRONZE
(240 XB), CLOISONNE NU ANTIQUE GOLD (222 CB), and CLOISONNE NU
ANTIQUE COPPER (340 XB) by ENGELHARD.
[0046] Still by way of example of a magnetic pigment that is
suitable for being used in the formulation of the composition,
mention may be made of black iron oxide particles, e.g. those sold
under the trade name SICOVIT noir E172 by BASF.
[0047] Magnetic pigments may also comprise metallic iron, in
particular passivated soft iron, e.g. obtained from carbonyl iron
by implementing the method described in U.S. Pat. No. 6,589,331,
the contents of which are incorporated herein by reference. The
particles may include a surface oxide layer.
[0048] Soft-iron based particles are sold in particular under the
trade name STAPA.RTM. WM IRON VP 041040 by ECKART.
[0049] The magnetic bodies may comprise fibers.
Magnetic Fibers
[0050] The term "fibers" means generally elongate bodies
presenting, for example, a form factor in the range 3.5 to 2500 or
5 to 500, e.g. 5 to 150. The form factor is defined by the ratio
L/D, where L is the length of the fiber and D is the diameter of
the circle in which the widest cross-section of the fiber is
inscribed.
[0051] By way of example, the cross-section of the fibers may be
inscribed in a circle having a diameter in the range 2 nm to 500
.mu.m, e.g. in the range 100 nm to 100 .mu.m, or even 1 .mu.m to 50
.mu.m.
[0052] By way of example, the fibers may present a length in the
range 1 .mu.m to 10 mm, e.g. 0.1 mm to 5 mm, or even 0.3 mm to 3.5
mm.
[0053] By way of example, the fibers may present a weight in the
range 0.15 denier to 30 denier (weight in grams for 9 km of
thread), e.g. 0.18 denier to 18 denier.
[0054] The cross-section of the fibers may be of any shape, e.g.
circular, or polygonal, in particular square, hexagonal, or
octagonal.
[0055] The composition may contain solid or hollow fibers that may
be independent or interlinked, e.g. braided.
[0056] The composition may contain fibers having ends that are
blunted and/or rounded, e.g. by polishing.
[0057] The shape of the fibers need not be significantly modified
when they are inserted into the composition, with said fibers being
initially rectilinear and sufficiently rigid to keep their shape.
In a variant, the fibers may present flexibility that enables them
to be substantially deformed within the composition.
[0058] The fibers may contain a non-zero amount, that may be as
great as 100%, of a magnetic material selected from soft magnetic
materials, hard magnetic materials, in particular based on iron,
zinc, nickel, cobalt, or manganese, and alloys and oxides thereof,
in particular Fe.sub.3O.sub.4, rare earths, barium sulfate,
iron-silicon alloys, possibly containing molybdenum, Cu.sub.2MnAl,
MnBi, or a mixture thereof, this list not being limiting.
[0059] When the composition contains fibers containing magnetic
particles, said magnetic particles may be present at least at the
surface of the fibers, or only at the surface of the fibers, or
only inside the fibers, or they may even be dispersed within the
fibers in substantially uniform manner, for example.
[0060] By way of example, each fiber may include a non-magnetic
core with a plurality of magnetic particles on its surface.
[0061] Each fiber may also include a synthetic matrix containing a
plurality of magnetic grains dispersed therein.
[0062] Where appropriate, a synthetic material filled with magnetic
particles may itself be covered by a non-magnetic membrane. By way
of example, such a membrane constitutes a barrier isolating the
magnetic material(s) from the surrounding environment and/or it can
provide color. Each fiber may comprise a one-piece magnetic core
and be covered by a non-magnetic membrane, or it may comprise a
one-piece non-magnetic core and be covered by a magnetic
membrane.
[0063] The composition may contain fibers made by extruding or
co-extruding one or more polymeric materials, in particular
thermoplastics and/or elastomers. One of the extruded materials may
contain a filler of dispersed magnetic particles.
[0064] Each fiber may comprise a synthetic material selected from
polyamides; polyethylene terephthalate (PET); acetates;
polyolefins, in particular polyethylene (PE) or polypropylene (PP);
polyvinyl chloride (PVC); polyester block amide; plasticized
Rilsan.RTM.; elastomers, in particular polyester elastomers,
polyethylene (PE) elastomers, silicone elastomers, nitrile
elastomers; or a mixture of these materials, this list not being
limiting.
[0065] The composition may contain composite fibers each comprising
a magnetic core that is covered, at least in part, by at least one
non-magnetic, synthetic, or natural material. By way of example,
the magnetic core may be covered by co-extruding a membrane made of
a non-magnetic material around the core.
[0066] The core may alternatively be covered in some other way,
e.g. by polymerization in situ.
[0067] The core may be a single piece or it may include a filler of
magnetic grains dispersed in a matrix.
[0068] The composition may also contain composite fibers obtained
by covering a non-magnetic, synthetic, or natural core, with a
synthetic material filled with magnetic particles, the core being
composed of a fiber made of wood; rayon; polyamide; plant matter;
or polyolefin, in particular polyethylene, Nylon.RTM.,
polyimideamide, or aramid, this list not being limiting.
[0069] The composition may also contain magnetic composite
particles, in particular a magnetic latex.
Magnetic Composite Particles
[0070] A magnetic composite particle is a composite material
constituted by an organic or an inorganic matrix and by magnetic
grains. At their surfaces and/or within themselves, the magnetic
composite particles may thus include grains of a magnetic material.
The composite particles may be constituted by a magnetic core
covered by an organic or an inorganic matrix, or they may be
constituted by an organic or an inorganic core covered by a
magnetic matrix.
[0071] The magnetic composite particles include one of the
above-mentioned magnetic materials, for example.
[0072] The size of the magnetic composite particles may be in the
range 1 nm to 1 mm, for example, preferably in the range 100 nm to
500 .mu.m, and more preferably in the range 500 nm to 100 .mu.m.
The term "size" means the size given by the statistical grain size
distribution at half the population, referred to as "ID50".
[0073] The thesis by C. GOUBAULT, dated Mar. 23, 2004, and
incorporated herein by reference, refers, in chapter 1, to the
prior art on the subject of magnetic composite particles, and draws
up a list of preparation methods that are suitable for being used
to prepare magnetic composite particles, namely separately
synthesizing the magnetic grains and the matrix, synthesizing the
magnetic grains in contact with the matrix, or synthesizing the
matrix in the presence of the magnetic grains.
[0074] KISKER markets inorganic-matrix magnetic composite particles
composed of silica. DYNAL, SERADYN, ESTAPOR, and ADEMTECH propose
organic-matrix magnetic composite particles that are also suitable
for being used in the invention.
[0075] More particularly, under the reference M1-070/60, ESTAPOR
markets magnetic latex constituted by grains of ferrite that are
evenly distributed in a polystyrene matrix, said latex including
65% iron oxide, the mean diameter of the polystyrene particles
being 890 nm, and the dry material mass content being 10%.
Ferrofluid
[0076] The composition may contain a ferrofluid, i.e. a stable
colloidal suspension of magnetic particles, in particular of
magnetic nanoparticles.
[0077] The particles, having a size of the order of several tens of
nanometers, for example, are dispersed in a solvent (water, oil,
organic solvent), either by means of a surfactant or a dispersant,
or by electrostatic interactions.
[0078] By way of example, the ferrofluids can be prepared by
grinding ferrites or other magnetic particles until nanoparticles
are obtained, which particles are then dispersed in a fluid
containing a surfactant which is absorbed by the particles and
stabilizes them, or else they can be prepared by precipitating a
metallic-ion solution in a basic medium.
[0079] Each particle of the ferrofluid presents a magnetic moment
that is determined by the size of the particle, and by the nature
of the magnetic material.
[0080] Under the action of a magnetic field, the magnetic moments
of the particles tend to come into alignment with the field lines,
with non-zero magnetization appearing in the liquid. If the field
is removed, there is no hysteresis and magnetization drops to
zero.
[0081] Beyond a field threshold value, it is also possible to cause
macroscopic changes in the liquid, e.g. the appearance of peaks, or
a change in rheological properties.
[0082] The term "ferrofluid" also encompasses an emulsion of
ferrofluid droplets in a solvent. Each drop thus contains colloidal
magnetic particles in stable suspension. This makes it possible to
have a ferrofluid in any type of solvent. The size of the magnetic
particles in suspension in the ferrofluid may be in the range 1 nm
to 10 .mu.m, for example, preferably in the range 1 nm to 1 .mu.m,
and more preferably in the range 1 nm to 100 nm. The term "size"
means the size given by the statistical grain size distribution at
half the population, referred to as "D50".
[0083] Mention can be made in particular of ferrofluids sold by
Liquids Research LTD under the references: [0084] WHKS1S9 (A, B, or
C), which is a water-based ferrofluid containing magnetite
(Fe.sub.3O.sub.4), having particles of 10 nm in diameter. [0085]
WHJS1 (A, B, or C), which is an isoparaffin-based ferrofluid,
containing magnetite (Fe.sub.3O.sub.4) particles that are 10 nm in
diameter. [0086] BKS25_dextran, which is a water-based ferrofluid
stabilized by dextran, containing magnetite (Fe.sub.3O.sub.4)
particles that are 9 nm in diameter.
Chains of Particles and/or of Magnetic Fibers
[0087] The composition may contain clumps of particles or fibers
having a largest dimension, e.g. length, that may, for example, be
in the range 1 nm to 10 mm, e.g. in the range 10 nm to 5 mm, or in
the range 100 nm to 1 mm, or even in the range 0.5 .mu.m to 3.5 mm,
e.g. in the range 1 .mu.m to 150 .mu.m. The term "size" means the
size given by the statistical grain size distribution at half the
population, referred to as "D50".
[0088] By way of example, chains of magnetic particles may be
obtained by assembling colloidal magnetic particles, as described
in the publications "Permanently linked monodisperse paramagnetic
chains", by E. M. Furst, C. Suzuki, M. Fermigier, A. P. Gast,
Langmuir, 14, 7334-7336 (1998), "Suspensions of magnetic
particles", by M. Fermigier, Y. Grasselli, Bulletin of the SFP
(105) July 1996, and "Flexible magnetic filaments as
micromechanical sensors", by C. Goubault, P. Jop, M. Fermigier, J.
Baudry, E. Bertrand, J. Bibette, Phys. Rev. Lett., 91, 26, 260802-1
to 260802-4 (2003), the contents of which are incorporated herein
by reference.
[0089] In particular, those articles describe how to proceed in
order to obtain chains of magnetic-latex particles that include a
polystyrene matrix containing grains of iron oxide with functions
on the surface, and that are bonded together in permanent manner
following a chemical reaction, in particular covalent bonds between
the surfaces of adjacent particles; a method is also described of
obtaining chains of ferrofluid-emulsion droplets that are bonded
together by physical interactions. The length and the diameter of
the permanent chains obtained in this way can be controlled. Such
magnetic chains constitute anisotropic magnetic objects that can be
oriented and displaced under the effect of a magnetic field.
[0090] The dimensions of the magnetic chains may satisfy the same
conditions as for the magnetic fibers.
Coloring Agents that are Sensitive to an External Stimulus
[0091] The composition containing the magnetic bodies may include
at least one photochromic agent.
Photochromic Agents
[0092] In general, a photochromic coloring agent is a coloring
agent having the property of changing hue when it is lit by
ultraviolet light, and of returning to its initial color when it is
no longer lit by said light, or even of passing from a non-colored
state to a colored state and vice-versa. In other words, such an
agent may present different hues depending on whether or not it is
lit by light containing a certain amount of UV radiation.
[0093] The photochromic agent may have a difference .DELTA.E of at
least 5. .DELTA.E is the observed difference in hue in the
photochromic substance, i.e. in the presence of UV radiation and in
the absence of UV radiation.
[0094] Reference may usefully be made to the examples of
photochromic agents described in US 2004/0228818, the contents of
which are hereby incorporated by reference, especially those with a
.DELTA.E of more than 5, as measured in the test presented in that
document.
[0095] Examples of photochromic agents that may be mentioned are
naphtopyrane derivatives of the 2H-naphto-[2,1-b]-pyrane type with
formula (I) or of the 3H-naphto-[2,1-b]-pyrane type with formula
(II):
##STR00001##
in which:
[0096] R1 represents:
[0097] (i) a hydrogen atom;
[0098] (ii) a linear, branched or cyclic, saturated or unsaturated
hydrocarbon group containing 1 to 30 carbon atoms, optionally
comprising 1 to 5 heteroatoms selected from N, O, S, Si and P
and/or optionally halogenated or perhalogenated;
[0099] (iii) a hydrocarbon cycle formed with one of the "f" or "gh"
bonds and the radical R.sub.7; or
[0100] (iv) a group selected from --COOR.sub.4,
--C(O)NR.sub.2R.sub.3, --NR.sub.2R.sub.3, --OR.sub.4 and
--SR.sub.4, in which: [0101] R.sub.2 and R.sub.3 either
independently of each other represent a linear, branched or cyclic,
saturated or unsaturated hydrocarbon group containing 1 to 20
carbon atoms, optionally comprising 1 to 5 heteroatoms selected
from N, O, S, Si and P; or
[0102] taken together with the nitrogen atom to which they are
bonded, they form a saturated or unsaturated hydrocarbon
heterocycle comprising 3 to 10 carbon atoms and optionally 1 to 5
other heteroatoms selected from N, O, S, Si and P, said cycle
optionally being substituted with at least one linear, branched or
cyclic, saturated or unsaturated hydrocarbon radical containing 1
to 20 carbon atoms optionally comprising 1 to 5 heteroatoms
selected from N, O, S, Si and P;
[0103] R.sub.4 represents a linear, branched or cyclic, saturated
or unsaturated hydrocarbon group containing 1 to 20 carbon atoms,
optionally halogenated or perhalogenated, and/or optionally
comprising 1 to 5 heteroatoms selected from N, O, S, Si and P;
[0104] R.sub.5 and R.sub.6 independently represent a group selected
from:
[0105] (i) saturated cyclic aminoaryl groups with formula (IIA) or
(IIB):
##STR00002##
in which the cycle comprising N and X is a saturated cycle
containing a total of 3 to 30 atoms including nitrogen, the
remainder being carbon atoms and/or heteroatoms selected from O, S,
Si, P and/or groups selected from --NH and --NR where R represents
a linear, branched or cyclic, saturated or unsaturated hydrocarbon
radical containing 1 to 20 carbon atoms optionally comprising 1 to
5 heteroatoms selected from N, O, S, Si and P; (ii) indolinoaryl
groups with formula (III):
##STR00003##
in which R.sub.10 and R.sub.11 independently represent a group
selected from (i) linear, branched or cyclic, saturated or
unsaturated hydrocarbons groups containing 1 to 30 carbon atoms
optionally comprising 1 to 5 heteroatoms selected from N, O, S, Si
and P and/or optionally halogenated or perhalogenated; (ii) halogen
atoms; (iii) --CN (nitrile), --COOH (carboxylate), --NO.sub.2
(nitro) groups; (iv) a hydrogen atom; (v) a group selected from
--C(O)NR.sub.2R.sub.3, --NR.sub.2R.sub.3, --OR.sub.4 or --SR.sub.4
where R.sub.2, R.sub.3 and R.sub.4 have the meanings given above;
(vi) radicals R.sub.10 and R.sub.11 may together form a saturated
or unsaturated hydrocarbon cycle containing a total of 5 to 8 atoms
(including the atoms of the indoline cycle), said atoms being
selected from C, O, S and/or NR where R represents H or a linear,
branched or cyclic, saturated or unsaturated hydrocarbon radical
containing 1 to 20 carbon atoms optionally comprising 1 to 5
heteroatoms selected from N, O, S, Si and P;
[0106] (iii) groups with formula (IV):
##STR00004##
in which m and p are independently whole numbers from 2 to 5;
[0107] (iv) unsaturated cyclic aminoaryl groups with formulae (VA),
(VB) or (VC):
##STR00005##
in which R.sub.8 and R.sub.9 independently represent a group
selected from (i) linear, branched or cyclic, saturated or
unsaturated hydrocarbon groups containing 1 to 30 carbon atoms
optionally comprising 1 to 5 heteroatoms selected from N, O, S, Si
and P and/or optionally halogenated or perhalogenated; (ii) halogen
atoms; (iii) --CN (nitrile), --COOH (carboxylate), --NO.sub.2
(nitro) groups; (iv) a hydrogen atom; (v) a group selected from
--C(O)NR.sub.2R.sub.3, --NR.sub.2R.sub.3, --OR.sub.4 or --SR.sub.4
where R.sub.2, R.sub.3 and R.sub.4 have the meanings given
above;
[0108] (v) a linear, branched or cyclic, saturated or unsaturated
hydrocarbon group containing 1 to 30 carbon atoms optionally
comprising 1 to 5 heteroatoms selected from N, O, S, Si and P; and
especially a group selected from
--C.sub.6H.sub.4--CONR.sub.2R.sub.3,
--C.sub.6H.sub.4--NR.sub.2R.sub.3 and --C.sub.6H.sub.4--OR.sub.4
where R.sub.2, R.sub.3 and R.sub.4 have the meanings given
above;
[0109] R.sub.7 represents a group selected from:
[0110] (i) linear, branched or cyclic, saturated or unsaturated
hydrocarbon groups containing 1 to 30 carbon atoms optionally
comprising 1 to 5 heteroatoms selected from N, O, S, Si and P
and/or optionally halogenated or perhalogenated;
[0111] (ii) halogen atoms;
[0112] (iii) --CN (nitrile), --COOH (carboxylate), --NO.sub.2
(nitro); --N.dbd.N-- (azo); .dbd.NH (imino); --CONH.sub.2 (amide)
groups;
[0113] (iv) a hydrogen atom;
[0114] (v) a group selected from --C(O)NR.sub.2R.sub.3,
--NR.sub.2R.sub.3, --OR.sub.4 or --SR.sub.4 where R.sub.2, R.sub.3
and R.sub.4 have the meanings given above;
[0115] (vi) the radical R.sub.7 may also form, with one of bonds
"i", "j", "k", or "g,h" taken with the radical R.sub.1, or "f"
taken with the radical R.sub.1, a saturated hydrocarbon cycle
containing a total of 3 to 8 carbon atoms, optionally comprising 1
to 5 heteroatoms selected from N, O, S, Si and P;
[0116] R'.sub.1 represents a group selected from:
[0117] (i) a hydrogen atom;
[0118] (ii) a linear, branched or cyclic, saturated or unsaturated
hydrocarbon group containing 1 to 30 carbon atoms optionally
comprising 1 to 5 heteroatoms selected from N, O, S, Si and P
and/or optionally halogenated or perhalogenated;
[0119] (iii) a group selected from --C(O)NR.sub.2R.sub.3,
--NR.sub.2R.sub.3, --OR.sub.4 and --SR.sub.4, where R.sub.2,
R.sub.3 and R.sub.4 have the meanings given above;
[0120] R'.sub.2 represents a group selected from:
[0121] (i) linear, branched or cyclic, saturated or unsaturated
hydrocarbon groups containing 1 to 30 carbon atoms optionally
comprising 1 to 5 heteroatoms selected from N, O, S, Si and P
and/or optionally halogenated or perhalogenated;
[0122] (ii) halogen atoms;
[0123] (iii) --CN (nitrile), --COOH (carboxylate), --NO.sub.2
(nitro); --N.dbd.N-(azo); .dbd.NH (imino); --CONH.sub.2 (amide)
groups;
[0124] (iv) a hydrogen atom;
[0125] (v) a group selected from --C(O)NR.sub.2R.sub.3,
--NR.sub.2R.sub.3, --OR.sub.4 or --SR.sub.4 where R.sub.2, R.sub.3
and R.sub.4 have the meanings given above.
[0126] Further examples of photochromic agents that may be
mentioned are diarylethene, with formula
##STR00006##
its derivatives;
[0127] le dihydroazulene/vinylheptafulvene, with formula
##STR00007##
its derivatives;
[0128] spironaphthoxazine, with formula
##STR00008##
its derivatives.
[0129] The photochromic agent may be an organic or inorganic
compound. An organic photochromic agent may produce a more rapid
and intense color change.
[0130] Examples of photochromic agents that may be mentioned are
Photosol.RTM. from PPG, which changes color reversibly when
activated by UV radiation with a wavelength in the range 300 nm to
360 nm, Reversacol.RTM. from J. ROBINSON and Photogenica.RTM. from
CATALYST & CHEMICALS.
[0131] The photochromic agent may be attached to magnetic bodies,
for example by coating magnetic cores with a substance containing
said photochromic agent, thereby producing bodies containing
magnetic grains and a synthetic matrix comprising the photochromic
agent, or by forming chains of particles containing magnetic bodies
and a photochromic agent. As an example, PHOTOGENICA pigments from
CATALYST & CHEMICALS may be combined with those known under the
reference STAPA WM IRON VP 041040 from ECKART.
Thermochromic Agents
[0132] A thermochromic agent is a pigment or colorant which can
change color as a function of temperature.
[0133] As an example, the thermochromic agent may have a color that
is lost when the temperature exceeds a certain value, for example
about 15.degree. C. or about 30.degree. C., depending on the nature
of the thermochromic agent.
[0134] The thermochromic agent may comprise capsules of a polymer
containing a solvent, said solvent, if it has dissolved them,
allowing the compounds to come into contact and modify the light
absorption properties.
[0135] The color change may be reversible.
[0136] The thermochromic agent is, for example, attached to the
magnetic bodies, in like manner to the photochromic agent, as
discussed above.
[0137] As an example, it is possible to use the thermochromic agent
sold with reference Kromafast.RTM. Yellow5GX 02 by KROMACHEM LTD,
or Chromazone.RTM. as a powder or a dispersion, namely
Thermobatch.RTM. or Thermostar.RTM., from CHROMAZONE.
Piezochromic and Tribochromic Agents
[0138] A piezochromic agent can change color in the presence of a
mechanical force.
[0139] An example of a piezochromic agent that may be mentioned is
diphenylflavylene.
[0140] A tribochromic agent can change color in the presence of a
mechanical force in a manner that lasts longer than with
piezochromic agents.
[0141] Reference should be made in this regard to the patent
publication WO-A-94/26729, the content of which is incorporated by
reference.
Solvatochromic Agents
[0142] A solvatochromic agent can change color in the presence of
at least one solvent.
[0143] DCRed27 dye is an example. In its anhydrous formulation,
that compound is free of color. Adding water reveals a pink
color.
Luminescent Agents
[0144] The composition may comprise at least one luminescent agent
which is capable of assuming an excited state in the presence of an
external stimulus; loss of that excited state is accompanied by
emission of light in the visible region. Fluorescent,
mechanoluminescent and phosphorescent agents are included in this
category of luminescent agents.
Mechanoluminescent Agents
[0145] These agents are capable of emitting light when they are
subject to mechanical stress such as a compression, shear or
friction.
[0146] The mechanoluminescent agent is preferably in the form of
particles which are insoluble in the cosmetic medium. The mean
particle size is between 0.01 .mu.m and 50 .mu.m, preferably
between 0.1 .mu.m and 10 .mu.m, for example.
[0147] Examples of mechanoluminescent materials that may be
mentioned are:
[0148] a) complexes and chelates of lanthanides, such as those
described in U.S. Pat. No. 6,071,632, US 2002/0015965 and WO
09/016,429 the contents of which are incorporated by reference. The
rare earths are preferably selected from europium, terbium,
samarium and dysprosium. In said materials, diketones are used as
the ligand for the trivalent lanthanide salts. Said materials are
in an organic medium.
[0149] b) Aluminates, silicates and aluminosilicates doped with
rare earth ions such as those described in U.S. Pat. No. 6,280,655,
EP 1 318 184, JP 2002/194349, JP 2004/59746, the contents of which
are incorporated by reference, especially
(Sr,Mg,Ba,Zn,Ca)Al.sub.2O.sub.4,
(SrLa,SrY)Al.sub.3O.sub.7(Sr.sub.2,SrMg,SrCa,SrBa)Al.sub.6O.sub.11,
Sr.sub.2(Mg,Al) (Al,Si) SiO.sub.7, Sr(Zn,Mn,Fe,Mg) Si.sub.2O.sub.6.
The elements in parentheses are completely or partially
interchangeable. Ions of rare earths such as cerium, europium,
samarium, neodymium, gadolinium, dysprosium and terbium may be
used, alone or as a mixture. Europium and dysprosium are
preferred.
[0150] c) Zinc sulfide, manganese sulfide, copper sulfide, cadmium
sulfide or zinc oxide, optionally doped with transition metal ions
or rare earth ions, as described in U.S. Pat. No. 6,117,574 and JP
2004/43656 the contents of which are incorporated by reference.
Preferred transition metal ions are copper and manganese. Preferred
rare earth ions are europium or cerium. Of said materials, ZnS:Mn
is preferred.
[0151] The materials listed under b) and c) may be synthesized by
solid phase reaction using a dry mixture followed by heat treatment
and high temperature sintering, or by a sol-gel process followed by
drying, heating and sintering. The sintering temperature is more
than 1000.degree. C., for example.
[0152] The materials listed under b) are preferred. Of these,
SrAl.sub.2O.sub.4 and SrMgAl.sub.10O.sub.17 doped with rare earth
metals are preferred.
[0153] Mechanoluminescent pigments SrAl.sub.2O.sub.4 doped with
rare earth metal ions are sold with reference TAIKO-M1-1 by TAIKO
Refractories Co., Ltd. The particles of this pigment have a
diameter in the range 5 .mu.m to 10 .mu.m and a green luminescence
under a small mechanical stress.
Fluorescent (ou Photoluminescent) Agents
[0154] This may be a compound which absorbs light in the
ultraviolet and re-emits it in the visible region.
[0155] The fluorescent agent may, for example, comprise silicon
nanoparticles such as those obtained using the processes described
in WO-A-01/38222 and US 2002/0070121.
[0156] The fluorescent agent may comprise at least one rare
earth.
[0157] The following publications: EP-A-0 962 224, U.S. Pat. No.
6,753,002, JP-A-2 805 373, FR-A-2 847 812 and FR-A-2 850 271
describe other photoluminescent agents.
Phosphorescent Agents
[0158] These are compounds which emit light in darkness.
[0159] Examples of phosphorescent compounds that may be mentioned
are the LumiNova.RTM. pigment from Nemoto and Co Ltd, described in
U.S. Pat. No. 5,424,006, herewith incorporated by reference.
[0160] Phosphorus sulphide (ZnS:Cu) is another example of a
phosphorescent compound.
[0161] The phosphorescent compound may be incorporated into an
inert matrix, or it may be coated to isolate it from the ambient
medium.
Other Coloring Agents
[0162] The composition comprising the magnetic bodies may contain
at least one coloring agent other than a coloring agent that is
sensitive to an external stimulus and producing a color by
absorbing at least a fraction of the visible spectrum. Said
coloring agent may be constituted by a magnetic or non-magnetic
pigment, which may be organic, inorganic, or a hybrid comprising
both an organic substance and an inorganic substance.
[0163] A color produced by light absorption is still sometimes
termed a chemical color, as opposed to colors produced by an
interference phenomenon, including diffraction, still termed
physical colors. Electron transitions may be the origin of the
phenomenon whereby the coloring agent absorbs light.
[0164] The coloring agent may optionally be a particulate
compound.
[0165] Where appropriate, the particles of a single magnetic
pigment constitute both the coloring agent, producing the color by
an absorption phenomenon, and the magnetic bodies.
[0166] When the coloring agent includes a colorant, said colorant
may be selected from amongst liposoluble and hydrosoluble
colorants.
[0167] Examples of liposoluble colorants are Sudan red, D&C Red
No. 17, D&C Green No. 6, .beta.-carotene, soybean oil, Sudan
brown, D&C Yellow No. 11, D&C Violet No. 2, D&C orange
No. 5, and quinoline yellow.
[0168] Examples of hydrosoluble colorants are beetroot juice and
methylene blue.
[0169] By way of example, the colorants may represent 0.1% to 20%
by weight of the first or second composition, or even 0.1% to 6%,
when present.
[0170] The coloring agents may also be a lake or an organic pigment
selected from the following materials and mixtures thereof: [0171]
cochineal carmine; [0172] the organic pigments of azo,
anthraquinone, indigo, xanthene, pyrene, quinoline,
triphenylmethane, or fluorane dyes; [0173] organic lakes or
insoluble salts of sodium, potassium, calcium, barium, aluminum,
zirconium, strontium, titanium, or of acid dyes such as azo,
anthraquinone, indigo, xanthene, pyrene, quinoline,
triphenylmethane, or fluorine dyes, which dyes may comprise at
least one carboxylic or sulfonic acid group.
[0174] Organic pigments that may be mentioned include those with
the following denominations: D&C Blue No. 4, D&C Brown No.
1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4,
D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11,
D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C
Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No.
28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33,
D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2,
D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10,
D&C Yellow No. 11, FD&C Blue No. 1, FD&C Green No. 3,
FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No.
6.
[0175] The coloring agent may be an organic lake supported by an
organic support such as colophane or aluminum benzoate, for
example.
[0176] Particular organic lakes that may be mentioned include those
with the following denominations: D&C Red No. 2 Aluminum lake,
D&C Red No. 3 Aluminum lake, D&C Red No. 4 Aluminum lake,
D&C Red No. 6 Aluminum lake, D&C Red No. 6 Barium lake,
D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6
Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7
Aluminum lake, D&C Red No. 7 Barium lake, D&C Red No. 7
Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red
No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red
No. 9 Aluminum lake, D&C Red No. 9 Barium lake, D&C Red No.
9 Barium/Strontium lake, D&C Red No. 9 Zirconium lake, D&C
Red No. 10 Sodium lake, D&C Red No. 19 Aluminum lake, D&C
Red No. 19 Barium lake, D&C Red No. 19 Zirconium lake, D&C
Red No. 21 Aluminum lake, D&C Red No. 21 Zirconium lake,
D&C Red No. 22 Aluminum lake, D&C Red No. 27 Aluminum lake,
D&C Red No. 27 Aluminum/Titanium/Zirconium lake, D&C Red
No. 27 Barium lake, D&C Red No. 27 Calcium lake, D&C Red
No. 27 Zirconium lake, D&C Red No. 28 Aluminum lake, D&C
Red No. 30 lake, D&C Red No. 31 Calcium lake, D&C Red No.
33 Aluminum lake, D&C Red No. 34 Calcium lake, D&C Red No.
36 lake, D&C Red No. 40 Aluminum lake, D&C Blue No. 1
Aluminum lake, D&C Green No. 3 Aluminum lake, D&C Orange
No. 4 Aluminum lake, D&C Orange No. 5 Aluminum lake, D&C
Orange No. 5 Zirconium lake, D&C Orange No. 10 Aluminum lake,
D&C Orange No. 17 Barium lake, D&C Yellow No. 5 Aluminum
lake, D&C Yellow No. 5 Zirconium lake, D&C Yellow No. 6
Aluminum lake, D&C Yellow No. 7 Zirconium lake, D&C Yellow
No. 10 Aluminum lake, FD&C Blue No. 1 Aluminum lake, FD&C
Red No. 4 Aluminum lake, FD&C Red No. 40 Aluminum lake,
FD&C Yellow No. 5 Aluminum lake, FD&C Yellow No. 6 Aluminum
lake.
[0177] The chemical materials corresponding to each of the organic
coloring substances listed above are mentioned in the work entitled
"International Cosmetic Ingredient Dictionary and Handbook", 1997
edition, pages 371 to 386 and 524 to 528, published by "The
Cosmetic, Toiletry, and Fragrance Association", the contents of
which are incorporated herein by reference.
[0178] The coloring agent producing a color by absorbing at least a
fraction of the visible spectrum may advantageously be a composite
pigment including a core that is coated at least in part by a
membrane.
Composite Pigments
[0179] A composite pigment may be composed of particles comprising:
[0180] an inorganic core; and [0181] at least one at least partial
coating of at least one organic coloring substance.
[0182] At least one binder may advantageously contribute to fixing
the organic coloring substance onto the inorganic core.
[0183] The particles of composite pigment may have a variety of
forms. In particular, said particles may be in the form of flakes
or they may be globular, in particular spherical, and may be hollow
or solid. The term "in the form of flakes" means particles for
which the ratio of the largest dimension to the thickness is 5 or
more.
[0184] A composite pigment may, for example, have a specific
surface area in the range 1 square meter per gram (m.sup.2/g) to
1000 m.sup.2/g, in particular in the range about 10 m.sup.2/g to
about 600 m.sup.2/g, and in particular in the range about 20
m.sup.2/g to about 400 m.sup.2/g. The specific surface area is the
value measured using the BET (Brunauer-Emmett-Teller) method.
[0185] The proportion by weight of the core may exceed 50% relative
to the total weight of the composite pigment, for example lying in
the range 50% to 70%, e.g. in the range 60% to 70%.
[0186] The composite pigment may be different from an
interferential pigment as described in U.S. Pat. No. 6,428,773, for
example. By way of example, an interferential pigment includes a
plurality of layers of constant thickness of materials selected so
as to be able to produce optical interferences.
[0187] The saturation C* of the composite pigment may be greater
than or equal to 30, measured in accordance with the following
protocol.
Protocol for Measuring the Saturation of the Composite Pigment
[0188] The values a* and b* in the CIE L*a*b* space of the
composite pigment are measured as follows:
[0189] Pure composite pigment is compacted in a rectangular dish
having dimensions of 2 centimeters (cm).times.1.5 cm and a depth of
3 mm, by applying pressure of 100 bars.
[0190] The values a* and b* of the compacted pigment are measured
with a MINOLTA 3700d spectrophotometer, in excluded specular mode,
under D65 lighting, medium aperture. Saturation is given by
C*=(a*.sup.2+b*.sup.2).sup.1/2.
Inorganic Core
[0191] The inorganic core may have any form that is suitable for
fixing particles of organic coloring substance, for example
spherical, globular, granular, polyhedral, acicular,
spindle-shaped, flattened in the form of a flake, a rice grain, or
a scale, and a combination of these forms, this list not being
limiting.
[0192] Preferably, the ratio of the largest dimension of the core
to its smallest dimension may be in the range 1 to 50.
[0193] The inorganic core may have a mean size in the range about 1
nm to about 100 nm, or even in the range about 5 nm to about 75 nm,
for example in the range about 10 nm to about 50 nm, in particular
20 nm or 25 nm.
[0194] The term "mean size" means the size given by the statistical
grain size distribution at half the population, referred to as
"D50". The mean size may be a number mean size determined by image
analysis (electron microscopy).
[0195] The inorganic core may present a refractive index that is
greater than or equal to 2, or even greater than or equal to 2.1,
e.g. greater than or equal to 2.2.
[0196] The inorganic core may be formed from an optionally-magnetic
material selected from a non-limiting list comprising metallic
salts and metal oxides, in particular oxides of titanium,
zirconium, cerium, zinc, iron, iron blue, aluminum, and chromium,
aluminas, glasses, ceramics, graphite, silicas, silicates, in
particular aluminosilicates and borosilicates, synthetic mica, and
mixtures thereof.
[0197] Oxides of titanium, in particular TiO.sub.2, of iron,
especially Fe.sub.2O.sub.3, of cerium, zinc, and aluminum,
silicates, in particular aluminosilicates and borosilicates, are
particularly suitable.
[0198] The inorganic core may have a specific surface area,
measured using the BET method, in the range about 1 m.sup.2/g to
about 1000 m.sup.2/g, preferably in the range about 10 m.sup.2/g to
about 600 m.sup.2/g, for example in the range about 20 m.sup.2/g to
about 400 m.sup.2/g.
[0199] The inorganic core may be colored if appropriate.
Organic Coloring Material
[0200] By way of example, the organic coloring material may
comprise at least one organic pigment, e.g. at least one organic
lake.
[0201] By way of example, the organic coloring material may be
selected from the insoluble particulate compounds in the
physiologically acceptable medium of the composition.
[0202] By way of example, the organic coloring material may
comprise pigments, e.g. organic lakes or other organic coloring
materials, that may be selected from the following compounds and
mixtures thereof: [0203] cochineal carmine; [0204] the organic
pigments of azo, anthraquinone, indigo, xanthene, pyrene,
quinoline, triphenylmethane, or fluorane dyes; [0205] organic lakes
or insoluble salts of sodium, potassium, calcium, barium, aluminum,
zirconium, strontium, titanium, or of acid dyes such as azo,
anthraquinone, indigo, xanthene, pyrene, quinoline,
triphenylmethane, or fluorine dyes, which dyes may comprise at
least one carboxylic or sulfonic acid group.
[0206] Organic pigments that may be mentioned include those with
the following denominations: D&C Blue No. 4, D&C Brown No.
1, D&C Green No. 5, D&C Green No. 6, D&C Orange No. 4,
D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11,
D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C
Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No.
28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 33,
D&C Red No. 34, D&C Red No. 36, D&C Violet No. 2,
D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10,
D&C Yellow No. 11, FD&C Blue No. 1, FD&C Green No. 3,
FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No.
6.
[0207] The organic coloring substance may comprise an organic lake
supported by an organic support such as colophane or aluminum
benzoate, for example.
[0208] Particular organic lakes that may be mentioned include those
with the following denominations: D&C Red No. 2 Aluminum lake,
D&C Red No. 3 Aluminum lake, D&C Red No. 4 Aluminum lake,
D&C Red No. 6 Aluminum lake, D&C Red No. 6 Barium lake,
D&C Red No. 6 Barium/Strontium lake, D&C Red No. 6
Strontium lake, D&C Red No. 6 Potassium lake, D&C Red No. 7
Aluminum lake, D&C Red No. 7 Barium lake, D&C Red No. 7
Calcium lake, D&C Red No. 7 Calcium/Strontium lake, D&C Red
No. 7 Zirconium lake, D&C Red No. 8 Sodium lake, D&C Red
No. 9 Aluminum lake, D&C Red No. 9 Barium lake, D&C Red No.
9 Barium/Strontium lake, D&C Red No. 9 Zirconium lake, D&C
Red No. 10 Sodium lake, D&C Red No. 19 Aluminum lake, D&C
Red No. 19 Barium lake, D&C Red No. 19 Zirconium lake, D&C
Red No. 21 Aluminum lake, D&C Red No. 21 Zirconium lake,
D&C Red No. 22 Aluminum lake, D&C Red No. 27 Aluminum lake,
D&C Red No. 27 Aluminum/Titanium/Zirconium lake, D&C Red
No. 27 Barium lake, D&C Red No. 27 Calcium lake, D&C Red
No. 27 Zirconium lake, D&C Red No. 28 Aluminum lake, D&C
Red No. 30 lake, D&C Red No. 31 Calcium lake, D&C Red No.
33 Aluminum lake, D&C Red No. 34 Calcium lake, D&C Red No.
36 lake, D&C Red No. 40 Aluminum lake, D&C Blue No. 1
Aluminum lake, D&C Green No. 3 Aluminum lake, D&C Orange
No. 4 Aluminum lake, D&C Orange No. 5 Aluminum lake, D&C
Orange No. 5 Zirconium lake, D&C Orange No. 10 Aluminum lake,
D&C Orange No. 17 Barium lake, D&C Yellow No. 5 Aluminum
lake, D&C Yellow No. 5 Zirconium lake, D&C Yellow No. 6
Aluminum lake, D&C Yellow No. 7 Zirconium lake, D&C Yellow
No. 10 Aluminum lake, FD&C Blue No. 1 Aluminum lake, FD&C
Red No. 4 Aluminum lake, FD&C Red No. 40 Aluminum lake,
FD&C Yellow No. 5 Aluminum lake, FD&C Yellow No. 6 Aluminum
lake.
[0209] The chemical compounds corresponding to each of the organic
coloring substances listed above are mentioned in the work entitled
"International Cosmetic Ingredient Dictionary and Handbook", 1997
edition, pages 371 to 386 and 524 to 528, published by "The
Cosmetic, Toiletry, and Fragrance Association", the contents of
which are incorporated herein by reference.
[0210] The proportion by weight of organic coloring material may
lie in the range about 10 parts to about 500 parts by weight per
100 parts of inorganic core, or even in the range about 20 parts to
about 250 parts by weight, e.g. in the range about 40 parts to
about 125 parts by weight per 100 parts of inorganic core.
[0211] The total content of organic coloring material of the
composition, coming from the composite pigment and from other
possible pigments, may be less than 10%, for example, relative to
the total weight of the composition.
[0212] The proportion of organic coloring material may exceed 30%
relative to the total weight of the composite pigment, for example
lying in the range 30% to 50%, e.g. in the range 30% to 40%.
Binder
[0213] The composite-pigment binder may be of any type provided
that it allows the organic coloring substance to adhere to the
surface of the inorganic core.
[0214] In particular, the binder may be selected from the following
non-limiting list: silicone materials, polymeric, oligomeric or
similar materials, in particular from organosilanes,
fluoroalkylated organosilanes and polysiloxanes, for example
polymethylhydrogen siloxane, as well as a variety of coupling
agents such as coupling agents based on silanes, titanates,
aluminates, zirconates, and mixtures thereof.
[0215] The silicone compound may be selected from the following non
limiting list: [0216] organosilanes (1) obtained from
alkoxysilanes; [0217] polysiloxanes (2) which may optionally be
modified, selected from the following non limiting list: [0218]
modified polysiloxanes (2A) comprising at least one radical
selected in particular from polyethers, polyesters and epoxy
compounds (henceforth termed "modified polysiloxanes"); [0219]
polysiloxanes (2B) carrying, on one silicon atom located at the end
of the polymer, at least one group selected from the following
non-limiting list: carboxylic acids, alcohols, and hydroxyl groups;
and [0220] fluoroalkylated organosilane compounds (3) obtained from
fluoroalkylsilanes.
[0221] The organosilane compounds (I) may be obtained from
alkoxysilane compounds represented by formula (I):
R.sup.1.sub.aSiX.sub.4-a (I)
in which: [0222] R.sup.1 represents C.sub.6H.sub.5--,
(CH.sub.3).sub.2CH--CH.sub.2-- or a C.sub.bH.sub.2b+1-- type
radical (in which b lies in the range 1 to 18); [0223] X represents
CH.sub.3O-- or C.sub.2H.sub.5O--; and [0224] a lies in the range 0
to 3.
[0225] Specific examples of alkoxysilane compounds may include
alkoxysilanes selected from: methyltriethoxysilane,
dimethyldiethoxysilane, phenyltriethoxysilane,
diphenyldiethoxysilane, methyltrimethoxysilane,
dimethyldimethoxysilane, phenyltrimethoxysilane,
diphenyldimethoxysilane, isobutyltrimethoxysilane,
decyltrimethoxysilane, and the like, in particular from
methyltriethoxysilane, phenyltriethoxysilane,
methyltrimethoxysilane, dimethyldimethoxysilane,
isobutyltrimethoxysilane, more preferably from
methyltriethoxysilane, methyltrimethoxysilane, and
phenyltriethoxysilane.
[0226] The polysiloxanes (2) may in particular have formula
(II):
##STR00009##
in which R.sup.2 represents H-- or CH.sub.3-- and d lies in the
range 15 to 450.
[0227] Polysiloxanes for which R.sup.2 represents H are
preferred.
[0228] The modified polysiloxanes (2A) may in particular have the
following formula (III): [0229] (a.sup.1) modified polysiloxanes
carrying polyethers, represented by formula (III):
##STR00010##
[0229] in which R.sup.3 represents --(CH.sub.2).sub.h--; R.sup.4
represents --(CH.sub.2).sub.i--CH.sub.3; R.sup.5 represents --OH,
--COOH, --CH.dbd.CH.sub.2, --C(CH.sub.3).dbd.CH.sub.2 or
--(CH.sub.2).sub.j--CH.sub.3; R.sup.6 represents
--(CH.sub.2).sub.k--CH.sub.3; g and h lie independently in the
range 1 to 15; j and k lie independently in the range 0 to 15; e
lies in the range 1 to 50, and f lies in the range 1 to 300; [0230]
(a.sup.2) modified polysiloxanes carrying polyesters, represented
by formula (IV):
##STR00011##
[0230] in which R.sup.7, R.sup.8, and R.sup.9 independently
represent --(CH.sub.2).sub.q--; R.sup.10 represents --OH, --COOH,
--CH.dbd.CH.sub.2, --C(CH.sub.3).dbd.CH.sub.2 or
--(CH.sub.2).sub.r--CH.sub.3; R.sup.11 represents
--(CH.sub.2).sub.n--CH.sub.3; n and q lie independently in the
range 1 to 15, r and s lie independently in the range 0 to 15; e
lies in the range 1 to 50, and f lies in the range 1 to 300, [0231]
(a.sup.3) modified polysiloxanes carrying epoxy radicals
represented by formula (V):
##STR00012##
[0231] in which R.sup.12 represents --(CH.sub.2).sub.v--; v lies in
the range 1 to 15; t lies in the range 1 to 50, and u lies in the
range 1 to 300; or mixtures thereof.
[0232] Preferred modified polysiloxanes (2A) are modified
polysiloxanes carrying polyethers with formula (III).
[0233] Polysiloxanes modified at the terminal portion (2B) may have
formula (VI):
##STR00013##
in which R.sup.13 and R.sup.14 may represent --OH, R.sup.16--OH, or
R.sup.17--COOH, independently of each other; R.sup.15 represents
--CH.sub.3 or --C.sub.6H.sub.5; R.sup.16 and R.sup.17 represent
--(CH.sub.2).sub.y--; y lies in the range 1 to 15; w lies in the
range 1 to 200; and x lies in the range 0 to 100.
[0234] Preferred polysiloxanes modified on at least one end include
those carrying at least a radical (R.sup.16 and/or R.sup.17)
carrying a carboxylic acid group on at least one terminal silicon
atom.
[0235] Fluoroalkylated organosilane compounds (3) may be obtained
from fluoroalkylsilanes represented by formula (VII):
CF.sub.3(CF.sub.2).sub.zCH.sub.2CH.sub.2(R.sup.18).sub.aSiX.sub.4-a
(VII)
in which: [0236] R.sup.18 represents CH.sub.3--, C.sub.2H.sub.5--,
CH.sub.3O-- or C.sub.2H.sub.5O--; [0237] X represents CH.sub.3O--
or C.sub.2H.sub.5O--; [0238] z lies in the range 0 to 15 and a lies
in the range 0 to 3.
[0239] In particular, the fluoroalkylsilanes may be selected from
the following non limiting list: trifluoropropyltrimethoxysilane,
tridecafluorooctyltrimethoxysilane,
heptadecafluorodecyltrimethoxysilane,
heptadecafluorodecylmethyldimethoxysilane,
trifluoropropyltriethoxysilane, tridecafluorooctyltriethoxysilane,
heptadecafluorodecyltriethoxysilane,
heptadecafluorodecylmethyldiethoxysilane and the like, in
particular trifluoropropyltrimethoxysilane,
tridecafluorooctyltrimethoxysilane and
heptadecafluorodecyltrimethoxysilane, and more preferably
trifluoropropyl trimethoxysilane and
tridecafluorooctyltrimethoxysilane.
[0240] The silane-based coupling agents may be selected from the
following non limiting list: vinyltrimethoxysilane,
vinyltriethoxysilane, .gamma.-aminopropyl-triethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
N-.beta.(aminoethyl)-.gamma.-aminopropyltrimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-chloropropyltrimethoxysilane, and the like.
[0241] The titanate-based coupling agents may be selected from the
following list: isopropylstearoyl titanate,
isopropyltris(dioctylpyrophosphate) titanate,
isopropyltri(N-aminoethyl-aminoethyl)titanate,
tetraoctyl-bis(ditridecylphosphate)titanate,
tetra(2,2-diaryloxymethyl-1-butyl)bis(ditridecyl)phosphate
titanate, bis(dioctylpyrophosphate)oxyacetate titanate,
bis(dioctylpyrophosphate)ethylene titanate, and the like.
[0242] The aluminate-based coupling agents may be selected from
acetoalkoxyaluminum diisopropylate, aluminum
diisopropoxymonoethylacetoacetate, aluminum triethylacetoacetate,
aluminum triacetylacetonate, and the like.
[0243] The zirconate-based coupling agents may be selected from the
following list: zirconium tetrakisacetylacetonate, zirconium
dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate,
zirconium tributoxymonoethylacetoacetate, zirconium
tributoxyacetylacetonate, and the like.
[0244] The compounds acting as a binder may have a molar mass in
the range 300 to 100 000.
[0245] To obtain a layer which uniformly coats the inorganic cores,
the binder is preferably in the liquid state or is soluble in water
or other solvents.
[0246] The quantity of binder may lie in the range 0.01% to 15%, in
particular from 0.02% to 12.5%, and more particularly from 0.03% to
10% by weight (calculated with respect to C or Si) relative to the
weight of particles comprising the core and the binder. Further
details regarding the calculation of the relative quantity of
binder can be found in patent application EP 1 184 426 A2. The
relative proportion of binder may be less than or equal to 5%, e.g.
less than or equal to 3%, relative to the total weight of the
composite pigment.
Preparation of Composite Pigment
[0247] The composite pigment may be prepared using any appropriate
method, e.g. a mechanical/chemical method or a method of
precipitation in solution, with the organic coloring material being
dissolved, then precipitated onto the surface of the core.
[0248] A binder may optionally be used.
[0249] A method comprising mechanically mixing an organic pigment
and the inorganic core is preferred.
[0250] A binder may be added or mixed to the inorganic core before
the organic coloring material is introduced.
[0251] The composite pigment may, for example, be produced using
one of the processes described in European patent applications EP 1
184 426 and EP 1 217 046, the contents of which are hereby
incorporated by reference, and advantageously by the process
described in EP 1 184 426.
[0252] In one implementation, the particles intended to constitute
the inorganic core are first mixed with the binder.
[0253] So that the binder can adhere uniformly to the surface of
the inorganic core, it is preferable to pass said particles
initially through a mill to disaggregate them.
[0254] The mixing and agitation conditions are selected so that the
core is uniformly coated with binder. Such conditions may be
controlled so that the linear load is in the range 19.6 N/cm
(newtons/centimeter) to 19160 N/cm, in particular in the range 98
N/cm to 14170 N/cm and preferably in the range 147 N/cm to 980
N/cm; the treatment time is in the range 5 minutes to 24 hours,
preferably in the range 10 minutes to 20 hours; the rotation rate
may be in the range 2 rpm (revolutions per minute) to 1000 rpm, in
particular in the range 5 rpm to 1000 rpm, and more preferably in
the range 10 rpm to 800 rpm.
[0255] After coating the inorganic core with binder, the organic
coloring substance is added and mixed with agitation so that it
adheres to the layer of binder.
[0256] Examples of addition methods are continuous addition in
large quantities, or in small quantities.
[0257] Mixing and agitation, whether of the inorganic cores with
the binder or of the organic coloring substance with the inorganic
cores coated with binder, may be carried out using an apparatus
which can apply a sharp shearing and/or compressive force to the
mixture of powders. Examples of apparatus of that type are roller
mixers, blade mixers, and the like. Roller mixers are particularly
suitable. A list of suitable apparatus is given in EP 1 184 426
A2.
[0258] A further method for manufacturing a composite pigment has
been described in Japanese patent JP 3286463, which discloses a
solution precipitation process.
[0259] The organic coloring substance is dissolved in ethanol and
the inorganic cores are then dispersed in said ethanolic
solution.
[0260] An aqueous alkaline solution of sodium or potassium
carbonate is then slowly added to these mixtures and finally, an
ethanolic calcium chloride solution is slowly added, with constant
agitation.
[0261] In addition to a coloring agent absorbing light by an
absorption phenomenon, the composition may include at least one
interferential or diffractive pigment and/or reflective
particles.
[0262] In an implementation of the invention, the first composition
contains at least one goniochromatic coloring agent in which a
color change can be observed as a function of the angle of
observation. The goniochromatic coloring agent may optionally be
magnetic.
[0263] When the first composition contains magnetic particles of a
certain color and a non-magnetic goniochromatic coloring agent,
said coloring agent may be selected so that its range of colors
passes substantially through the color of the magnetic
particles.
[0264] By way of example, this can make the magnetic particles more
difficult to detect so long as they are not oriented under the
effect of a magnetic field.
[0265] This can also allow the pattern induced by orienting the
magnetic particles to appear only when the made-up surface is under
certain observation and/or lighting conditions, thereby making it
possible to create pattern disposition and appearance effects that
are particularly attractive.
Goniochromatic Coloring Agents
[0266] The composition containing the magnetic bodies may contain
at least one interferential coloring agent, in particular a
goniochromatic coloring agent, which may present magnetic
properties, where appropriate.
[0267] The term "goniochromatic coloring agent" as used in the
context of the present invention means a coloring agent that makes
it possible, when the composition is spread on a surface, to obtain
a color path in the a*b* plane of the 1976 CIE color space which
corresponds to a variation Dh.sup.o of the hue angle h.sup.o of at
least 200 when the angle of observation is varied relative to the
normal in the range 0.degree. to 80.degree. for light at an angle
of incidence of 45.degree..
[0268] By way of example, the color path may be measured by means
of a spectrogonioreflectometer, from INSTRUMENT SYSTEMS and
referenced GON 360 GONIOMETER, after the first composition has been
spread in the fluid state to a thickness of 300 .mu.m by means of
an automatic spreader on a contrast card from ERICHSEN and
referenced Typ 24/5, the measurements being performed on the black
background of the card.
[0269] By way of example, the goniochromatic coloring agent may be
selected from multilayer interference structures and liquid crystal
coloring agents.
[0270] By way of example, a multilayer structure may comprise at
least two layers, each layer 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.
[0271] The multilayer structure may optionally be symmetrical with
respect to a central layer as regards the chemical nature of the
stacked layers. Depending on the thickness and nature of the
various layers, different effects are obtained.
[0272] Examples of symmetrical multilayer interference structures
are as follows:
Fe.sub.2O.sub.3/SiO.sub.2/Fe.sub.2O.sub.3/SiO.sub.2/Fe.sub.2O.su-
b.3, a pigment having this structure 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, pigments with these structures
being sold under the trade name XIRONA by MERCK (Darmstadt).
[0273] By way of example, liquid crystal coloring agents comprise
silicones, or cellulose ethers onto which mesomorphic groups have
been grafted. Examples of suitable liquid crystal goniochromatic
particles are those sold by CHENIX, and those sold under the trade
name HELICONE.RTM. HC by WACKER.
[0274] Suitable goniochromatic coloring agents are some nacres;
pigments having effects on synthetic substrates, in particular
alumina, silica, borosilicate, iron oxide, or aluminum type
substrates; or holographic interference flakes coming from a
polyterephthalate film.
[0275] The material may further contain dispersed goniochromatic
fibers. Such fibers could present a length that is less than 80
.mu.m, for example.
[0276] The composition containing the magnetic bodies may also
include at least one diffractive pigment, which may present
magnetic properties, where appropriate.
Diffractive Pigments
[0277] The term "diffractive pigment" as used in the context of the
present invention means a pigment that is capable of producing a
variation in color depending on the angle of observation when lit
by white light, because of the presence of a structure which
diffracts the light. Such a pigment is also sometimes referred to
as a holographic or rainbow-effect pigment.
[0278] A diffractive pigment may include a diffraction grating that
is capable of diffracting an incident ray of monochromatic light in
defined directions.
[0279] The diffraction grating may comprise a periodic pattern, in
particular a line, with the distance between two adjacent patterns
being the same as the wavelength of the incident light.
[0280] When the incident light is polychromatic, the diffraction
grating separates the various spectral components of the light and
produces a rainbow effect.
[0281] With regard to the structure of diffractive pigments,
reference 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, the contents of which are incorporated herein by
reference.
[0282] The diffractive pigment may be made with patterns having
various profiles, in particular triangular, optionally symmetrical,
notched, of optionally constant width, sinusoidal, or stepped.
[0283] The spatial frequency of the grating and the depth of the
patterns are selected as a function of the degree of separation of
the various desired orders. The frequency may be in the range 500
lines per mm to 3000 lines per mm, for example.
[0284] Each of the particles of the diffractive pigment preferably
presents a flat shape, and in particular a wafer shape.
[0285] A single pigment particle may include two crossed
diffraction gratings that are optionally perpendicular, and that
optionally have the same ruling.
[0286] The diffractive pigment may present a multilayer structure
comprising a layer of reflective material that is covered on at
least one side by a layer of dielectric material. The dielectric
material may make the diffractive pigment stiffer and longer
lasting. For example, the dielectric material may thus 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. For
example, the reflective material may be selected from metals and
alloys thereof, and also from non-metallic reflective materials:
Metals that may be used include Al, Ag, Cu, Au, Pt, Sn, Ti, Pd, Ni,
Co, Rd, Nb, Cr, and materials, combinations, or alloys thereof.
Such a reflective material may, on its own, constitute the
diffractive pigment which then comprises a single layer.
[0287] In a variant, the diffractive pigment may include a
multilayer structure comprising a core of dielectric material with
a reflective layer covering at least one side, or indeed completely
encapsulating, the core. A layer of dielectric material may also
cover the reflective layer(s). The dielectric material used is thus
preferably inorganic, and may, for example, be selected from metal
fluorides, metal oxides, metal sulfides, metal nitrides, metal
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 carbons, and
combinations thereof.
[0288] In a variant, the diffractive pigment may be composed of a
preformed dielectric or ceramic material such as a naturally
lamellar mineral, e.g. mica peroskovite or talc; or synthetic
platelets formed from glass, alumina, SiO.sub.2, carbon, an iron
oxide/mica, mica covered in BN, BC, graphite, or bismuth
oxychloride, and combinations thereof.
[0289] Instead of a layer of dielectric material, other materials
that improve the mechanical properties may be suitable. Such
materials may include silicone, metal silicides, semiconductor
materials formed from elements of groups III, IV, and V, metals
having a body centered cubic crystal structure, metal-ceramic
compositions or materials, semiconductor glasses, and various
combinations thereof.
[0290] In particular, the diffractive pigment used may be selected
from those described in US patent application No. 2003/0031870
published on Feb. 13, 2003.
[0291] A diffractive pigment may, for example, have the following
structure: MgF.sub.2/Al/MgF.sub.2, a diffractive pigment having
this structure being sold by FLEX PRODUCTS under the trade names
SPECTRAFLAIR 1400 Pigment Silver 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 weight of the pigment.
[0292] Other diffractive pigments are sold under the trade names
Metalure.RTM. Prismatic by ECKART.RTM..
[0293] Other possible structures are Fe/Al/Fe or Al/Fe/Al, which
present non-zero magnetic susceptibility.
[0294] By way of example, the quantity of diffractive pigment may
be in the range 0.1% to 5% by weight relative to the total weight
of the first composition.
[0295] By way of example, the size of the diffractive pigment may
be in the range 5 .mu.m to 200 .mu.m, and preferably in the range 5
.mu.m to 100 .mu.m, e.g. in the range 5 .mu.m to 30 .mu.m.
[0296] The thickness of the diffractive-pigment particles may be
less than or equal to 3 .mu.m or preferably 2 .mu.m, e.g. about 1
.mu.m.
Reflective Particles
[0297] The composition containing the magnetic bodies may include
reflective particles, in particular optionally-magnetic flakes,
amongst others.
[0298] The term "reflective particles" means particles the size and
structure of which, in particular the thickness of the layer or
layers constituting them and their physical and chemical natures,
and their surface state, allow them to reflect incident light. If
appropriate, said reflection may have sufficient intensity to
create highlight points on the surface of the composition or of the
mixture, when the composition or the mixture is applied to the
surface to be made up, which highlight points are visible to the
naked eye, i.e. they are points of greater brightness that contrast
with their environment and appear to shine.
[0299] The reflective particles may be selected in a manner such
that they do not significantly alter the coloring effect generated
by the coloring agents associated therewith, and more particularly
to optimize that effect in terms of color yield. More particularly,
they may have a yellow, pink, red, bronze, orangey, brown, and/or
copper glint.
[0300] The reflective particles may be present in the first
composition in an amount in the range 0.5% to 60% by weight
relative to the total weight of the first composition, specifically
1% to 30% by weight, and in particular 3% to 10% by weight.
[0301] Said particles may be in various forms, in particular they
may be in the form of flakes, or they may be globular, in
particular spherical.
[0302] Regardless of their form, the reflective particles may
optionally have a multilayer structure; for example, with a
multilayer structure, they may have at least one layer of uniform
thickness, in particular of a reflective material.
[0303] When the reflective particles do not have a multilayer
structure, they may, for example, be composed of metal oxides, in
particular oxides of titanium or iron obtained by synthesis.
[0304] When the reflective particles have a multilayer structure
they may, for example, comprise a natural or synthetic substrate,
in particular a synthetic substrate which is at least partially
coated with at least one layer of a reflective material, in
particular at least one metal or metallic material. The substrate
may be a single material or multiple materials, and it may be
organic and/or inorganic.
[0305] More particularly, it may be selected from glasses,
ceramics, graphite, metal oxides, aluminas, silicas, silicates, in
particular aluminosilicates and borosilicates, synthetic mica, and
mixtures thereof, this list not being limiting.
[0306] The reflective material may comprise a layer of metal or of
a metallic material.
[0307] Reflective particles have been described in particular in
Japanese patent documents JP-A-09188830, JP-A-10158450,
JP-A-10158541, JP-A-07258460 and JP-A-05017710.
[0308] Further examples of reflective particles comprising a
mineral substrate coated with a metal layer that may be mentioned
are particles comprising a substrate of borosilicate coated with
silver.
[0309] Glass substrate particles coated with silver in the form of
flakes are sold under the trade name MICROGLASS METASHINE REFSX
2025 PS by TOYAL. Glass substrate particles coated with
nickel/chromium/molybdenum alloy are sold under the trade name
CRYSTAL STAR GF 550, GF 2525 by the same company.
[0310] Reflective particles of any form may also be selected from
particles of synthetic substrate at least partially coated with at
least one layer of at least one metallic material, in particular a
metal oxide selected, for example, from oxides of titanium, in
particular TiO.sub.2, of iron, in particular Fe.sub.2O.sub.3, of
tin, or of chromium, barium sulfate, and the following materials:
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.
[0311] Examples of such particles that may be mentioned are
particles comprising a substrate of synthetic mica coated with
titanium dioxide, or glass particles coated either with brown iron
oxide, titanium oxide, tin oxide, or one of their mixtures such as
those sold under the trade name REFLECKS.RTM. by ENGELHARD.
[0312] The composition containing the magnetic bodies may include
at least one optionally-magnetic nacre.
Nacres
[0313] The term "nacre" means colored particles of any form, which
may optionally be iridescent, as produced in the shells of certain
mollusks, or which are synthesized, and which exhibit a
"pearlescent" coloring effect by optical interference.
[0314] Nacres may be selected from nacre pigments such as mica
titanium coated with iron oxide, mica coated with bismuth
oxychloride, mica titanium coated with chromium oxide, mica
titanium coated with an organic colorant, in particular of the type
mentioned above, and nacre pigments based on bismuth oxychloride.
They may also be particles of mica on the surface of which at least
two successive layers of metal oxides and/or organic coloring
substances have been superimposed.
[0315] More particularly, the nacres may have a yellow, pink, red,
bronze, orangey, brown, gold, and/or coppery color or glint.
[0316] Illustrative examples of nacres suitable for being
introduced into the first composition and that may be mentioned are
gold color nacres, in particular those sold by ENGELHARD under the
trade names Brillant gold 212G (Timica), Gold 222C (Cloisonne),
Sparkle gold (Timica), Gold 4504 (Chromalite), and Monarch gold
233X (Cloisonne); bronze nacres, in particular those sold by MERCK
under the trade names Bronze fine (17384) (Colorona) and Bronze
(17353) (Colorona), and by ENGELHARD under the trade name Super
bronze (Cloisonne); orange nacres especially those sold by
ENGELHARD under the trade names Orange 363C (Cloisonne) and Orange
MCR 101 (Cosmica), and by MERCK under the trade names Passion
orange (Colorona) and Matte orange (17449) (Microna); brown-tinted
nacres sold by ENGELHARD under the trade names 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 glint, especially those sold by MERCK
under the trade name Sienna fine (17386) (Colorona); nacres with a
yellow glint, especially those sold by ENGELHARD under the trade
name Yellow (4502) (Chromalite); red-tinted nacres with gold
glints, especially those sold by ENGELHARD under the trade name
Sunstone G012 (Gemtone); pink nacres, especially those sold by
ENGELHARD under the trade name Tan opale G005 (Gemtone); black
nacres with a glint, especially those sold by ENGELHARD under the
trade name Nu antique bronze 240 AB (Timica); blue nacres,
especially those sold by MERCK under the trade name Matte blue
(17433) (Microna); white nacres with silvery glints, especially
those sold by MERCK under the trade name Xirona Silver; and
orangepink green-gold highlight nacres sold by MERCK under the
trade names Indian summer (Xirona) and mixtures thereof.
Other Components
[0317] Typically, the composition containing the magnetic bodies
includes a physiologically acceptable medium. The term
"physiologically acceptable medium" means a non-toxic medium that
can be applied to the skin, to the nails, to hair, or to the lips
of human beings. The physiologically acceptable medium is generally
adapted to the nature of the surface onto which the composition is
to be applied, and to the form in which the composition is
packaged.
[0318] The composition may include ingredients other than those
described above, in particular at least one solvent, one oily
phase, one film-forming polymer, and/or one dermatologically or
cosmetically active ingredient, in particular as a function of its
dosage or "galenical" form.
Solvents
[0319] The composition containing the magnetic bodies may include
at least one aqueous or organic solvent, in particular a volatile
organic solvent.
[0320] The first composition may advantageously include a volatile
solvent, in particular a volatile organic solvent.
[0321] The term "volatile solvent" as used in the context of the
present invention means a solvent that is liquid at ambient
temperature, having a non-zero vapor pressure at ambient
temperature and atmospheric pressure, in particular a vapor
pressure in the range 0.13 pascals (Pa) to 40000 Pa (10.sup.-3
millimeters of mercury (mm Hg) to 300 mm Hg), and preferably in the
range 1.3 Pa to 13000 Pa (0.01 mm Hg to 100 mm Hg), and preferably
in the range 1.3 Pa to 1300 Pa (0.01 mm Hg to 10 mm Hg).
[0322] When the composition contains one or more organic solvents,
the solvents may be present in an amount in the range 0.1% to 99%,
relative to the total weight of the composition under
consideration.
[0323] In general, the quantity of solvent(s), in particular
organic solvent(s), depends on the nature of the surface to which
the composition is intended to be applied.
[0324] The first composition may include at least one volatile
solvent constituted by a volatile oil.
[0325] The oil may be a silicone oil or a hydrocarbon oil, or may
include a mixture of such oils.
[0326] The term "silicone oil" as used in the context of the
present invention means an oil including at least one silicon atom,
and in particular at least one Si--O group.
[0327] The term "hydrocarbon oil" means an oil containing mainly
hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur,
and/or phosphorus atoms.
[0328] The volatile hydrocarbon oils may be selected from
hydrocarbon oils having 8 to 16 carbon atoms, and in particular
C8-C16 branched alkanes (also termed isoparaffins) such as
isododecane (also termed 2,2,4,4,6-pentamethylheptane), isodecane,
isohexadecane, and oils sold under the trade names Isopars.RTM. or
Permethyls.RTM., for example.
[0329] Volatile oils that may also be used are volatile silicones,
such as volatile linear or cyclic silicone oils, for example, in
particular oils having a viscosity .ltoreq.8 centistokes (cSt)
(8.times.10.sup.-6 square meters per second (m.sup.2/s)), and
having in particular 2 to 10 silicon atoms, and in particular 2 to
7 silicon atoms, the silicones possibly including alkyl or alkoxy
groups having 1 to 10 carbon atoms. In the invention, suitable
volatile silicone oils that may be mentioned are in particular
dimethicones having a viscosity of 5 cSt to 6 cSt,
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane,
heptamethyloctyltrisiloxane, hexamethyldisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane,
dodecamethylpentasiloxane, and mixtures thereof.
[0330] Mention may also be made of volatile alkyltrisiloxane linear
oils of general formula (I):
##STR00014##
in which R represents an alkyl group comprising 2 to 4 carbon atoms
and having one or more hydrogen atoms that can be substituted by a
fluoride or chloride atom.
[0331] Amongst the oils of general formula (I), mention can be made
of: [0332] 3-butyl 1,1,1,3,5,5,5-heptamethyltrisiloxane; [0333]
3-propyl 1,1,1,3,5,5,5-heptamethyltrisiloxane; and [0334] 3-ethyl
1,1,1,3,5,5,5-heptamethyltrisiloxane; corresponding to oils of
formula (I) for which R is respectively a butyl group, a propyl
group, or an ethyl group.
[0335] It is also possible to use fluorinated volatile oils such as
nonafluoromethoxybutane or perfluoromethylcyclopentane, and
mixtures thereof.
[0336] A composition of the invention may contain 0.01% to 95% by
weight of volatile oil relative to the total weight of the
composition, for example, and preferably 1% to 75% by weight.
[0337] The composition may comprise at least one organic solvent
selected from the following list: [0338] ketones that are liquid at
ambient temperature, such as methylethylketone,
methylisobutylketone, diisobutylketone, isophorone, cyclohexanone,
or acetone; [0339] alcohols that are liquid at ambient temperature,
such as ethanol, isopropanol, diacetone alcohol, 2-butoxyethanol,
or cyclohexanol; [0340] glycols that are liquid at ambient
temperature, such as ethylene glycol, propylene glycol, pentylene
glycol, or glycerol; [0341] propylene glycol ethers that are liquid
at ambient temperature, such as propylene glycol monomethyl ether,
the acetate of propylene glycol monomethyl ether, or dipropylene
glycol mono n-butyl ether; [0342] short-chain esters (containing a
total of 3 to 8 carbon atoms), such as ethyl acetate, methyl
acetate, propyl acetate, n-butyl acetate, or isopentyl acetate; and
[0343] alkanes that are liquid at ambient temperature, such as
decane, heptane, dodecane, or cyclohexane.
[0344] The composition may also comprise water or a mixture of
water and hydrophilic organic solvents which are routinely used in
cosmetics, such as alcohols, in particular linear or branched lower
monoalcohols containing 2 to 5 carbon atoms, such as ethanol,
isopropanol or n-propanol, polyols such as glycerine, diglycerine,
propylene glycol, sorbitol, penthylene glycol, or polyethylene
glycols. The first composition may also contain hydrophilic C.sub.2
ethers and C.sub.2-C.sub.4 aldehydes. The water or mixture of water
and hydrophilic organic solvents may be present in the first and/or
second composition in an amount in the range 0% to 90%, in
particular 0.1% to 90% by weight, and preferably 0% to 60% by
weight, more particularly 0.1% to 60% by weight relative to the
total weight of the composition.
Oily Phase
[0345] When it is to be applied to the lips, the composition may,
for example, include an oily phase and in particular at least one
fat that is liquid at ambient temperature (25.degree. C.) and/or a
fat that is solid at ambient temperature, such as waxes, pasty
fats, gums, and mixtures thereof. The oily phase may also contain
lipophilic organic solvents.
[0346] By way of example, the composition may have a continuous
oily phase which may contain less than 5% water, in particular less
than 1% water relative to its total weight, and in particular it
may be in the anhydrous form.
[0347] Fats that are liquid at ambient temperature, usually termed
"oils", that may be mentioned are: hydrocarbon-containing vegetable
oils such as liquid fatty acid triglycerides containing 4 to 10
carbon atoms, for example heptanoic or octanoic acid triglycerides,
or sunflower, corn, soybean, grapeseed, sesame seed, apricot
kernel, macadamia nut, castor, or avocado stone oil,
caprylic/capric acid triglycerides, jojoba oil, shea nut butter
oil, lanolin, acetylated lanolin; linear or branched hydrocarbons
of mineral or synthetic origin, such as paraffin oils and their
derivatives, Vaseline, polydecenes, hydrogenated polyisobutene such
as Parleam; synthesized esters and ethers, in particular fatty
acids such as Purcellin oil, isopropyl myristate, 2-ethylhexyl
palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate,
isostearyl isostearate; hydroxylated esters such as isostearyl
lactate, octylhydroxystearate, octyldodecyl hydroxystearate,
diisostearylmalate, triisocetyl citrate, fatty alcohol heptanoates,
octanoates, or decanoates; isononyl isonanoate, isopropyl lanolate,
tridecyl trimellilate, diisostearyl malate; polyol esters such as
propylene glycol dioctanoate, neopentylglycol diheptanoate,
diethyleneglycol diisononanoate; and pentaerythritol esters; fatty
alcohols containing 12 to 26 carbon atoms, such as octyldodecanol,
2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, or oleic
alcohol; hydrocarbon-containing and/or silicone-containing
fluorinated oils; silicone oils such as volatile or non-volatile,
linear or cyclic polymethylsiloxanes (PDMS) which may be liquid or
pasty at ambient temperature, such as cyclomethicones or
dimethicones, optionally comprising a phenyl group, such as phenyl
trimethicones, phenyltrimethylsiloxydiphenyl siloxanes,
diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyl
dimethicones, polymethylphenylsiloxanes; and mixtures thereof. The
oils may be present in an amount in the range 0.01% to 90%, and
preferably 0.1% to 85% by weight relative to the total weight of
the composition.
[0348] The presence of an oily phase may impart a gloss effect, and
may present a refractive index in the range 1.47 to 1.51, for
example, and preferably in the range 1.48 to 1.50. The refractive
index is measured at ambient temperature (25.degree. C.) by means
of a refractometer.
[0349] The composition may include at least one structuring agent
for the liquid oily phase (formed by the above-described volatile
or non-volatile organic solvents and/or oils) selected from waxes,
semi-crystalline polymers, lipophilic gelling agents, and mixtures
thereof.
[0350] Pasty fats are generally hydrocarbon-containing compounds
with a melting point in the range 25.degree. C. to 60.C, preferably
in the range 30.degree. C. to 45.degree. C., and/or with hardness
in the range 0.001 megapascals (MPa) to 0.5 MPa, preferably in the
range 0.005 MPa to 0.4 MPa, such as lanolins and derivatives
thereof.
[0351] Waxes may be solid at ambient temperature (25.degree. C.)
with a reversible solid/liquid change of state, with a melting
point of more than 30.degree. C. and up to 200.degree. C., a
hardness of more than 0.5 MPa, and with an anisotropic crystalline
organization in the solid state. In particular, the waxes may have
a melting point of more than 25.degree. C., and preferably more
than 45.degree. C. The waxes may be hydrocarbon-containing,
fluorinated and/or silicone-containing and may be of animal,
mineral, vegetable and/or synthetic origin. Suitable waxes that may
be mentioned are beeswax, carnauba wax or candellila wax, paraffin,
microcrystalline waxes, ceresin, or ozokerite; synthetic waxes such
as polyethylene or Fischer-Tropsch waxes or silicone waxes such as
alkyl or alkoxydimethicone containing 16 to 45 carbon atoms. The
composition may contain 0 to 50% by weight of waxes relative to the
total weight of the composition, or even 1% to 30% by weight.
[0352] Suitable gums are generally high molecular weight
polydimethylsiloxanes (PDMS) or cellulose gums or
polysaccharides.
Film-Forming Polymers
[0353] By way of example, the composition may also include a
film-forming polymer, in particular for a mascara, a nail varnish,
or a foundation. The term "film-forming polymer" means a polymer
that can form, by itself or in the presence of an additional
film-forming agent, a continuous film that adheres to a surface, in
particular to keratinous substances.
[0354] Suitable film-forming polymers for use in the composition in
accordance with the invention that may be mentioned include
synthetic polymers, of the radical or polycondensate type, natural
polymers such as nitrocellulose or cellulose esters, and mixtures
thereof.
[0355] Radical type film-forming polymers may in particular be
vinyl polymers or copolymers, in particular acrylic polymers.
[0356] Vinyl film-forming polymers may result from polymerizing
monomers with an ethylenically unsaturated bond containing at least
one acid group and/or esters of said acid monomers and/or amides of
said acid monomers, such as .alpha.,.beta.-ethylenically
unsaturated carboxylic acids, for example acrylic acid, methacrylic
acid, crotonic acid, maleic acid, or itaconic acid.
[0357] Vinyl film-forming polymers may also result from
homopolymerizing or copolymerizing monomers selected from vinyl
esters such as vinyl acetate, vinyl neodecanoate, vinyl pivalate,
vinyl benzoate, and vinyl t-butyl benzoate, and styrene monomers
such as styrene and alphamethyl styrene.
[0358] Examples of film-forming polycondensates that may be
mentioned include polyurethanes, polyesters, polyester amides,
polyamides, and polyureas, this list not being limiting.
[0359] Polymers of natural origin, which may optionally be
modified, may be selected from shellac resin, gum sandarac, dammar
resin, gum elemi, copal resin, cellulose polymers such as
nitrocellulose, ethylcellulose, or nitrocellulose esters selected,
for example, from cellulose acetate, cellulose acetobutyrate, and
cellulose acetopropionate, and mixtures thereof.
[0360] The film-forming polymer may be present in the form of solid
particles in an aqueous or oily dispersion, generally known as
latexes or psuedolatexes. The film-forming polymer may comprise one
or more stable dispersions of generally spherical polymer particles
of one or more polymers in a physiologically acceptable liquid oily
phase. Said dispersions are generally termed polymer NADs
(non-aqueous dispersions), in contrast to latexes which are aqueous
polymer dispersions. Said dispersions may be in the form of
nanoparticles of polymers in stable dispersion in said oily phase.
The nanoparticle size is preferably in the range 5 nm to 600 nm.
Techniques for preparing said dispersions are well known to the
person skilled in the art.
[0361] Aqueous film-forming polymer dispersions which may be used
are acrylic dispersions sold under the trade names NEOCRYL
XK-90.RTM., NEOCRYL A-1070.RTM., NEOCRYL A-1090.RTM., NEOCRYL
BT-620, NEOCRYL A-1079.RTM., NEOCRYL A-523.RTM. by
AVECIA-NEORESINS, and DOW LATEX 432.RTM. by DOW CHEMICAL; DAITOSOL
5000 AD.RTM. by DAITO KASEI KOGYO; or aqueous polyurethane
dispersions sold under the trade names NEOREZ R-9810 and NEOREZ
R-9740 by AVECIA-NEORESINS; AVALURE UR-405.RTM., AVALURE
UR-410.RTM., AVALURE UR-425.RTM., AVALURE UR-450.RTM., SANCURE
875.RTM., SANCURE 861.RTM., SANCURE 878.RTM., and SANCURE 2060.RTM.
by GOODRICH; IMPRANIL 85.RTM. by BAYER; AQUAMERE H-1511.RTM. by
HYDROMER; and sulfopolyesters sold under the trade mark Eastman AQ
by Eastman Chemical Products.
Sequenced Film-Forming Polymer
[0362] In an embodiment of the invention, the composition includes
at least one film-forming polymer that is a film-forming linear
sequenced ethylene polymer. The polymer preferably comprises at
least a first sequence and at least a second sequence having
different glass transition temperatures (Tg), said first and second
sequences being connected together by an intermediate sequence
comprising at least one monomer that constitutes the first sequence
and at least one monomer that constitutes the second sequence.
[0363] The first and second sequences of the sequenced polymer are
advantageously incompatible with each other.
[0364] By way of example, such polymers are described in documents
EP 1 411 069 or WO04/028488 which are incorporated herein by
reference.
[0365] The composition containing the magnetic bodies may contain
at least one optionally-magnetic filler.
Fillers
[0366] The term "filler" means particles of any form which are
insoluble in the composition medium regardless of the temperature
at which the composition is manufactured. A filler primarily acts
to modify the rheology or texture of the composition. The nature
and quantity of the particles could depend on the desired
mechanical properties and textures.
[0367] Examples of fillers that may be mentioned include amongst
others talc, mica, silica, kaolin, and sericite, and powders of
polyamide, polyolefin, e.g. polyethylene, polytetrafluoroethylene,
polymethylmethacrylate, or polyurethane, powdered starch, and
silicone resin beads.
[0368] Amongst other things, the fillers may be intended to create
a fuzzy effect, in particular for a foundation, so as to conceal
skin imperfections.
[0369] The composition containing the magnetic bodies may also
include a film-forming auxiliary agent that encourages the
formation of a film with the film-forming polymer.
Active Ingredients
[0370] The composition may include at least one cosmetically or
dermatologically active ingredient.
[0371] Suitable cosmetically, dermatologically, hygienically, or
pharmaceutically active ingredients for use in the compositions of
the invention that may be mentioned are moisturizing agents
(polyols such as glycerine), vitamins (C, A, E, F, B, or PP),
essential fatty acids, essential oils, ceramides, sphingolipids,
liposoluble or nanoparticle sun screens, and specific skin
treatment active ingredients (protective agents, antibacterials,
anti-wrinkle agents, etc), self-tanning agents. Said active
ingredients may be used in concentrations in the range 0 to 20%,
for example, in particular in the range 0.001% to 15% relative to
the total weight of the composition.
[0372] The composition may also contain ingredients that are
routinely used in cosmetics, such as thickeners, surfactants,
oligo-elements, moisturizing agents, softeners, sequestrating
agents, fragrances, alkalinizing or acidifying agents,
preservatives, antioxidants, UV filters, colorants, or mixtures
thereof.
[0373] Depending on the envisaged application, the composition of
the invention may include constituents which are conventionally
used in the fields under consideration, and which are present in
quantities appropriate to the desired dosage form.
Dosage Forms
[0374] The composition may be in a variety of forms, depending on
its purpose. The composition may thus be in any dosage form that is
normally used for topical application, in particular in the
anhydrous form, in the form of an oily or aqueous solution, an oily
or aqueous gel, an oil-in-water or a water-in-oil emulsion, a
waxin-water or a water-in-wax emulsion, a multiple emulsion or a
dispersion of oil in water due to vesicles located on the oil/water
interface.
[0375] The composition may be in the form of a powder, or even a
gel.
Magnetic Devices
[0376] The magnetic device may comprise a permanent magnet or an
electromagnet powered by at least one optionallyrechargeable
battery, for example. For a battery, the magnetic device may
include a switch enabling the electromagnet to be powered
selectively with electricity.
[0377] The magnetic device may be arranged so as to create a
magnetic field of orientation that varies over time. When the
magnetic device comprises a magnet, the device may, for example,
include a motor enabling the magnet to be rotated. In a variant,
the magnetic device may comprise a plurality of solenoids disposed
so as to generate a rotating magnetic field when powered
sequentially with electricity.
[0378] By way of example, a rotating magnetic field may make it
possible to obtain a pattern presenting circular symmetry, e.g. a
pattern giving the impression of a sphere in relief.
[0379] The electromagnet(s) may be powered continuously or
intermittently, as desired by the user. In particular, the magnetic
device may be arranged so that the electromagnets(s) need not be
powered while the magnetic device is not correctly positioned close
to the surface coated with the first composition.
[0380] The magnetic field is at least 50 milli teslas (mT), for
example, even at least 66 mT, better at least 0.2 T, or even at
least 1 T (10000 Gauss).
[0381] In order to make it easier to apply the magnetic field, the
magnetic device may include a member enabling it to be positioned
relative to the surface on which the composition has been
deposited. This makes it possible to prevent the magnetic device
from accidentally coming into contact with the composition and/or
makes it possible to center the pattern formed on the region under
consideration.
[0382] In an implementation of the invention, the magnetic device
is secured to an applicator that is used to apply the cosmetic
composition. This makes it possible to reduce the number of objects
that need to be manipulated by the user and makes it easier to
apply makeup.
[0383] In another implementation of the invention, the magnetic
device comprises a magnet mounted at a first end of a rod having a
second end that is connected to a handle of an applicator that is
used to apply the cosmetic composition.
[0384] The magnetic field may also be exerted by means of a
magnetic structure, in particular a flexible structure, including
alternate N and S poles. By way of example, such a structure may
make it possible to form repeated patterns, e.g. stripes, on the
first composition.
Kits for Implementing the Method
[0385] In another of its aspects, the invention also provides, a
kit for implementing the method as defined above, said kit
comprising: [0386] a magnetic device enabling a magnetic field to
be generated; and [0387] a cosmetic composition including: [0388]
at least one body that presents non-zero magnetic susceptibility
and that is movable under the effect of a magnetic field; and
[0389] at least one coloring agent having optical properties that
are sensitive to an external stimulus; the magnetic device being
capable of creating a magnetic field that is capable, when the
keratinous substance covered in a deposit of said composition is
inserted in said magnetic field, of modifying the orientation
and/or the position of the magnetic bodies inside the deposit.
[0390] In particular, the magnetic device may be arranged so as to
generate a magnetic field that is sufficiently strong to be able to
modify the orientation and/or the position of the magnetic bodies
within the composition after it has been applied to a surface such
as the skin, the lips, the nails, or hair, in order to change their
appearance.
[0391] By way of example, when the first composition contains a
volatile solvent, the magnetic field is exerted shortly after it
has been deposited, so as to change the appearance of said
composition before it has dried.
[0392] By way of example, the composition may be a nail varnish, a
foundation, or a lipstick, and may present the characteristics as
defined above.
[0393] The magnetic device may be as defined above.
[0394] The kit may comprise a compact housing the first cosmetic
composition and the magnetic device. In this event, the compact
may, for example, include a plurality of magnets of various shapes
in order to produce different patterns.
[0395] The kit may also include an additional cosmetic composition
for applying to the above-mentioned composition, or to the surface
before the above-mentioned composition is applied.
Promotion Method
[0396] The invention also provides a method of promoting the sale
of a composition presenting magnetic properties, the method
comprising the step consisting in demonstrating the possibility of
creating a pattern or a portion in relief by applying a magnetic
field and/or the possibility of changing appearance by exposure to
an external stimulus such as a variation in temperature, or
exposure to UV radiation, for example.
[0397] The invention can be better understood on reading the
following detailed description of non-limiting implementations
thereof, and on examining the accompanying drawings, in which:
[0398] FIG. 1 is a diagram showing an example of a kit of the
invention;
[0399] FIG. 2 is a diagrammatic and fragmentary axial section view
showing the magnetic device of FIG. 1;
[0400] FIGS. 3 and 4 are diagrams showing the kit being used;
[0401] FIG. 5 shows an example of a pattern that can be obtained by
means of the invention;
[0402] FIG. 6 is a diagram showing a receptacle containing an
additional composition that is suitable for being applied to the
surface;
[0403] FIG. 7 is a diagram showing, in isolation, another example
of a magnetic device that can be used;
[0404] FIG. 8 is a diagram showing the FIG. 7 magnetic device
provided with a positioning member for positioning the magnet
facing the made-up surface;
[0405] FIGS. 9 and 10 are diagrams of other examples of kits of the
invention;
[0406] FIG. 11 shows the FIG. 10 kit being used;
[0407] FIG. 12 is a diagram showing, in elevation and in isolation,
an example of an applicator secured to a magnetic device;
[0408] FIG. 13 is an axial and diagrammatic section of another
example of a kit of the invention;
[0409] FIG. 14 is a diagram showing another example of a kit of the
invention;
[0410] FIG. 15 shows another example of a packaging device for the
composition;
[0411] FIG. 16 shows a perforated mask that is suitable for being
used during implementation of the method of the invention; and
[0412] FIG. 17 shows a magnetic sheet that is suitable for being
used during implementation of the method of the invention; and
[0413] In the figures, magnetic bodies are shown in the form of
dots in order to make the drawings easy to understand, but in
reality the individual bodies need not be visible to the naked
eye.
[0414] FIG. 1 shows a kit 1 comprising a cosmetic composition
C.sub.1 containing magnetic particles P having orientation and/or
position that affects the appearance of the composition after it
has been deposited on a surface such as the skin, the lips, the
nails, hair, or even false nails.
[0415] In the embodiment shown, the composition C.sub.1 is a nail
varnish contained in a receptacle 2 that is closed by a cap 3. The
cap supports a non-magnetic cosmetics applicator 4 including an
applicator member 5 constituted by a brush enabling the varnish to
be applied to the nails.
[0416] The kit 1 further comprises a magnetic device 10 that makes
it possible to generate a magnetic field that is useful for
changing the appearance of the composition C.sub.1 without making
contact therewith.
[0417] In the embodiment under consideration, the magnetic device
10 comprises a permanent magnet 12 supported by a support member 13
of longitudinal axis X, the polar axis of the magnet 12 being
substantially perpendicular to the axis X.
[0418] In the embodiment under consideration, the magnetic device
10 is arranged to generate a rotating magnetic field, and includes
a motor (not shown), housed in a casing 15, so as to rotate the
support member 13 about it axis X.
[0419] A switch 16 is present on the casing 15 so as to enable the
user to switch on the motor, thereby rotating the support member 13
together with the magnet 12.
[0420] In a variant not shown, the rotating magnetic field is
generated by a plurality of solenoids that are powered sequentially
so as to generate a rotating field.
[0421] In order to use the kit 1, the user can begin, as shown in
FIG. 3, by applying the composition C.sub.1 by means of an
applicator 4 to the surface S to be made up, specifically a
fingernail.
[0422] In the subsequent step shown in FIG. 4, the user brings the
magnetic device 10 over a central region R of the surface S and
actuates the switch 16 so as to make the magnet 12 turn.
[0423] The magnetic particles contained in the composition C.sub.1
tend to come into alignment with the field lines of the magnet 12
and change orientation, thereby leading to a change in the
appearance of the composition C.sub.1.
[0424] The user can choose the length of time the magnetic field is
to be applied as a function of the desired result.
[0425] By way of example, the pattern obtained can give the
impression of a sphere in relief, as shown in FIG. 5.
[0426] If necessary, the user can apply a second composition
C.sub.2, e.g. a transparent varnish, contained in a receptacle
shown in FIG. 6, once the composition C.sub.1 has dried.
[0427] Applying the second composition C.sub.2 makes it possible to
create an effect of additional depth, for example.
[0428] In the nail varnish embodiment in FIGS. 1 to 5, the
composition C.sub.1 may have the following formulation, with
quantities being expressed in percentages by weight in all of the
examples below.
EXAMPLE A
Nail Varnish Incorporating a Photochromic Agent
TABLE-US-00001 [0429] Nitrocellulose 11 N-ethyl
o,p-toluenesulfonamide 5 Alkyde resin 10 Isopropanol 4 Magnetic
pigment* 0.5 Photochromic coloring agent** 3 Butyl acetate/ethyl
acetate 50/50 Qsp 100 *STAPA WM IRON VP 041040 by ECKART
**Reversacol from James ROBINSON
[0430] Once the composition has dried, the pattern generated by
magnetic induction is frozen. Its color depends on the photochromic
coloring agent. Depending on the magnetic excitation, the pigment
presents a dull or lively color, thus optionally enhancing the
decorative effect obtained by the magnetic pigment.
[0431] The appearance of such a nail varnish can be changed by
applying a magnetic field before the varnish has had time to
dry.
[0432] By way of example, when a second composition C.sub.2 is
applied to the first, said second composition has the following
formulation.
EXAMPLE B
TABLE-US-00002 [0433] Nitrocellulose 11 N-ethyl
o,p-toluenesulfonamide 5 Alkyde resin 10 Isopropanol 4 Butyl
acetate/ethyl acetate 50/50 Qsp 100
[0434] Such a composition makes it possible to create an effect of
additional depth.
[0435] In a variant, the second composition may be intended to
create a colored base, and it is applied before the first. By way
of example, the second composition then has the following
formulation.
EXAMPLE C
TABLE-US-00003 [0436] Nitrocellulose 11 N-ethyl
o,p-toluenesulfonamide 5 Alkyde resin 10 Isopropanol 4 DC RED7 CI
15850 pigment 2 Butyl acetate/ethyl acetate 50/50 Qsp 100
EXAMPLE D
Nail Varnish Incorporating a Thermochromic Agent
TABLE-US-00004 [0437] Nitrocellulose 11 N-ethyl
o,p-toluenesulfonamide 5 Alkyde resin 10 Isopropanol 4 Magnetic
pigment* 0.5 Thermochromic coloring agent** 3 Butyl acetate/ethyl
acetate 50/50 Qsp 100 *Colorona Blackstar Red from Merck
**Thermostar .RTM. from CHROMAZONE
[0438] Once the composition has dried, the pattern generated by
magnetic induction is frozen. Its color depends on the
thermochromic coloring agent. Depending on the magnetic excitation,
the thermochromic pigment presents a dull or lively color as a
function of the temperature, thus optionally enhancing the
decorative effect obtained by the magnetic pigment.
[0439] Naturally, whatever the nature of said composition, the
magnetic field applied thereto need not rotate. By way of example,
FIG. 7 shows a magnetic device which, at its end, includes a
permanent magnet 12 in the form of a bar.
[0440] When the magnetic field does not rotate, the user can, for
example, move the magnet into the vicinity of the composition
C.sub.1 as a function of the desired result.
[0441] Whatever its nature, the magnetic device may include a
member enabling it to be positioned relative to the surface S.
[0442] By way of example, the positioning member serves to prevent
the magnetic device from touching the composition while the
magnetic field is being exerted.
[0443] The positioning member can also serve to center the pattern
that is produced relative to the surface S, e.g. the nail.
[0444] Depending on the nature of the surface, the positioning
member could take various forms, e.g. that of an extension 17
offering an abutment surface for engaging the end of the finger, as
shown in FIG. 8.
[0445] FIG. 9 shows another embodiment of a kit 1 of the invention,
including a first composition C.sub.1 constituted in this
embodiment by a liquid lipstick or a lipgloss.
[0446] In this embodiment, the applicator 4 comprises a flocked
endpiece 20 supported by the cap 3 of the receptacle 2.
[0447] By way of example, the magnetic device 10 is in the form of
a flexible structure, e.g. made of plastics material filled with
magnetized particles, creating alternate N and S poles, thereby
making it possible to form repeated patterns, e.g. stripes, on the
surface coated with the first composition.
[0448] By way of example, for lipstick, the composition C.sub.1
presents the following formulation.
EXAMPLE E
Lipstick Incorporating a Solvatochromic Agent
TABLE-US-00005 [0449] Octyl-2 dodecanol 10 Ditertiobutyl
4-hydroxytoluene 0.07 Polybutene (monoolefins/isoparaffins 95/5) 50
(PM: 2060) A mixture of isopropyl, isobutyl, and n-butyl 0.4
p-hydroxybenzoates (40/30/30) Pentaerythrityl tetraisostearate
11.33 Tridecyle trimellitate 13 2-decyl tetradecanoic acid
triglyceride 14.8 (GUERBET C24) Magnetic pigment* 0.2
Solvatochromic coloring agent 0.2 *Colorona blackstar gold from
Merck **DCRED27
[0450] Once the composition has been applied, the pattern is
generated by magnetic induction. Its color depends on the
solvatochromic coloring agent. Depending on the magnetic
excitation, the compound presents a color that is pink or not as a
function of the hydration, thus optionally enhancing the decorative
effect obtained by the magnetic pigment.
[0451] Another kit 1 of the invention is shown in FIG. 10. In this
embodiment, the kit 1 includes a compact 30 constituted by a base
body 31 and a lid 32 hinged thereon.
[0452] The base body 31 includes a compartment 33 housing the
composition C.sub.1, which, in the embodiment shown, is constituted
by a foundation in the form of a paste.
[0453] The base body 31 includes a housing 34 arranged to receive
at least one magnet 12.
[0454] By way of example, the magnet 12 may present an adhesive
face 25 or any other mounting means enabling the user to fix it to
the end of a finger so as to bring it into the vicinity of the
made-up zone, e.g. a region of the face as shown in FIG. 11.
[0455] After applying the composition C.sub.1 to the skin, the user
can modify the clarity of said composition by exposing it to the
magnetic field generated by the magnet 12.
[0456] By way of example, for a composition for making up the skin,
said composition can have the following formulation.
EXAMPLE F
Foundation Incorporating a Photochromic Agent
TABLE-US-00006 [0457] Magnesium sulfate 1.5 Sodium
carboxymethylcellulose 0.5 Distearyldimethylammonium modified
hectorite 1 Cyclopenta dimethylsiloxane 15 Glycerol 5 A mixture of
oxyethylenated 9 polymethylketyldimethyl methylsiloxane,
polyglycerol isostearate (4 moles), hexyl laurate Water 30.6 A
mixture of ethylene glycol acetyl stearate, 0.3 glyceryl
tristearate Brown iron oxide coated with aluminum stearoyl 1.58
glutamate (97/3) Anatase titanium oxide coated with stearoyl 17.17
glutamate (97/3) Yellow iron oxide coated with aluminum 4.56
stearoyl glutamate (93/3) Black iron oxide coated with aluminum
stearoyl 0.69 glutamate (97/3) Polydimethylsiloxane (viscosity: 5
cSt) 6 Magnetic pigment* 0.5 Xchromic coloring agent** 3
1,2-pentanediol 3 *Nacres with at least 14% of Fe.sub.3O.sub.4,
sold by Merck under the reference TIMICA NU ANTIQUE BRONZE 240 AB.
**Photogenica .RTM. from CATALYST & CHEMICALS
[0458] Whatever the type of applicator, the magnet 12 may, where
appropriate, be incorporated in the applicator.
[0459] In the embodiment in FIG. 12, the closure cap 3 is
surmounted by the magnet 12 on the side remote from the applicator
member 5.
[0460] In the embodiment in FIG. 13, the magnet 12 is supported by
a support member 13 surmounted by a cap 51, and can, when not in
use, be housed in a compartment 50 of the cap 3 for closing the
receptacle 2 containing the first composition C.sub.1. The cap 51
serves as a handle for the magnet 12, and also serves to close the
compartment 50.
[0461] It is not beyond the ambit of the present invention for the
magnetic field to be generated by an electromagnet instead of by a
permanent magnet.
[0462] FIG. 14 shows a kit 1 comprising a receptacle 2 constituted
by a pot containing the first composition C.sub.1, and a magnetic
device 10 comprising an electromagnet 40 at one end of a casing 44
housing the power supply.
[0463] A switch 45 enables the electromagnet 40 to be switched on
selectively by the user.
[0464] Various devices other than those described above for
packaging and/or dispensing or applying the composition C.sub.1 can
be used.
[0465] By way of example, the composition C.sub.1 can be deposited
on the surface S without using an applicator, but in the form of a
spray, e.g. by using a pump 60 as shown in FIG. 15. The spray can
also be generated by means of an airbrush or by a pressurized
receptacle, for example.
[0466] A perforated mask 70, as shown in FIG. 16 in which its
perforation pattern 71 is in the shape of a star, can be interposed
between the spray and the surface to be made up.
[0467] An optionally-perforated sheet 75 that is permeable to the
magnetic field can be interposed between the magnet 12 or the
electromagnet 40 and the surface S, so as to change the shape of
the field lines and create novel effects.
[0468] Naturally, the invention is not limited to the examples
given above.
[0469] For example, the kit may include a plurality of magnets
having various shapes, so as to create various patterns.
[0470] The expression "comprising a" should be understood as being
synonymous with "comprising at least one", and the expression "in
the range" should be understood as including the limits of the
range.
* * * * *