U.S. patent application number 12/710883 was filed with the patent office on 2010-09-30 for method of making up with light-sensitive makeup in which an optical agent is used to protect the result obtained.
This patent application is currently assigned to L'OREAL. Invention is credited to Maxime DE BONI, Franck GIRON, Henri SAMAIN.
Application Number | 20100243514 12/710883 |
Document ID | / |
Family ID | 41211750 |
Filed Date | 2010-09-30 |
United States Patent
Application |
20100243514 |
Kind Code |
A1 |
SAMAIN; Henri ; et
al. |
September 30, 2010 |
METHOD OF MAKING UP WITH LIGHT-SENSITIVE MAKEUP IN WHICH AN OPTICAL
AGENT IS USED TO PROTECT THE RESULT OBTAINED
Abstract
The present invention provides a method of making up human
keratinous material with light-sensitive makeup, in which method: a
thermally stable photochromic first composition comprising a
photochromic agent capable of being developed under the effect of
radiation of wavelength .lamda. is applied to the keratinous
material; the first composition is exposed to said radiation to
develop the photochromic agent and create a light-sensitive makeup
look; and the thermally stable photochromic composition is, at
least temporarily and at least in part, before or after being
exposed to said radiation, covered by a photoprotective layer,
exposure to said radiation for developing the photochromic agent
being performed through the photoprotective layer when said layer
is applied before the thermally stable photochromic composition is
exposed to said radiation, in order to create a light-sensitive
makeup look.
Inventors: |
SAMAIN; Henri; (Bievres,
FR) ; GIRON; Franck; (Ferrieres-En-Brie, FR) ;
DE BONI; Maxime; (Tokyo, JP) |
Correspondence
Address: |
OLIFF & BERRIDGE, PLC
P.O. BOX 320850
ALEXANDRIA
VA
22320-4850
US
|
Assignee: |
L'OREAL
Paris
FR
|
Family ID: |
41211750 |
Appl. No.: |
12/710883 |
Filed: |
February 23, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61159449 |
Mar 12, 2009 |
|
|
|
Current U.S.
Class: |
206/581 ;
132/200 |
Current CPC
Class: |
A61K 2800/884 20130101;
A61K 2800/438 20130101; A61K 8/70 20130101; A61K 2800/434 20130101;
A61K 2800/81 20130101; A61K 2800/88 20130101; A61Q 17/04 20130101;
A61Q 1/08 20130101 |
Class at
Publication: |
206/581 ;
132/200 |
International
Class: |
B65D 85/00 20060101
B65D085/00; A45D 44/00 20060101 A45D044/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 23, 2009 |
FR |
09 00818 |
Claims
1. A method of making up human keratinous material with
light-sensitive makeup, the method comprising: applying to the
keratinous material a thermally stable photochromic first
composition comprising a photochromic agent developable by
radiation of a wavelength .lamda.; exposing the first composition
to said radiation to develop the photochromic agent and create a
light-sensitive makeup look; wherein: the thermally stable
photochromic composition is, at least temporarily and at least in
part, before or after being exposed to said radiation, covered by a
photoprotective layer, and exposure to said radiation for
developing the photochromic agent being performed through the
photoprotective layer when said layer is applied before the
thermally stable photochromic composition is exposed to said
radiation.
2. The method according to claim 1, wherein the photoprotective
layer comprises a second composition comprising an optical agent
that forms a screen to said radiation.
3. The method according to claim 2, wherein the photoprotective
layer is formed by applying a second composition, causing an
optical agent present in the first composition in an inactive or in
a precursor state to become active in order to screen said
radiation.
4. The method according to claim 1, wherein the photoprotective
layer comprises a coating that is transparent, at least in
part.
5. The method according to claim 1, wherein said radiation is UV
radiation and the photoprotective layer screened the UV radiation
and/or the near UV radiation.
6. The method according to claim 5, wherein the photoprotective
layer has a solar UV radiation screening power F that is greater
than 2.
7. The method according to claim 6, wherein the screening power F
is greater than 3.
8. The method according to claim 6, wherein the screening power F
is greater than 5.
9. The method according to claim 6, wherein the screening power is
greater than 10.
10. The method according to claim 1, wherein the photoprotective
layer is applied before the first composition is exposed to said
radiation.
11. The method according to claim 2, wherein the optical agent is
an optical diffusing agent.
12. The method according to claim 2, wherein the optical agent is
colored.
13. The method according to claim 2, wherein the optical agent is
colorless.
14. The method according to claim 2, wherein the optical agent is
fluorescent.
15. The method according to claim 1, wherein the photoprotective
layer is configured to screen a second radiation that is capable of
returning the photochromic agent to a non-developed state.
16. The method according to claim 1, wherein the photoprotective
layer comprising a peelable cohesive coating.
17. A kit comprising, within a single packaging: a thermally stable
photochromic first composition comprising a thermally stable
photochromic agent capable of being developed by exposure to
radiation of wavelength .lamda.; a photoprotective second
composition or a garment that is transparent, at least in part, for
application to the first composition, and including an optical
agent that screens said radiation of wavelength .lamda.; and an
irradiator for creating a light-sensitive makeup look.
18. The kit according to claim 17, wherein: the photochromic agent
is selected from the group consisting of diarylethenes and
thermally stable fulgides, the photochromic agent is developable by
exposure to UV radiation, and the optical agent forms a screen to
UV radiation.
19. The kit according to claim 18, wherein the second composition
has a solar UV radiation screening power F of 2 or more.
20. The kit according to claim 17, further comprising a system for
informing a user about an intensity of said radiation of wavelength
.lamda. in ambient lighting.
Description
[0001] The present invention relates to a method of making up human
keratinous material with light-sensitive makeup, e.g. making up the
skin, lips or the integuments, in particular the nails, or the
hair.
PRIOR ART
[0002] When making up, it is usual to use a colored substance that
is deposited on the body or face.
[0003] The final result not only depends on the quality of the
products used, in particular the ingredients and the formulation
techniques employed, but also on the dexterity of the user.
[0004] Some users undertake training with the hope of improving
dexterity and thus of improving the results of making up. Others do
not, considering themselves poorly equipped to deal with training
or not having the time to dedicate to it.
[0005] It has been discovered that it is possible to obtain
satisfactory makeup results using light-sensitive makeup. The
precision of the result exceeds that which users normally obtain
with conventional makeup, without the need either for particular
dexterity or for training.
[0006] Further, light-sensitive makeup may produce color effects
that go beyond what is normally accepted for makeup. This may be
any pattern imitating a conventional makeup pattern, or a text, a
sign, a logo, etc.
[0007] Light-sensitive makeup is based on using at least one
thermally stable photochromic composition that is capable of being
developed by light radiation, for example UV radiation, and that
retains a change in appearance linked to irradiation for at least
one hour.
[0008] In order to create a light-sensitive makeup look, at least
one thermally stable photochromic composition is deposited on the
zone to be treated in the form of at least one layer.
[0009] When the thermally stable photochromic composition is
applied, it is in the non-developed state and it may be colored or
colorless, depending on the ingredients used.
[0010] Irradiation of the layer of thermally stable photochromic
composition may be carried out selectively, by irradiating in a
non-uniform manner. Thus, certain regions need not be developed
while others are, and/or some regions may be developed to varying
extents, leading to different intensities of colors.
[0011] The light energy used remains relatively low and does not
cause the skin to tan.
[0012] One method of making up with light-sensitive makeup is
described in patent EP-A-0 938 887, which is incorporated by
reference and which employs thermally stable photochromic agents
that are applied to the skin. That patent describes a photochromic
agent selected from diarylethenes and fulgides.
[0013] There exists a need for further improvement to
light-sensitive makeup.
[0014] The light-sensitive makeup obtained is relatively
short-lasting; the sharpness of the colors tends to reduce over
time, sometimes quite quickly.
[0015] This is due to the fact that the zones that are not
irradiated by the UV radiation change over time under the effect of
ambient light. Thus, the contrast between the zones exposed to UV
radiation and the non-exposed zones softens. This is also due to
the fact that the zones irradiated by the UV radiation also tend to
lose their color.
[0016] Patent FR-A-2 780 275 describes a system with two
compositions, namely the photochromic composition and the
composition containing a UV screen. This UV screen composition is
applied as a second layer in order to produce a pattern on the
thermally stable photochromic composition by a stenciling effect.
Thus, the UV screen does not overcome the problem of loss of
sharpness of the light-sensitive makeup encountered with
photochromic agents.
SUMMARY OF THE INVENTION
[0017] Exemplary embodiments of the invention provide a method of
making up human keratinous material with light-sensitive makeup,
wherein: [0018] a thermally stable photochromic first composition
comprising a photochromic agent capable of being developed under
the effect of radiation of wavelength .lamda. is applied to the
keratinous material; [0019] the first composition is exposed to
said radiation to develop the photochromic agent and create a
light-sensitive makeup look; and [0020] the thermally stable
photochromic composition is, at least temporarily and at least in
part, before or after being exposed to said radiation, covered by a
photoprotective layer, exposure to said radiation for developing
the photochromic agent being performed through the photoprotective
layer when said layer is applied before the thermally stable
photochromic composition is exposed to said radiation in order to
create a light-sensitive makeup look.
[0021] The photoprotective layer may, for example, comprise a
second composition including an optical agent forming a screen to
said radiation.
[0022] The photoprotective layer may, for example, be formed by
applying a second composition, causing an optical agent present in
the first composition in an inactive or in a precursor state to
become active in order to screen said radiation.
[0023] The photoprotective layer may, for example, comprise a
coating that is transparent, at least in part.
[0024] The radiation may be UV radiation and the photoprotective
layer, in particular the optical agent, may screen the UV and/or
the near UV, in particular in the range 320 nm [nanometer] to 400
nm and/or 400 nm to 440 nm. The photoprotective layer may, for
example, present a screening power F as regards solar UV radiation
that is greater than 2 or 3, better greater than 5 or 10. By means
of the invention, the durability of the light-sensitive makeup is
improved. The degradation in the contrast of the patterns that have
been created is delayed.
[0025] The photoprotective layer may cover the thermally stable
photochromic composition entirely, or it may even extend beyond
said composition. The patterns of the light-sensitive makeup may be
independent of the photoprotective layer.
[0026] In an exemplary embodiment of the invention, the
light-sensitive makeup look is created, and then the
photoprotective layer is applied. The photoprotective layer, e.g. a
photoprotective composition or a garment, may be applied after the
first composition has dried.
[0027] In another exemplary embodiment of the invention, the
thermally stable photochromic composition is applied, then the
photoprotective layer is applied, and then the light-sensitive
makeup look is created. Under such circumstances, irradiation is
stronger so as to compensate for the absorption of the radiation by
the photoprotective layer.
[0028] Preferably, in both circumstances, the photoprotective layer
is applied before the person wearing the light-sensitive makeup is
exposed to outdoor light.
[0029] The screening power of the photoprotective layer need not be
uniform, and the non-uniform screening power may advantageously be
used to create esthetic effects during exposure to the radiation
that develops the thermally stable photochromic composition. These
effects may be variations in the intensity of the color of the
photochromic agent, for example. The optical agent may thus have a
dual role, namely to contribute to the formation of one or more
esthetic effects, and to protect the non-developed zones. Under
such circumstances, the light-sensitive makeup look may include
patterns having an appearance that is associated both with the
presence of the photoprotective layer and with the image projected
on the zone being treated in order to create the light-sensitive
makeup look.
[0030] The photoprotective layer may be applied in the form of an
uniform or a non-uniform layer. For a non-uniform layer, variations
in screening power due to the variations in thickness or in
concentration may advantageously be used to create esthetic effects
as indicated above.
[0031] An intermediate layer may possibly be interposed between the
layer of thermally stable photochromic composition and the layer of
photoprotective composition, e.g. to improve the retention of the
second layer, or, on the contrary, make it easier to remove.
[0032] The photochromic agent may be thermally stable.
[0033] The optical agent may be an optical diffusing agent, colored
or colorless, or it may even be fluorescent.
[0034] The photoprotective layer may be arranged to screen second
radiation that tends to return the photochromic agent to its
non-developed state.
[0035] The photoprotective layer may form a peelable cohesive
coating, thereby making it easy to remove.
[0036] The first and second layers may present ionic natures that
are complementary and/or surface tensions that are
complementary.
[0037] In the invention, it is possible to deposit a single layer
containing the optical agent(s), or a plurality of layers
containing a plurality of different optical agents.
[0038] For example, it is possible to deposit a single layer that
provides protection for the layer of thermally stable photochromic
composition as regards UV radiation and visible light.
[0039] It is also possible to deposit a specific layer for UV
protection and an additional layer for additional protection in the
UV and/or in the visible, the additional layer including a colorant
or a thermally unstable photochromic agent, for example.
[0040] It is also possible to deposit a layer for UV protection,
and an additional layer including a fluorescent compound that
provides additional protection in UV.
[0041] In one particular circumstance, a multi-layer film is
applied comprising a first layer of thermally stable photochromic
composition and a second photoprotective layer including an optical
agent forming a screen to the radiation that develops the thermally
stable photochromic composition. The film may be self-supporting or
it may be applied by transfer.
[0042] Other exemplary embodiments of the invention also provide a
kit comprising, within a single packaging: [0043] a thermally
stable photochromic first composition comprising a thermally stable
photochromic agent capable of being developed by exposure to
radiation of wavelength .lamda.; [0044] a photoprotective second
composition or a garment that is transparent, at least in part, for
application to the first composition, and including an optical
agent that screens said radiation of wavelength .lamda.; and [0045]
an irradiator for creating the light-sensitive makeup look.
[0046] The photochromic agent may be selected from diarylethenes
and fulgides, the photochromic agent being capable of being
developed by exposure to UV radiation, and the optical agent may
form a UV screen, in particular with a screening power F as regards
solar UV radiation that is 2 or more.
[0047] The kit may include a system that makes it possible to
inform the user about the intensity of said radiation in ambient
lighting. That makes it possible to select the photoprotective
composition accordingly, for example.
Thermally Stable Photochromic Composition
[0048] In accordance with the invention, the light-sensitive makeup
look is created using a suitable thermally stable photochromic
composition.
[0049] The thermally stable photochromic composition of the
invention contains one or more thermally stable photochromic agents
that are suitable for creating a light-sensitive makeup look, i.e.
they change appearance under the influence of light radiation.
[0050] The thermally stable photochromic agent or agents used in
the invention may, for example, be irreversible photochromic
agents, i.e. once the change in appearance is obtained, it is
permanent.
[0051] Depending on the thermally stable photochromic agent or
agents used, the light-sensitive makeup look may be created by
progressively developing said thermally stable photochromic agent
or agents by exposure to suitable radiation, for example UV and/or
near UV, or by starting from a thermally stable photochromic
composition comprising one or more thermally stable photochromic
agents in the already developed state that are brought into a
non-developed state by the application of suitable radiation, for
example visible beyond near-UV.
[0052] The light-sensitive makeup may implement both development of
one or more thermally stable photochromic agents and erasure of one
or more thermally stable photochromic agents, for example
successively or alternately, in order to obtain precisely the
desired makeup result.
[0053] The thermally stable photochromic composition may be
contained, with the thermally stable photochromic agent or agents
in the non-developed state, in a packaging device before
application to the keratinous material. In this configuration, the
thermally stable photochromic composition may be applied to the
keratinous material with the thermally stable photochromic agent or
agents in the non-developed state, then the radiation allowing to
change said photochromic agent or agents into the developed state
is applied.
[0054] In a variation, the photochromic composition is applied to
the keratinous material with the thermally stable photochromic
agent or agents in the non-developed state, then they are brought
into a developed state, and thereafter radiation is applied
selectively to change the thermally stable photochromic agent or
agents into the non-developed state, for example in a localized
manner, in order to create one or more patterns, for example,
and/or to obtain the desired color.
[0055] In another variation, the thermally stable photochromic
composition is contained in a packaging device with the thermally
stable photochromic agents being in the developed state. The
thermally stable photochromic composition is then applied with the
thermally stable photochromic agent or agents being in the
developed state, and these are brought into a non-developed state
in a selective manner in order to form one or more patterns and/or
to obtain the desired color.
[0056] When seeking to use a thermally stable photochromic
composition in which the thermally stable photochromic agent or
agents is/are already in the developed state when the composition
is applied to the keratinous material, it is optionally possible to
use a packaging device including a light source suitable for
exposing the thermally stable photochromic composition to light
radiation, for example within the enclosure of the receptacle
containing it or at a distribution orifice or an application
member, which light radiation is of a wavelength suitable for
developing the thermally stable photochromic agent or agents.
[0057] The thermally stable photochromic composition may comprise a
thermally stable photochromic agent capable, for example, of
generating a color in the developed state, and, for example, that
is colorless in the non-developed state, or a mixture of thermally
stable photochromic agents producing respectively different colors
in the developed state while having another color or being
colorless in the non-developed state.
[0058] As an example, it may be possible to use a thermally stable
photochromic composition comprising a mixture of respective yellow,
blue, and magenta thermally stable photochromic agents with, for
example, a larger proportion of thermally stable photochromic agent
of color that is yellow in the developed state, the proportions
being selected, for example when all of the thermally stable
photochromic agents are in the developed state, to obtain a hue
close to that of the skin. Thus, in one example of the invention, a
mixture of respectively yellow, magenta, and blue thermally stable
photochromic agents is used in relative proportions of
approximately 50%, 35% and 15%.
[0059] When the thermally stable photochromic composition comprises
a plurality of thermally stable photochromic agents, it is possible
to use thermally stable photochromic agents capable of being
developed by exposure to radiation with respective different
dominant wavelengths so that, by selecting the wavelength of the
radiation to which the thermally stable photochromic composition is
exposed, it is possible to develop one color rather than another.
It is also possible to use thermally stable photochromic agents in
a thermally stable photochromic composition capable of being erased
when exposed to the respective dominant wavelengths, which means
that, by selecting the characteristics of the light used to erase
the thermally stable photochromic composition, a given color may be
erased rather than another.
Measurement of the Thermal Stability of a Thermally Stable
Photochromic Agent
[0060] The test to determine whether a photochromic agent is
thermally stable is as follows. The agent to be tested, initially
with color E.sub.1 in the non-developed state, is irradiated using
UV radiation for 1 minute at 1 J/cm.sup.2 [joule per square
centimeter], then its final color E.sub.f is determined using a
spectrocolorimeter, for example that from MINOLTA CM 2002 (d/8,
SCI, D65, 2.degree. observer); a color difference
.DELTA.E.sub.i,f= {square root over
((a.sub.f-a.sub.i).sup.2+(b.sub.f-b.sub.i).sup.2+(L.sub.f-L.sub.i).sup.2)-
}{square root over
((a.sub.f-a.sub.i).sup.2+(b.sub.f-b.sub.i).sup.2+(L.sub.f-L.sub.i).sup.2)-
}{square root over
((a.sub.f-a.sub.i).sup.2+(b.sub.f-b.sub.i).sup.2+(L.sub.f-L.sub.i).sup.2)-
}
is obtained in CIE Lab space, which corresponds to the maximum
development. Said compound is then left in total darkness for 60
minutes at 25.degree. C., then its color E.sub.r is determined
using the above method. If the new value of .DELTA.E.sub.i,r is at
least 50% of the value of .DELTA.E.sub.i,f corresponding to the
maximum development, it is considered that the compound is
thermally stable. Preferably, the thermally stable photochromic
agent is selected so that once developed, the makeup obtained may
be visually conserved for more than one hour, preferably more than
four hours.
[0061] The thermally stable photochromic composition may be free of
thermally reversible photochromic compounds such as doped titanium
oxide, spiropyrans, spirooxazines, or chromenes, unless certain
forms of those compounds fall within the definition of thermally
stable photochromic agents.
[0062] The thermally stable photochromic agent or agents of the
invention are advantageously such that under an initial irradiation
I.sub.1, this or these agents are developed by becoming colored,
starting from a substantially colorless or faintly colored state;
and under a second irradiation I.sub.2 that differs from the first,
this or these agents go back to being substantially colorless or
faintly colored. In exemplary embodiments of the invention, the
irradiation I.sub.1 is UV irradiation (290 nm to 400 nm), in
particular UVA (320 nm to 400 nm) and/or UVB, better in the near UV
(400 nm to 440 nm), while irradiation I.sub.2 is irradiation in the
visible, for example white light.
Thermally Stable Photochromic Agents
[0063] Preferred examples of photochromic agents that may be used
are compounds which belong to the diarylethene family and those
which belong to the fulgide family; this list is not limiting,
however. The skilled person may make reference to patent EP-A-0 938
887 that describes examples of thermally stable photochromic
agents.
[0064] Diarylethenes may be represented by the following formula
(I):
##STR00001##
in which the radicals R.sub.1 and R.sub.2 are always "cis" relative
to the double bond.
[0065] These radicals R.sub.1 and R.sub.2, independently of each
other, may be selected from C.sub.1-C.sub.16 alkyl radicals, which
may be fluorinated or perfluorinated, and nitriles.
[0066] Compounds with the following formula may be mentioned in
particular:
##STR00002##
[0067] They may also form a cycle containing 5 or 6 carbon atoms,
which may be fluorinated or perfluorinated, in particular with the
following formula:
##STR00003##
form a 5 carbon atom anhydride cycle, in particular with the
following formula:
##STR00004##
in which X may be an oxygen atom or a --NR3 radical, where R3
represents a C2-C16 alkyl and/or hydroxyalkyl radical.
[0068] Radicals A and B may also be equal or different and in
particular may represent a 5-atom cycle or a 5- or 6-atom bi-cycle
with the following structures:
##STR00005##
in which: [0069] X and Y may be the same or different, and may
represent an oxygen atom, a sulfur atom, an oxidized form of
sulfur, a nitrogen atom or a selenium atom; [0070] Z and W may be
the same or different, and may represent a carbon or nitrogen atom;
[0071] the radicals R.sub.3 to R.sub.12 may be the same or
different, and may represent a hydrogen, a linear or branched
C.sub.1-C.sub.16 alkyl or alkoxy group, a halogen, a linear or
branched, fluorinated or perfluorinated C.sub.1-C.sub.4 group, a
carboxylic group, a C.sub.1-C.sub.16 alkylcarboxylic group, a
C.sub.1-C.sub.16 mono- or dialkyl-amino group, a nitrile group, a
phenyl group, a naphthalene group or a heterocycle (pyridine,
quinoline, thiophene) may be substituted onto said radicals.
[0072] However, groups A and B must not both be equal to an indole
type structure such as that below:
##STR00006##
[0073] Groups A and B may be separated from the cycle by one or
more double bonds.
[0074] In the positions ortho to the junction, between the double
bond and the residues A and B, there must always be a group other
than hydrogen, for example CH.sub.3, CN, or COOEt, i.e. groups
R.sub.3 or R.sub.5, R.sub.4, R.sub.7 and R.sub.8 must be other than
hydrogen.
[0075] An example that may be mentioned is the following compound
that changes from colorless to red as follows, after irradiation at
404 nm-436 nm (return at 546 nm-578 nm):
##STR00007##
[0076] One example of a diarylethene is that which is blue in color
in the developed state, sold under the trade name: DAE-MP by Yamada
Chemical (Japan), with chemical name and formula: 1,
2-bis(2-methyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluorocyclopentene:
##STR00008##
[0077] Another example of a diarylethene is that with a yellow
color in the developed state, with formula:
##STR00009##
sold under the trade mark: DAE-2BT by YAMADA CHEMICALS (Japan) and
with chemical name:
1,2-bis(3-methylbenzo(b)thiophen-2-yl)perfluorocyclopentene.
[0078] Fulgides may be represented by the following formula:
##STR00010##
in which: [0079] group A has the meaning given above; [0080] groups
R.sub.13 to R.sub.15 may be the same or different, and may
represent a C.sub.1-C.sub.16 linear or branched alkyl group, or
groups R.sub.13 and R.sub.14 may form a cycle containing 3 to 12
carbon atoms, such as a cyclopropane or an adamantylene.
Other Thermally Stable Photochromic Agents
[0081] These photochromic compounds are compounds that change
appearance, for example changing from a colorless or faintly
colored form to a colored form via a mechanism controlled by light
irradiation.
[0082] The mechanism may be direct, in the sense that light causes
the appearance to change, for example by changing from the
colorless form to the colored form. This applies, for example, with
compounds carrying a photodegradable or photorelease function.
[0083] Preferably, compounds are used wherein the photodegradable
or photorelease function is inert relative to keratinous
material.
[0084] Preferably, a compound is used wherein the photodegradable
or photorelease function is immobilized or carried by a polymer or
other solid or bulk structure.
[0085] As an example, the 3-5-dimethoxybenzoin function and colored
products as described in the article: C. P. McCoy et al., J. Am.
Chem. Soc., 2007, 129, 9572, may be used.
[0086] The above mechanism may also be indirect, in the sense that
light causes the compound, which is initially colorless, for
example, to change into another form, then a third action
transforms that modified, but still colorless, compound into a form
with a different appearance, for example colored.
[0087] The mechanism is also indirect when a third action acts
differently on the compound that has not been modified by light and
on the modified compound and, for example, the unmodified compound
is transformed and changes appearance, becoming colored, for
example, while the modified compound conserves its appearance for
example colorless.
[0088] As an example, it is possible to use the diazotype
principle, which uses a diazonium salt compound and another
aromatic compound that is capable of reacting by a coupling
reaction. Irradiation destroys the diazonium salt (liberation of
nitrogen). The diazonium compound that has not been irradiated then
reacts by a simple jump in pH (in the presence of ammonia, for
example) with the coupler to produce an azo compound. Under such
circumstances, non-colored diazonium salt compounds are selected,
such as an aromatic compound carrying the diazonium function but
not carrying an amine or hydroxyl function on the cycle. The
coupler may be a simple aromatic amine such as an aniline or phenol
derivative.
[0089] Thus, the non-irradiated portions are developed, in
accordance with the reaction:
##STR00011##
[0090] The photochromic agent or agents used may become thermally
stable upon development or only after a specific action has been
carried out, for example being brought into the presence of
chemical compounds endowing them with the desired thermal
stability.
[0091] The thermally stable photochromic composition may contain a
total of 0.001% to 20% by weight of photochromic agent(s), in
particular thermally stable photochromic agent(s).
[0092] The photochromic composition may also contain any solvent
that is appropriate for cosmetic application, in particular
selected from those mentioned in patent EP-A-0 938 887.
[0093] The composition may comprise the ingredients named in
paragraphs [0029] to [0041] of EP-A1-0 938 887; the list is hereby
incorporated by reference.
Reduced Sensitivity Thermally Stable Photochromic Composition
[0094] The thermally stable photochromic composition may include at
least one optical agent reducing its sensitivity to UV or near UV
radiation.
[0095] The thermally stable photochromic composition may in
particular comprise one or more optical agents in a quantity
sufficient for its screening power F as defined below to be 2 or
more, or even 5, 10, 15, or 20.
Protocol for Measurement of Screening Power
[0096] A protocol similar to that used to determine the SPF is
used, the difference being that the erythemal response of the skin
is not taken into account.
[0097] The composition of screening power that is to be discerned
is applied in an amount of 1.2 mg/cm.sup.2 [milligram per square
centimeter] to a sanded polymethyl methacrylate (PMMA) plate
(without UV screen) measuring 5 cm [centimeter] by 5 cm, 3 mm
[millimeter] in thickness, with a roughness of 4.5.+-.1 .mu.m, from
EUROPLAST. The plates are pre-treated with a deposit of 10.+-.1 mg
of Vaseline 145B. The composition may be deposited in 14 dots of
composition and spreading is carried out for 20 seconds using a
finger, making zigzags and turning the plate by one fourth of a
turn every 5 seconds.
[0098] After spreading, 0.6 mg/cm.sup.2 of composition subsists. It
is allowed to dry for 20 minutes (min), and is then spread
again.
[0099] A spectroradiometer is used (for example a Labsphere UV
transmittance analyzer with an integrating sphere), which measures
diffuse transmittance from 290 nm to 400 nm. Each value for
transmission T(.lamda.) is recorded. T(.lamda.) is the ratio, for a
given irradiation wavelength 2, of the transmitted light energy
over the incident light energy. 5 measurements are taken per plate
(moving the plates) and the mean of these 5 measurements is taken.
The operation is carried out on 5 plates. The means of the 5
measurements is taken.
[0100] The screening power F relative to solar UV radiation (290 nm
to 400 nm) is given by the ratio of the following two
integrals:
F = .intg. 290 nm 400 nm I ( .lamda. ) .lamda. .intg. 290 nm 400 nm
I ( .lamda. ) T ( .lamda. ) .lamda. ##EQU00001##
where I(.lamda.) is a function representing the occurrence of each
wavelength of the solar spectrum. I(.lamda.) is the same as that
used to calculate the in vitro SPF in the publication COLIPA
GUIDELINES Edition of 2007: A METHOD FOR THE IN VITRO DETERMINATION
OF UVA PROTECTION PROVIDED BY SUNSCREEN PRODUCTS. If F=1, then the
composition does not screen.
[0101] The term "act as a screen to radiation with wavelength
.lamda.." means that the optical agent attenuates radiation with a
wavelength .lamda. by at least an attenuation factor of 2, the
measurement being carried out using an apparatus for measuring the
absorption spectrum, restricting the irradiating light to a zone
with a wavelength .lamda..+-.10 nm. The ratio
F .lamda. - 10 , .lamda. + 10 = .intg. .lamda. - 10 .lamda. + 10 I
( .lamda. ) .lamda. .intg. .lamda. - 10 .lamda. + 10 I ( .lamda. )
T ( .lamda. ) .lamda. ##EQU00002##
where I(.lamda.) and T(.lamda.) are as defined above, provides the
attenuation factor at wavelength .lamda..
[0102] The thermally stable photochromic composition may have at
least one range P of wavelengths in the interval .lamda..sub.1 to
.lamda..sub.2 where the irradiation is less screened, the screening
power in this range being a mean of F.sub..lamda.1,.lamda.2, where
F/F.sub..lamda.1,.lamda.2>2, preferably
F/F.sub..lamda.1,.lamda.2>5. The width of the range P may be
less than 80 nm, preferably less than 40 nm.
[0103] F.sub..lamda.1,.lamda..lamda.2 is defined by:
.intg. .lamda.1 .lamda.2 I ( .lamda. ) .lamda. .intg. .lamda.1
.lamda.2 I ( .lamda. ) T ( .lamda. ) .lamda. ##EQU00003##
and measured as described above, replacing the limits 290 and 400
by .lamda..sub.1 and .lamda..sub.2, where
.lamda..sub.2>.lamda..sub.1.
[0104] Where appropriate, the thermally stable photochromic
composition may comprise a color-change colorant, for example a
coloring agent of color that develops over time and if possibly
slowly, for example DHA or polyphenols, which may slowly become
colored in contact with air. The thermally stable photochromic
composition may, for example, comprise a coloring agent that takes
more than half an hour to become 90% developed. The advantage of
such a coloring agent may be that it develops a screening power
once the light-sensitive makeup look has been created in order, for
example, to retard the degradation of the light-sensitive makeup
patterns under the effect of ambient light.
Second Layer Acting as Activator for an Optical Agent Present in
the First Layer
[0105] In one exemplary embodiment of the invention, a first layer
is constituted by the thermally stable photochromic composition and
contains an optical agent in the partially or completely
deactivated form or as a precursor. This agent in the deactivated
form or in the precursor state has not yet been the sufficient
activity to protect the result of the light-sensitive makeup.
[0106] After the light-sensitive makeup, application of a second
layer serves to activate the deactivated optical agent or bring the
precursor into the form of an optical agent that is effective in
forming a screen to the radiation developing the thermally stable
photochromic composition.
[0107] As an example, in a precursor form in one of the layers, the
optical agent may be a coloring agent from the porphyrin class,
rendered more active by the presence in the other layer of a salt
in solution, for example a zinc, iron, or magnesium salt.
Galenical Forms
[0108] The thermally stable photochromic composition may be
presented in various galenical forms depending on the applications
and the nature of its constituents.
[0109] The thermally stable photochromic composition of the
invention contains a cosmetically acceptable medium, i.e. a medium
that is compatible with all keratinous materials such as the skin,
the nails, the hair, the eyelashes and eyebrows, the mucous
membranes and the semi-mucous membranes, and any other cutaneous
zone of the body and face. In particular, said medium may comprise
or be in the form of a suspension, a dispersion, a solution in a
solvent or hydroalcoholic medium, optionally thickened or gelled;
an oil-in-water emulsion, a water-in-oil emulsion, or a multiple
emulsion; a gel or a foam; a gel emulsion; a spray; a loose,
compact, or cast powder; an anhydrous paste; or a film, inter
alia.
Treated Zones
[0110] Any part of the body that is normally made up may receive
light-sensitive makeup in accordance with the invention, for
example the nails, eyelashes, hair, skin and in particular that of
the face, for example the cheeks, the forehead, the lips or eye
contour, the neck, the chest or the legs.
[0111] It is also possible to treat parts of the body that are
rarely made up, such as the ears, the hands, or the teeth. These
zones have complex shapes that do not assist in making the
application of conventional makeup products easy. Light-sensitive
makeup enables esthetic results to be obtained, despite their
complex shapes.
[0112] Light-sensitive makeup may be used to camouflage a skin
blemish.
[0113] Light-sensitive makeup may optionally repeat a pattern from
clothing or an accessory worn by the user, for example a pattern on
a piece of jewelry, a purse, eyeglasses, shoes, a piece of
furniture, a personal digital assistant (PDA), or a cell phone.
[0114] Where appropriate, sale of such clothing or such an
accessory may be accompanied by the provision of a file or an
internet link that allows a light-sensitive makeup look to be
created that coordinates with the accessory or clothing.
[0115] The file or internet link may provide access to the data
necessary for producing an image that has been designed or selected
in order to coordinate with the clothing or accessory. As an
example, it may repeat all or part of the patterns or it may
complete them.
DESCRIPTION OF THE FIGURES
[0116] FIG. 1 is a diagrammatic and fragmentary view of an example
of a system for processing light-sensitive makeup produced in
accordance with the invention;
[0117] FIG. 2 illustrates how the zone to be treated is held during
light irradiation;
[0118] FIG. 2a illustrates the formation of a pattern within a
pixelated image;
[0119] FIGS. 3 to 6 are diagrammatic and partial views of
variations of the irradiator;
[0120] FIGS. 7 to 10 and 10A illustrate different examples of
addressable matrix imagers using several technologies;
[0121] FIGS. 11 to 13 show examples of light-sensitive makeup;
[0122] FIGS. 14A to 14C and 15A to 15C show examples of the
progress of light-sensitive makeup; and
[0123] FIG. 16 represents an example of a packaging device enabling
the composition to be developed before it is applied.
MODES OF APPLICATION
[0124] The or each composition suitable for use in implementing the
invention may be applied in the form of a powder, fluid, spray, or
film. The fluid may have different rheologies. It may, for example,
be a block of product that spreads when rubbed onto keratinous
material, or it may be a liquid.
[0125] The layer of thermally stable photochromic or optionally
photoprotective composition, and rather the photoprotective
composition layer, may be applied in the form of a dry or nearly
dry powder.
[0126] The or each composition may optionally be in the form of a
pre-formed film.
[0127] Preferably, when using a multilayer application, the second
layer is preferably applied without deteriorating the first layer
that has already been applied. To this end, it may be preferred to
apply the composition intended to form the second layer by
spraying.
[0128] Application may also be carried out using a printer, for
example an inkjet printer, using an apparatus that is brought into
contact with the zone to be treated, and optionally that is moved
over it. When one or more layers are sprayed, any spray technique
may be used, for example spraying by means of a propellant gas, an
airbrush, or electrostatic or piezoelectric spraying. The
application may also be carried out by transfer, using a support
sheet carrying at least one of the compositions, or even the
various layers to be formed. The transfer may be accomplished by
pressure, by heat, and/or by using a solvent deposited on the
support sheet and/or keratinous material that are to be treated in
accordance with the invention.
[0129] The application may be carried out manually or in an
automatic manner, e.g. using a manipulator arm.
[0130] Each layer may be applied after drying any layer that
precedes it.
[0131] The application may be made using applicators, possibly
single use applicators, comprising an application member loaded
with composition to be applied.
[0132] The compositions may be applied at a point of sale, in a
beauty salon, or in the home, inter alia.
[0133] Each composition may be packaged before use into any
suitable receptacle.
[0134] The compositions, and in particular the thermally stable
photochromic composition, may be applied after verifying that the
intensity of the ambient light is not prejudicial to the quality of
the light-sensitive makeup look. Verification may be carried out
using a warning device that alerts the user if the ambient light
contains UV or near UV radiation that is too strong, for example
with a fluence of 0.1 mW/cm.sup.2 or 0.5 mW/cm.sup.2, the threshold
being adjustable if necessary. Such a device may be autonomous or
integrated with a packaging device or a device for application of
the thermally stable photochromic composition, or even a packaging
device or device for application of a photoprotective
composition.
[0135] Where appropriate, the information delivered by the warning
device may also be useful for selecting a thermally stable
photochromic composition, a photoprotective composition, and/or a
composition serving as a base layer amongst a plurality of
compositions, depending on the level of the UV radiation.
[0136] As mentioned above, where appropriate, the thermally stable
photochromic composition may be applied in the completely developed
state or in the non-developed state.
[0137] The thermally stable photochromic composition and the
composition intended to form the coating layer or the base layer or
the photoprotective layer may be in a variety of forms, for example
creams, gels, liquids, in the form of compositions to be spread
with the hand or using an applicator, for example a roll-on.
[0138] The composition may be applied by moving a block of
composition in contact with the keratinous material, such as a
lipstick, for example. Further, the composition may be applied by
spraying using an aerosol can, a pump bottle, or an electrostatic,
piezoelectric, or airbrush spray device.
[0139] The composition may be in dry form, such as a powder, which
may be applied with a brush or paintbrush if required.
[0140] When the photochromic composition is intended to be applied
in the developed state, it may be contained in a packaging and
application device as shown in FIG. 16, comprising a recipient 1000
containing the composition, a light source 1010 emitting in the UV,
for example, to develop the composition, and applicator means, for
example an applicator paintbrush 1020.
System for Processing Light-Sensitive Makeup
[0141] The light-sensitive makeup look may be created using a
system 1 for processing light-sensitive makeup comprising an
irradiator 3 comprising at least one light source 2, as may be seen
diagrammatically in FIG. 1. Depending on circumstances, the imager
may serve to develop the thermally stable photochromic composition,
for example by causing the photochromic agent or agents it contains
to pass from a non-developed state to a developed state and/or by
serving to erase the photochromic agent or agents contained in the
thermally stable photochromic composition by causing them to pass
from a developed state to a non-developed state. When the
composition is initially in the non-developed state, the irradiator
may, for example, emit in the UV or near UV when the thermally
stable photochromic composition may be developed by UV or near UV
radiation.
[0142] The image may be defined by a mask or a negative disposed in
the path of the light traveling to the zone to be treated, and
optionally in contact with the zone to be treated.
[0143] The irradiator preferably comprises one or more imagers 4
for forming at least one image at a distance on the zone to be
treated Z.
[0144] In a simplified version, the imager or imagers may use a
mask or a negative and optics for projection on the zone to be
treated. The negative may be a UV negative that allows an image to
be formed in UV or near UV light.
[0145] The source 2 may comprise any type of luminous element, for
example an incandescent lamp, a halogen lamp, a discharge lamp,
and/or an electroluminescent element, in particular one or more
light-emitting diodes (LEDs), organic LEDs (OLEDs) or other
electroluminescent technologies.
[0146] As is described in detail below, the irradiator 3 may
comprise a plurality of sources in order to emit, on the one hand,
in the UV or near UV and, on the other hand, in the visible, in
particular the visible beyond the near-UV.
[0147] Advantageously, the irradiator comprising the light source
or sources and the imager or imagers are capable of emitting
selectively in the UV or near UV and in the visible.
[0148] Changing a projection of an image in visible light to a
projection of an image in UV light may be accomplished by changing
the source by using a movable mirror, by using a semi-transparent
surface, by adding or removing a filter, and/or by using a
frequency doubler or tripler, for example.
[0149] As is described in detail below, using visible light enables
the image projected on the zone to be treated to be seen before
carrying out development and/or causing the light-sensitive makeup
to be removed from a zone that has already been at least partially
developed, when the photochromic agent or agents allow this.
[0150] As may be seen in FIG. 1, the system for processing
light-sensitive makeup may comprise a computer 10 that may be
associated with a user interface 11 comprising, for example, a
keyboard, a mouse, a touch screen, a voice recognition engine, a
graphics tablet, a joystick, and/or a touch pad; this list is not
limiting.
[0151] The computer 10 may comprise a microcomputer and, more
generally, any computing means, analog and/or digital, produced
using microcontrollers, microprocessors, and/or programmable logic
arrays, for example.
[0152] The computer 10 may be produced in the form of one or more
appliances, and when an electronic imager is used, where
appropriate the imager may carry out all or some of the
computations. The computer 10 may also be associated with a display
means 12 that is, for example, a color screen, for example of the
LCD, plasma, OLED or cathode ray type, optionally a touch screen.
As described below, this display means 12 may be used to display
the treated zone during treatment, enabling the treatment to be
controlled and/or a simulation to be displayed.
[0153] The computer 10 may also be associated with data storage
means 13, for example a hard disk, a magnetic tape, an optical
disk, and/or flash memory, the data storage means possibly being
integrated into the computer 10, the irradiator 3, and/or at least
partially remote in an external data storage system.
[0154] The computer 10 may be associated with a network interface
14 that serves, for example, to download data pertaining to
light-sensitive makeup or to cause data concerning the
light-sensitive makeup that is being applied or has been applied to
be transmitted to third parties or to a server.
[0155] Where appropriate, the computer 10 may advantageously
control the source or sources producing the light used to form the
image, so that the image is formed with a pre-defined
illuminant.
[0156] The imager is advantageously an electronic addressable
matrix imager as is described below, to which the computer may send
data in order to cause a pre-defined image to be projected onto the
zone Z to be treated.
[0157] The system for processing light-sensitive makeup may be
provided with at least one optical and/or electronic system
enabling the image to be focused manually or automatically, and
advantageously with means to prevent movements.
[0158] In order to keep the zone being treated still relative to
the irradiator, the system for processing light-sensitive makeup
may comprise means for keeping the person still, meaning that
movement and fuzzy results may be avoided.
[0159] When the image is formed on a face, the system for
processing light-sensitive makeup may be configured to detect that
the face is relaxed, and to control the imager as a function of
that detection.
[0160] The system 1 for processing light-sensitive makeup may
comprise a flat portion or it may follow the shape of a part of the
body and that part may be placed against the zone to be
treated.
[0161] In a variation or in addition, the system for processing
light-sensitive makeup may comprise a system for rectifying
movements, e.g. of the same type as those used to stabilize images
in still or motion picture cameras.
[0162] When the face is treated, the system for processing
light-sensitive makeup may comprise a means 8 for immobilizing the
individual to be treated, in the form of a chin rest, as may be
seen in FIG. 2.
[0163] In a variation, the irradiator 3 is portable and may be
fastened on a mount carried by the individual to be treated, in
order to illuminate the face, for example.
[0164] The system 1 for processing light-sensitive makeup may
comprise an optical acquisition device 16 that, in one exemplary
embodiment of the invention, may transmit data to the computer 10
so as to cause it to propose a light-sensitive makeup look and/or
so as to control the production thereof, as is described in detail
below. The optical acquisition device 16 may advantageously have a
viewing axis that is substantially parallel to the direction of
projection of the image. The optical acquisition device may be
monopixel or multipixel, and it may receive the light emitted by
the imager directly or it may receive the light reflected by the
zone Z to be treated.
[0165] The optional optical acquisition device, the irradiator, the
optional computer, and the optional view screen may be produced in
the form of separate elements or they may be integrated in the same
casing. The irradiator and the optical acquisition device may
advantageously be integrated in the same casing or they may be
fastened together by other means.
[0166] The view screen may be fastened to the back of the casing of
the irradiator or integrated into the casing. Where appropriate,
the optical acquisition device comprises an internal lighting means
for close-up acquisition.
[0167] The casing of the irradiator may also be movable and may be
applied to the skin, for example, or it may be held in the hand. In
one exemplary embodiment of the invention, the casing of the
irradiator may, for example, be placed on a table. The face may
then be moved close to be placed on the casing, e.g. by
leaning.
[0168] The system for processing light-sensitive makeup may be
provided with means for detecting opening or closing of the eyes
and/or the mouth in order to stop or not begin irradiation if the
eyes and/or the mouth are open. The optical acquisition device 16
may provide an image that is analyzed for this purpose by the
computer 10.
[0169] When the image is formed on a face, the system for
processing light-sensitive makeup may be configured to identify the
face and the imager may be controlled as a function at least of
this identification.
[0170] The system for processing light-sensitive makeup is
advantageously designed to allow a user to evaluate progress of the
light-sensitive makeup, visually or otherwise.
[0171] To this end, the system for processing light-sensitive
makeup may include a window allowing direct viewing of the zone
being treated during irradiation, this viewing being carried out,
where appropriate, through a UV screen. In order to allow room for
direct viewing, the light may be emitted from an offset position
and optical fibers or at least one mirror or a prism may be used to
direct the light and focus the radiation on the zone to be
treated.
[0172] FIG. 3 is a diagram showing part of a system for processing
light-sensitive makeup that comprises two imagers 4a and 4b,
respectively emitting ultraviolet light and visible light, towards
the zone Z to be treated. A window 403 is provided between these
imagers 4a and 4b, to allow observation of the zone Z during
treatment.
[0173] The viewing zone may also be offset using a mirror 404 or
any other optical system, for example optical fibers or a prism, as
may be seen in FIG. 4.
[0174] In the presence of an optical acquisition device such as a
video camera or a digital photographic apparatus, the treated zone
Z may be viewed on a screen that may be placed on the irradiator or
that may be offset.
[0175] FIG. 5 illustrates the possibility of producing the
irradiator 3 by offsetting the light beam directed towards the zone
Z to be treated by using mirrors 18, which allows the user to
observe the treated zone Z through a window 20 of the
irradiator.
[0176] FIG. 6 illustrates the possibility of producing the
irradiator 3 with two light sources 2a and 2b respectively emitting
in the UV and in the visible. The irradiator shown in FIG. 6
comprises a color filter 302, for example a green filter, placed in
front of the source 2b, adjustable collimation optics 303, and a
movable mirror 304. The irradiator 3 in this example allows a
negative 308 to be placed in the optical path. The adjustable
collimation optics 303 causes the image of the negative to appear
at a certain distance from the optical outlet of the irradiator 3,
for example at about twenty centimeters.
[0177] The irradiator 3 is provided with two switches 306 and 307.
The first actuates the sources 2a and 2b. The movable mirror is
disposed so that only visible light is directed towards the optical
outlet for a given position of the second switch. Actuating the
switch moves the movable mirror, for example by activating a
micromotor or an electromagnet, and the UV irradiation is then
directed towards the negative 308.
[0178] As mentioned above, the system for processing
light-sensitive makeup advantageously comprises an electronic
addressable matrix imager.
Electronic Addressable Matrix Imager
[0179] By way of example, an addressable matrix imager is suitable
for projecting a pixilated image with a resolution of more than 10
by 10 pixels, preferably more than 10 by 100 pixels.
[0180] When the imager is an electronic addressable matrix imager,
the image formed on the zone to be treated is formed by pixels that
are on or off, optionally each at a pre-defined gray level. As an
example, FIG. 2A shows a detail of FIG. 2 where the light-sensitive
makeup P that is produced consists of a lip outline. FIG. 2A shows
the placement of the various pixels of the projected image; only
the pixels corresponding to the outline to be produced have been
switched on. Development of the thermally stable photochromic
composition matches the states of the pixels.
[0181] The light leaving the addressable matrix imager may be
monochromatic or multichromatic; preferably, the addressable matrix
imager is capable of selectively emitting in the UV or near UV and
also in the visible beyond the near UV, the light emitted in the
visible possibly being white light or a colored light, optionally
monochromatic light.
[0182] The computer 10 may determine the digital image on the basis
of which the electronic imager is controlled, in particular the
gray level of each pixel, and optionally also the dominant
wavelength of the light at each pixel.
[0183] Several technologies may be used to produce the addressable
matrix imager.
[0184] It is possible to use the technology known as DLP (digital
light processing) invented by TEXAS INSTRUMENTS, which uses a DMD
(digital micromirror device) chip composed of thousands of
micromirrors of orientations that are individually controllable by
using an electric pulse, and depending on their orientation they
may optionally reflect an incident beam of light in order to
transmit or not transmit it to the optical outlet of the imager.
The image to be projected is formed on the matrix of mirrors. The
gray level in each pixel (for example 256 levels) may be controlled
by adjustment of the mark space ratio.
[0185] FIG. 7 shows an example of an electronic imager 4 produced
using this technology, using a DMD chip with reference numeral 111.
The chip may be fastened on a platen 112 that may also include a
processor 113 to control the chip, and also an optional memory 114.
In the example shown, the chip is shown on the same platen as the
processor 113 and the memory 114, but these items may be placed
elsewhere.
[0186] The imager 4 shown in FIG. 7 receives light from a source 2
that may be a source capable of emitting both in the UV and/or in
the visible or a source capable of emitting selectively in the
visible or in the UV.
[0187] The source 2 may be a halogen lamp emitting in the UV and
visible spectra, a discharge lamp, or one or more LEDs that are
capable of emitting in the UV and of emitting white light, or light
of a given color, for example.
[0188] As illustrated, the imager 4 may include optics 118, 119,
and 120 respectively to condense the light, focus it on the DMD
chip, and bring it to the zone to be treated.
[0189] When the source 2 has an emission spectrum in both the UV
and in the visible, as illustrated, the imager 4 may have a filter
wheel 130 that intersects the light beam between the condensation
optics 118 and the focusing optics 119, for example. Depending on
the position of the filter wheel 130, the chip receives UV or
visible light that is then directed towards the optical outlet.
Thus, it is possible to form an image on the zone to be treated
selectively from visible light and/or UV light.
[0190] The irradiator in the variation of FIG. 8 uses a plurality
of DMD chips fastened on a prism that divides the incident light
from the source 2 into at least two beams with different dominant
wavelengths, for example respectively in the UV or near UV and in
the visible.
[0191] The light beams reflected by the DMD chips are projected
towards the zone to be treated.
[0192] By controlling the DMD chip associated with the UV or near
UV beam and the chip associated with the beam of visible light,
either a beam of UV light or of visible light or possibly of both
at once may be projected onto the zone to be treated; when
development takes place relatively slowly, this may be useful in
order to be able to visually monitor the proper positioning of the
light acting to carry out the development.
[0193] The irradiator may also use liquid crystal display (LCD)
technology.
[0194] In the example of FIG. 9, the source 2 is directed onto
dichroic mirrors 125 that generate at least two light beams with
different dominant wavelengths, one of said beams having a dominant
wavelength in the UV or near UV and the other in the visible, for
example.
[0195] The beams are directed by the mirrors 125 and 126 towards
the LCD matrix screens 127 on which the image to be projected is
formed, producing monochrome images directed towards a system of
prisms 128, enabling the image to be sent via the projection optics
120 to the surface to be treated. Depending on the degree of
opacity of the screens 127, the light emitted is in the visible
region or in the UV region.
[0196] The irradiator 3 illustrated in FIG. 10 comprises an LCD
matrix screen 132 and a source 2 that illuminates the screen 132.
The image formed thereon is projected onto the zone to be treated
by means of the projection optics 120. By way of example, the
source 2 is capable of selectively emitting in the UV or in the
visible.
[0197] In a variation, the screen 132 may replace the negative 308
of the example of FIG. 6.
[0198] The projection system may also be based on liquid crystal on
silicon (LCOS) technology. LCD technology is termed transmissive
because the light passes through an LCD screen, while DLP
technology is termed reflective since the light is reflected by the
micromirrors of the DMD chip. In LCOS technology, the mirrors of
the DMD chips are replaced by a reflective surface covered with a
layer of liquid crystals that may be switched between a
light-passing state and a light-blocking state. By modulating the
frequency at which the liquid crystals are turned on and off, the
gray level of a pixel may be varied.
[0199] By way of example, the arrangements illustrated in FIGS. 7
and 8 may be used, replacing the DMD chips with LCOS chips.
[0200] FIG. 10A shows an LCOS chip irradiator. A system of lenses
901 may be disposed between the source 2, e.g. a UV lamp, and a
semi-transparent mirror 903. This reflects light from the source to
the chip 900. The chip reflects the light again to a focusing
system 120 that projects the pixelated image onto the zone to be
treated.
[0201] In general, the image delivered by the addressable matrix
imager comprises a matrix of pixels of gray levels that are
individually addressable, each gray level, for example, being coded
into at least 4 bits, preferably 8 bits. The light associated with
each pixel may also be coded where appropriate.
[0202] The image to be projected may be supplied to the electronic
imager in the form of a video signal complying with the VGA, SVGA,
composite, HDML, SVIDEO, YC.sub.BC.sub.R, optical video signal, or
other standard, or in the form of a video or digital image file,
e.g. a .jpeg, .pdf, .ppt, etc file. When these images are not
monochrome, a pre-defined color on the image in the file may
control the quantity of UV or near UV, for example.
[0203] The electronic imager is advantageously produced so as to be
able to change the nature of the light emitted without changing the
image; as an example, the pixels of the image retain their gray
levels and only the emission spectrum of the source used upstream
changes. This enables an image to be visualized on the zone to be
treated and then the zone may be developed, simply by modifying the
emission spectrum of the source.
[0204] The imager may be used to project visible light in order to
selectively erase one or more photochromic agents and to create a
light-sensitive makeup look from a thermally stable photochromic
composition in the developed state. The imager may then be a
conventional video projector, for example.
Choice of Projected Image
[0205] In particular when using an electronic addressable imager,
the system for processing light-sensitive makeup is preferably
provided with a means for selecting the projected image. This may
be accomplished by selecting from a library of images, possibly by
displaying a succession of images from said library and the user
selecting a displayed image. The images may be stored in the
digital or photographic form, for example in the data storage
means. The image library may be included in the system for
processing light-sensitive makeup, or it may be downloaded.
[0206] In one exemplary embodiment of the invention, a tailored
image is used starting from the individual intended to receive the
light-sensitive makeup, or from a model such as a celebrity or an
individual of given style, the images possibly being derived from
made-up or non made-up persons. It is also possible to use images
derived from drawings, tables, sketches, or caricatures to generate
the projected image.
[0207] The computer may have in its memory or may download at least
one pictorial model in the form of lines or brush strokes, or even
a single point or a series of lines, strokes, or points.
[0208] The image formed may be determined automatically as a
function of the acquired image. This enables the projected image to
be adapted to the morphology and/or to the color of the face.
[0209] Starting from the position of the captured face, the
computer may correctly position the image intended to create the
light-sensitive makeup look.
[0210] The system for processing light-sensitive makeup may thus be
used in a method comprising the steps consisting in: [0211]
acquiring at least one image of the zone of the subject to be made
up; [0212] controlling the imager as a function of the acquired
image.
[0213] As an example, the image may be acquired using an optical
acquisition device 16 that may be adapted to capture all or a
portion of the face or any other treated zone of the body.
[0214] As an example, in order to create a light-sensitive makeup
look on the upper eyelids, it is possible to carry out the
following steps: [0215] capturing the image of the face, and
deducing the eyelid zone therefrom; [0216] once the thermally
stable photochromic composition has been applied to the eyelid
zone, irradiating the pictorial model to be produced at the region
of the eyelid zone; hence, the resulting light-sensitive makeup is
formed at the correct location. Irradiation at the position of the
zone to be treated may be carried out by lighting only the
corresponding pixels, in a situation where the image is capable of
covering a much more extensive zone when all of the pixels are lit.
In order to benefit from better resolution, the treated zone may,
for example, involve at least 2/3 of the total number of pixels of
the image.
[0217] The computer may also modify the shape of the pictorial
model in order to adapt it to the shape of the face. Thus, for
example, if it is desired to make up the lips, the following steps
may be carried out: [0218] capturing the image of the face, and
deducing the zone of the lips therefrom; [0219] comparing the shape
of the lips with the pictorial model to be reproduced; [0220]
modifying the pictorial model so that it is inscribed within the
shape of the lips; [0221] once a thermally stable photochromic
composition has been applied to the lips, irradiating them to
produce the modified pictorial model. This method may also be
applied to other regions of the body.
[0222] Thus, the system for processing light-sensitive makeup may
be provided with the following four functions: [0223] capturing the
image of the face or any other region of the body to be treated;
[0224] locking the position of the pictorial model to be produced
on the portion of the face of body that is to receive it, by
analyzing the image of the face or any other part to be treated;
[0225] optionally, modifying the shape of the pictorial model to
adapt it to the shape of the face; [0226] controlling projection of
the image intended to produce the light-sensitive makeup.
[0227] The system for processing light-sensitive makeup may
comprise means for acquiring the 3D shape of the face. The system
for processing light-sensitive makeup may comprise an optical
acquisition device that is adapted to detect relief, by projecting
fringes, for example, and/or it may be adapted to detect shine.
[0228] In one exemplary embodiment of the invention, the pictorial
model used is determined automatically. This choice may be made in
a random manner or by using programmed logic that uses rules to
optimize the appearance of the face, for example to fit in with a
color harmony scheme or a natural harmony scheme for the face.
Thus, for example, for a white-skinned face, it is possible to
produce freckles.
[0229] The choice may also be made by applying logic to
re-establish symmetry for faces with asymmetries and/or by applying
light and shade to cause a face that is too angular to be rendered
rounder or vice versa, or to correct natural or unattractive
proportions.
[0230] In one exemplary embodiment of the invention, the system for
processing light-sensitive makeup proposes a plurality of pictorial
models, leaving the user at liberty to select one. These proposals
may be expressed graphically, for example by display on a screen.
The proposed pictorial model may be superimposed on an image of the
subject intended to receive the light-sensitive makeup, or the
model may be displayed on a screen describing the face by a
diagram. Any interface that allows the user to select a pictorial
model may be used. As an example, the description of a pictorial
model proposed to the user may be given verbally by describing the
actions that the system for processing light-sensitive makeup
proposes to carry out.
[0231] The system for processing light-sensitive makeup may be
configured to automatically detect a skin blemish on the zone to be
treated and the imager may be controlled as a function of the
nature of the detected blemish.
[0232] The system for processing light-sensitive makeup may be
provided with particular recognition functions intended, for
example, to recognize blemishes, for example: [0233] spots,
blackheads, pimples, strawberry spots, blotches; [0234] wrinkles,
cracks, stretch marks, veins; [0235] raised or recessed portions in
relief such as scars; [0236] asymmetries; [0237] desquamation;
[0238] matt or shiny skin; [0239] hairs.
[0240] The blemishes may be detected by image analysis and/or
relief analysis. The image analysis may be 3D image analysis. The
image analysis may include analysis of color and/or shine.
[0241] The system for processing light-sensitive makeup may also be
provided with functions that allow a pictorial model to be computed
or selected for the purpose of limiting the visibility of said
blemishes. Examples of these pictorial models that may be mentioned
are those intended to blur some portions that are detected as
having blemishes and those intended to alter the outlines of
certain parts, especially scars or asymmetries.
[0242] In another exemplary embodiment of the invention, the user
or a third person may define the pictorial model to be produced.
Thus, the user or the third person may transmit commands that are
interpreted by the system for processing light-sensitive makeup.
These commands may be graphical and the system for processing
light-sensitive makeup may comprise a man-machine interface of the
touch screen type. The user transmits makeup orders by designating,
on the image of the face or on a diagram of the face, the zones on
which a makeup line is to be produced. The system for processing
light-sensitive makeup may be configured to interpret the
instructions from the user, to adapt them to the topography of the
face, and then to create the light-sensitive makeup look.
[0243] The commands may be descriptions, for example "fill the lip
zone with red" or they may be intuitive, for example "eyelid
makeup". The system for processing light-sensitive makeup will then
act, in a conventional or a specifically programmed manner, to
interpret the default pictorial model that is to be used.
[0244] The commands may be programmed and the programs may be
personalized.
[0245] The person who selects from the proposed pictorial models or
who determines the pictorial models to be produced may be the
person who is being made up or some other person, such as a
professional makeup artist. Selection or production of the
pictorial models may be made at the location where the
light-sensitive makeup look is being created, or remotely. When
acting remotely, the system for processing light-sensitive makeup
may be provided with communications means enabling the image of the
zone for treatment to be communicated, for example the
above-mentioned network interface 14.
[0246] The system for processing light-sensitive makeup may
optionally be provided with a means for capturing makeup looks from
magazines or other media and of making pictorial models from them
that could then be reproduced on the zone to be treated, for
example a scanner or an RFID chip reader, the chip containing the
description of the makeup look or an internet link allowing it to
be downloaded. This chip could be contained in packaging containing
the composition or compositions to be used to create the
light-sensitive makeup look or be contained in an article of
clothing or other accessory with a particular pattern, which could
be reproduced with light-sensitive makeup.
[0247] The system for processing light-sensitive makeup may be
configured to display a succession of many sorts of pictorial
model, in the form of simulations, in order to allow a person to
select the model to be reproduced from among them.
[0248] The system for processing light-sensitive makeup may offer
the possibility of rapidly trying out many sorts of models,
directly on the face. Thus, the person may find out on a real
version whether the models will suit him or her. These models could
be images projected in visible light onto the face, which do not
develop the thermally stable photochromic composition, or
light-sensitive makeup looks created using a thermally stable
photochromic composition that is also erasable, for example by
irradiation with visible light.
[0249] The system for processing light-sensitive makeup may
advantageously have several pre-recorded models in its memory in
the storage means 13 and may memorize the pictorial models that it
has been able to create. In this manner, the user may use or
exchange the recorded pictorial models.
[0250] In one exemplary embodiment of the invention, once a
pictorial model has been selected, adaptation of the pictorial
model to the topography of the face of the person and creation of
the light-sensitive makeup by projecting the image are carried out
automatically. The time interval separating capture of the face and
production of the image may be rendered relatively short, for
example less than one second.
[0251] In another exemplary embodiment of the invention, the person
receiving the light-sensitive makeup or a third person may
intervene while the operations are being carried out. Creating the
makeup may then be slower than before. The system for processing
light-sensitive makeup may be configured so as to allow the person
or the third person to view the progress of the light-sensitive
makeup, for example on the screen 12, in order to slow down or stop
its progress.
[0252] The system for processing light-sensitive makeup may
optionally regularly recapture the face in order to re-commence the
operations of locking and adapting the pictorial model to the face,
thereby eliminating any problems that might be caused by movement
of the person during irradiation intended to develop the thermally
stable photochromic composition.
[0253] It is possible to create several partial light-sensitive
makeup looks in succession. Thus, during the course of creating the
light-sensitive makeup look, each pictorial model may be
determined, its effect may be estimated by eye, then the next
pictorial model may be selected and so on, thereby progressively
constructing the light-sensitive makeup.
[0254] As mentioned above, the system for processing
light-sensitive makeup may be configured to evaluate the pictorial
models that are the most adapted to a face or part of a face by
means of one or more specialized programs. Thus, the
light-sensitive makeup look may be created by producing a first
pictorial model, then by evaluating the face a second time to
deduce therefrom the new pictorial model to be produced, and so
on.
[0255] It is possible to treat one portion of the face in a
semi-automatic manner and another portion in an automatic manner.
It is also possible to treat a portion of the face in an automatic
manner up to a certain point, then to continue the light-sensitive
makeup in a semi-automatic manner, or vice versa.
[0256] The system for processing light-sensitive makeup may be
configured to take an image, for example using the above-mentioned
optical acquisition device, optionally extract a portion
corresponding to the zone to be treated, and where appropriate to
rectify this image to thereby improve the result once
projected.
[0257] The system for processing light-sensitive makeup used is
preferably configured to allow the user, starting from an image
projected on the face or any other zone to be treated, to rectify
the shape, for example by enlarging, or shrinking in one or two
dimensions. The modifications may also be more complex. Thus, for
example, it is possible to rectify a portion of the image, stretch
a particular zone, change the size of the lines, etc. For this, it
is possible to use the tools normally present in software for
producing and editing images, such as Photoshop.RTM. for example.
Where appropriate, the image may be edited by feedback via the
optical acquisition device; the computer will know the result of
the projected image and automatically modify it until the desired
result is obtained by means of the system for processing
light-sensitive makeup program executing a loop.
Creating Light-Sensitive Makeup Progressively
[0258] The light-sensitive makeup may be created by carrying out
the steps consisting in: [0259] applying a thermally stable
photochromic composition to a zone to be treated; [0260]
irradiating the zone with light selected either to progressively
develop the thermally stable photochromic composition, or else to
progressively erase the thermally stable photochromic composition;
[0261] interrupting and/or modifying the characteristics of the
irradiation when the desired appearance is achieved, this
appearance corresponding, for example, either to partial
development of the thermally stable photochromic compound, or else
to partial erasure of the thermally stable photochromic
composition.
[0262] Thus, it is easier to obtain makeup results of the intended
intensity. During progressive illumination, the user and/or the
system for processing light-sensitive makeup may monitor the
progress of the light-sensitive makeup and may stop it changing
once the desired result is achieved.
[0263] Similarly, if the thermally stable photochromic composition
allows it, editing may be carried out to further refine the
light-sensitive makeup, either at the time of light-sensitive
making up or later on.
[0264] Irradiation may be interrupted then recommenced at least
once.
[0265] The dominant wavelength and/or intensity of the irradiation
may be modified before the desired appearance is achieved. As an
example, by modifying the intensity of the irradiation, the rate of
development or erasure of the thermally stable photochromic
composition may be changed. By adjusting the dominant wavelength,
it is possible to adjust the irradiation energy and/or the effect
exerted on the photochromic agents.
[0266] The whole of the image may be treated progressively, but it
is also possible to treat the image portion-by-portion in a
progressive manner, for example in an automatic, programmed, or
programmable manner.
[0267] The light-sensitive makeup may be used to create several
patterns in succession. At least one pattern that has achieved the
desired appearance may stop being irradiated while at least one
other pattern is still being irradiated. The patterns are, for
example, freckles, which may be created in succession.
[0268] Thus, a specific program may be executed to produce
freckles, as can be seen in FIG. 13. The program may cause the
freckles to appear, via suitable progressive irradiation, either
from the center of the zone towards the outside of the zone (FIGS.
13A to 13C), or from a sparse distribution to a dense distribution
(FIGS. 14A to 14C), or from a distribution of small freckles to a
distribution of large freckles, or in a random manner (not
shown).
[0269] Irradiation may be sufficiently weak not to cause major
development in the moment following its commencement.
[0270] In order to allow sufficiently slow development, the energy
E of irradiation per second may be less than or equal to 0.5
E.sub.0, preferably 0.2 E.sub.0, where E.sub.0 is the energy
necessary per second to develop 80% of the thermally stable
photochromic composition. It is possible for E 0.2 E.sub.0. It is
considered that 80% of the thermally stable photochromic
composition has been developed when the color change .DELTA.E
compared with the non-developed state corresponds to 80% of the
maximum attainable color change.
[0271] Similarly, when it is to be erased, the energy E' of
irradiation per second may be 0.5 E'.sub.0 or less, where E'.sub.0
is the energy necessary per second to erase 80% of the thermally
stable photochromic composition. It is possible for E'.ltoreq.0.2
E'.sub.0.
[0272] The system for processing light-sensitive makeup may be
configured to analyze the color of the zone to be treated, then the
result of this analysis may serve to automatically control the
irradiation. As an example, the color may be analyzed after
application of the thermally stable photochromic composition and
before the desired appearance has been achieved. This may, for
example, allow light-sensitive making up to be stopped
automatically when the desired appearance has been achieved. The
color may, for example, be measured by analyzing the color of the
pixels of an image formed on the treated zone.
[0273] The system for processing light-sensitive makeup may be
configured to carry out an analysis of pre-defined regions of the
image and the irradiation may be controlled by adjusting the
intensity of the irradiation in the various zones observed, as a
function of the color in the corresponding regions. When the
irradiation is carried out with an addressable matrix imager, then
the irradiation in multiple pixels of the treated zone may be
monitored precisely.
[0274] The irradiation may be constant or variable. In particular,
it may be fairly strong for a given time, termed the "bring-up"
time, then be weakened for a "fine tune" phase.
[0275] The system for processing light-sensitive makeup may be
programmed to deliver the irradiation intermittently, an example
being constant irradiation followed by a stop period, for example
for a period of 30 seconds or less, and so on. The user may stop
the process when satisfied.
[0276] When the user intervenes to stop the irradiation and then
recommences it, the irradiation may be sufficiently slow to allow
the user to see the color change, the irradiation changing, for
example, at a rate of 3 or fewer units of E per second in CIE Lab
space, for example approximately 2 units of E per second.
[0277] When the intensity of the irradiation is modulatable, the
system for processing light-sensitive makeup may be provided with a
control member to adjust the speed and/or the amplitude of the
reduction or increase of the irradiation, for example a button,
sensor, joystick, voice control interface, or control pad, which
may act on the intensity of the irradiation, in particular upstream
from the imager.
[0278] Depending on the implementation of the invention, the user
may stop or throttle back the irradiation as desired in order to
consider and/or observe the result.
[0279] Provision may be made for irradiation to be carried out as a
function of the execution of an irradiation program by the system
for processing light-sensitive makeup, and the user may either
interrupt or pause the program during its execution, or change from
one program to another. The program enabling the change in the
irradiation over time to itself be defined or specified by the
user, for example in order to adjust the rate of increase or
reduction of the irradiation.
[0280] The increase or reduction of the irradiation intensity does
not necessarily cause a change in the shape or extent of the image.
Thus, in order to modulate the irradiation, it is possible to use
electrical and/or optical systems that adjust the light flux
produced, for example at least one filter, diaphragm, and/or
polarizer, and/or a device for varying the electric power in order
to control the source. The intensity of the irradiation may also
depend on the gray level of the pixels of the image.
[0281] The system for processing light-sensitive makeup may be
configured to automatically determine a progressive illumination
program as a function of the light-sensitive makeup to be produced.
As an example, if the light-sensitive makeup on a given zone
consists in producing a color with fairly low saturation, the
system for processing light-sensitive makeup may propose and/or
apply a program specifying weak illumination. If the
light-sensitive makeup on another zone consists in producing an
intense color, the system for processing light-sensitive makeup may
propose and/or apply a program consisting in illuminating more
strongly at first then illuminating less strongly, to allow the
user to fine tune the results of light-sensitive making up. The
illumination carried out initially may be carried out with a
fluence that is at least double that which is subsequently
applied.
[0282] In order to determine the intensity of the irradiation, the
system for processing light-sensitive makeup may be based on a
calculation of the dose to be applied in order to create the final
light-sensitive makeup look and to apply a rule in order to deduce
the illumination program therefrom. As an example, if it calculates
that a dose of X J is required, it could rapidly apply 80% of X
(over one second, for example) then apply the last 20% at 5% per
second, for example.
[0283] As mentioned above, the system for processing
light-sensitive makeup may be provided with an optical acquisition
device that allows the color of the skin or other keratinous
material to be measured either at the beginning of irradiation or
during light-sensitive making up. It may use this information to
compute or modulate the progressive illumination. As an example, it
may use this information in order to identify the time when
illumination needs to be reduced or stopped.
[0284] The sensor or sensors for the optical acquisition device may
be monochrome or polychrome, with monopixel or multipixel
measurement.
[0285] Information representative of the progress of
light-sensitive making up may be transmitted to the user in various
manners, for example by displaying a value representative of the
color of the light-sensitive makeup being created, or a value
representative of the degree of completion of the process, for
example as a percentage. A color representing the measured color
may also be displayed on the screen.
Backtracking
[0286] The system for processing light-sensitive makeup may act to
progressively reduce the intensity of the light-sensitive makeup,
in order to cause one or more portions of the light-sensitive
makeup to disappear or regress, by using illumination suitable for
returning the photochromic agent or agents to a non-developed
state.
[0287] In this manner, the user may retrace earlier steps and
better adjust the final result. The system for processing
light-sensitive makeup is advantageously produced so that the user
may stop the backtracking when desired, restart light-sensitive
making up, and so on.
[0288] For certain photochromic agents, for example selected from
diarylethenes and fulgides, the light-sensitive makeup may be
backtracked by replacing all or some of the UV illumination by
visible illumination, for example white light.
[0289] The system for processing light-sensitive makeup is
preferably configured so that this visible illumination extends
over at least the same surface as the UV illumination.
Case of a Thermally Stable Photochromic Composition with Multiple
Photochromic Agents
[0290] When the thermally stable photochromic composition comprises
a plurality of photochromic agents with maximum sensitivities at
respective different wavelengths, one or more of said photochromic
agents may be selectively developed by adjusting the
wavelength.
[0291] It is also possible to use a thermally stable photochromic
composition with a plurality of different photochromic agents that
are in the already-developed state and that are best erased at
respective different wavelengths. Where appropriate, these
photochromic agents may be developed by the same UV light, but have
different erasure rates in the visible region that vary as a
function of wavelength, such that by selecting wavelength, erasure
of one photochromic agent rather than another is favored.
Similarly, when the photochromic agents are capable of being
developed by UV light, they may be developed at different rates
depending on the wavelength in the UV region, and by adjusting this
UV wavelength, development of one photochromic agent may be favored
over others.
Simulation of Change of Light-Sensitive Makeup
[0292] In one exemplary embodiment of the invention, the system for
processing light-sensitive makeup is provided with a system for
simulating the change in the light-sensitive makeup look, in
addition to or replacing a system for viewing the change in the
light-sensitive makeup.
[0293] Thus, before and/or during light-sensitive making up, the
user may observe this simulation and may use this to decide whether
to slow down or stop the light-sensitive making up or even to
backtrack.
[0294] The system for processing light-sensitive makeup may be
configured to make it possible to simulate the result of
light-sensitive making up after applying the thermally stable
photochromic composition and before the desired appearance has been
achieved. The progress of the simulation may be linked to the
progress of the irradiation on the zone to be treated, whether it
acts to develop the thermally stable photochromic composition or,
on the contrary, to erase it. A simulation of the change in the
appearance of the light-sensitive makeup may be displayed on a
screen and/or projected onto the treated zone when the irradiator
used makes that possible. The simulation may be projected in a
light that does not cause the thermally stable photochromic
composition to be developed or erased, at least over a short
period, long enough for the observer to decide how to continue the
treatment.
Use of Tools
[0295] When the system for processing light-sensitive makeup
includes an electronic imager, it may be controlled as a function
of a tool manipulated by the user, the computer being able to
modify the projected image and/or the intensity of the irradiation
as a function of a movement of the tool. The tool may include a
portion to be positioned in front of or on the zone to be treated
or in front of or on a screen for viewing the zone to be treated.
The tool may also control the movement of a pointer on a screen for
viewing the zone to be treated or within the image formed on the
zone to be treated.
[0296] The system for processing light-sensitive makeup may be
configured to allow the user to control the particular zones that
are to be treated with progressive irradiation, and to this end to
make use of display means that may, for example, comprise a touch
screen via which the user may control progress of the irradiation
by pressing a particular region of the screen. More preferably, the
touch screen is sensitive to the intensity of the pressure exerted
by the user, and the system for processing light-sensitive makeup
analyzes the pressure exerted on the screen and translates that
pressure into the intensity of the light-sensitive makeup by
controlling the intensity of the light and/or the duration of
irradiation on the region corresponding to the zone to be treated.
Thus, for example, a stronger pressure exerted on the touch screen
is translated into an increased intensity of color.
[0297] In one exemplary embodiment of the invention, the system for
processing light-sensitive makeup may detect a tool placed on or in
front of the touch screen, and the user may use the tool to adjust
the light-sensitive makeup look.
[0298] As an example, the user may have several tools available,
each provided with identification means, for example a bar code or
an RFID chip, so that it is capable of being identified by the
system for processing light-sensitive makeup. When the user takes a
particular tool, it is recognized and each tool may be associated
by the system for processing light-sensitive makeup with a
particular type of makeup.
[0299] As an example, the user will have a plurality of tools
corresponding to lines of makeup that are of varying thickness
and/or varying intensities of color, or even different colors of
makeup. The user takes the selected tool and may move it over the
image on the display means in order to change the makeup look. A
makeup simulation may appear on the viewing screen and after any
required validation by the user, the makeup look appearing on the
display means may be automatically created by light-sensitive
making up performed by controlling the irradiator.
Adjustment and/or Modification of the Contents of the Image
[0300] In one exemplary embodiment of the invention, a layer of
light-sensitive makeup is developed with the same simulation image
as that projected in visible light. To this end, the system for
processing light-sensitive makeup may be configured to transmit an
image to the zone to be treated, for example the face, representing
the simulation, leaving it up to the user to lock this image on the
face, or even to modify it. Then, once the image has been correctly
adjusted and defined, the same optics or a parallel optical system
is used to transmit an image that differs from the preceding image
only in that it is formed with UV light or near UV light. In
particular, the mask, negative, or matrix of addressable pixels
used to define the image does not need to have been modified when
changing the illuminant from visible light to UV light. To this
end, a system for processing light-sensitive makeup provided with a
UV source and a visible source, is suitable for use with one or two
imagers.
[0301] If the image is obtained from a slide, it may be designed to
allow an image to be produced both with the visible source and with
an image with the UV source. To this end, the slide may be produced
with a material that filters both UV and visible light.
[0302] If the image is obtained with at least one matrix of
addressable pixels of an electronic imager, several configurations
are possible: [0303] two light sources, namely a UV source and a
visible source, and a single matrix; [0304] two light sources,
respectively UV and visible, and two matrices, respectively UV and
visible. The images are combined, for example with an X prism, or
projected from sites located either side of the treated zone;
[0305] a light source emitting both in the UV and in the visible
and a UV or visible imager with, for example, a dichroic mirror, a
movable mirror, or a filter to select the outgoing radiation;
[0306] a light source emitting both in the UV and in the visible
and two matrices, respectively for the UV and for the visible.
[0307] The projected image may be restricted to an outline or to a
few reference points. The light-sensitive makeup then created may
be inscribed within these points or this outline.
[0308] As an example, when treating the lips, two reference points
may be employed. The user applies a layer of thermally stable
photochromic composition. The two points are projected in a visible
wavelength that is incapable of producing a light-sensitive makeup
effect, for example at a wavelength in the range 450 nm to 800 nm,
and preferably in the range 500 nm to 700 nm. The user positions
these two points over the two corners of the lips. Once the
positioning has been carried out, the UV irradiation forms an image
of the lips included between these two points.
[0309] During UV illumination, the visible image may be cropped,
reduced, or limited to the reference points or left in the same
state as it was during the stage of projection in the visible.
Use of Light-Sensitive Makeup to Produce a Treatment Template on
the Face then to Use it to Treat the Zone
[0310] A photochromic agent is applied to the zone, with the
photochromic agent being selected, for example, from diarylethenes
and fulgides, so as to have thermal stability that is sufficient
for the image that is produced to hold for at least 20 seconds, and
preferably for at least 1 minute. The template may be an image
comprising points and/or reference lines, as shown in FIG. 11,
which shows the lines defining the zones A, B, and C produced by
light-sensitive making up. If necessary, an indicator is produced
in the same way, for example an alphanumeric indicator, to inform
the user about the composition and/or the applicator to be used in
this zone.
[0311] The user may create the makeup look or other treatment as a
function of the template that is thus developed. To this end, the
user may use conventional makeup tools. The user may also use the
template produced by the light-sensitive makeup to apply care
products.
[0312] As an example, a diagnosis is carried out of zones requiring
particular care, for example by image analysis and/or using one or
more sensors that are sensitive to the condition of the skin, for
example, and a map is produced of the treatment to be carried out,
which map may be stored. Next, the system for processing
light-sensitive makeup is used to cause a template to appear on the
face where the zones requiring care are developed in color, at
least temporarily. The user may then apply the care product or
products to the zones that have been shown up.
Positioning of Reference Points on the Face, then Use of an
Appliance Recognizing Said Points and Serving to Create the Makeup
Look
[0313] The user may position reference points on the face by
light-sensitive makeup.
[0314] Once the reference points have been placed on the zone to be
treated, an appliance provided with means for reading the reference
points may be used; it is preferably also capable of interpreting
them if necessary. In one implementation, the appliance may be
provided with a multipixel sensor, internal lighting, and
applicator means, for example an inkjet printing head.
[0315] The points represent a line, for example. The user moves the
appliance over the skin, which appliance is configured to analyze
the surface optically. As an example, assuming that the zone to be
treated is defined by a closed outline, when the appliance
determines that it crosses a line a first time, it starts to
deposit a colored material, then when it crosses a line a second
time, it stops depositing the colored material.
[0316] When they are connected, the points may represent a shape.
The appliance may be provided with means that may recognize these
points and the corresponding shape. The appliance may deposit a
colored material in order to produce this shape. To this end, the
appliance may start from a model that it causes to coincide with
the points by carrying out geometrical corrections.
[0317] The deposited colored material may define a curve or a
surface inscribed within a curve.
[0318] The curvature of the line and/or the surface may be
homogeneous, randomly heterogeneous, or geometrically
heterogeneous, i.e. comprising a repeating pattern.
[0319] The points present on the zone to be treated may define a
code. The appliance may be provided with means for interpreting the
code corresponding to these points, and for applying a composition
that is selected and/or applied in a manner that depends on the
recognized code.
[0320] As an example, certain points are formed with a first
pattern and others with a different pattern. The appliance applies
two different compositions or the same composition in different
concentrations as a function of the pattern that is detected.
Photoprotective Composition
[0321] As disclosed above, a photoprotective composition may be
applied to the thermally stable photochromic composition once the
desired appearance has been achieved. This photoprotective
composition may act as a screen to UV radiation when the
irradiation that is used to develop the thermally stable
photochromic composition is UV irradiation.
[0322] If necessary, the photoprotective composition may also act
as a screen at least one predefined wavelength in the visible, with
a view to limiting the risk of erasing a photochromic agent, where
appropriate.
[0323] One or more optical agents may be used that provide the
photochromic composition with a screening power F for solar
radiation (290 nm to 400 nm) in the range 2 to 20, preferably in
the range 4 to 10.
[0324] Where appropriate, the photoprotective composition may be a
glossing composition, an oily or emollient composition, a
mattifying composition, a cream blusher, a powder blusher, a
polish, or a finishing composition.
Optical Agents
Optical Agents Forming a Screen to Radiation Serving for
Development, in Particular UV or Near UV
[0325] The optical agent or agents mentioned above may be selected
from screens and diffusing particles or other agents limiting the
transmission of UV, especially UVA and/or UVB.
[0326] This or these optical agents may be selected from inorganic
screens, in particular in particulate form and on a nanometric
scale, and organic screens.
[0327] The optical agent or agents may be hydrophilic or
lipophilic.
[0328] The organic filters may be selected from anthranilate
derivatives, cinnamic derivatives, salicylic derivatives, camphor
derivatives, benzimidazole derivatives, benzotriazole derivatives,
benzalmalonate derivatives, imidazolines, bis-benzoazolyl
derivatives, benzoxazole derivatives, triazine derivatives,
benzophenone derivatives, dibenzoylmethane derivatives, beta
diphenylacrylate derivatives, p-aminobenzoic derivatives, polymer
screens and silicone screens described in application WO 93/04665,
dimers derived from alpha-alkylstyrene, 4,4-diarylbutadienes, and
mixtures thereof.
[0329] The hydrophilic screens may be selected from those described
in the application EP-A-0 678 292, for example 3-benzylidene
2-camphor, especially Mexoryl SX.RTM..
[0330] Examples of lipophilic screens that may be mentioned are
dibenzoylmethane derivatives, described in publications FR-A-2 326
405, FR-A-2 440 933, EP-A-0 114 607, Parsol.RTM. 1789 from
Givaudan, Eusolex from Merck. It is also possible to mention
2-ethylhexyl a-cyano-b, b-diphenylacrylate, known as octocrylene
and available under the trade name Uvinul N 539 from BASF.
[0331] It is also possible to mention p-methylbenzylidene camphor,
sold under the trade name Eusolex EX 6300 by Merck.
[0332] A screen selected from the following may also be used as the
optical agent: benzophenone-3 (oxybenzone), benzophenone-4
(sulisobenzone), benzophenone-8 (dioxybenzone),
bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT or Tinosorb
S), diethylamino hydroxybenzoyl hexyl benzoate (Uvinul +),
ethylhexyl methoxycinnamate, ethylhexyl salicylate, ethylhexyl
triazone, methyl anthranilate (meradimate), (4-)methyl-benzylidene
camphor (Parsol 5000), methylene bis-benzotriazolyl
tetramethylbutylphenol (Tinosorb M), para-aminobenzoic acid (PABA),
phenylbenzimidazole sulfonic acid (Ensulizole), polysilicone 15
(Parsol SLX), triethanolamine salicylate.
[0333] The optical agent used may also be formed by diffusing
particles such as titanium or zinc oxide nanopigments that are
suitable for use as a screen, with various surface treatments
depending on the selected medium. The nanopigments have a typical
mean dimension of 5 nm to 1000 nm.
[0334] The total concentration by weight of said optical agent(s)
may lie in the range 0.001% to 30%, or even more with dry or
near-dry formulas, relative to the weight of the photoprotective
composition prior to application.
[0335] Preferably, screens or combinations are used in the
composition that acts as a screen to radiation in the range from
320 nm to 400 nm, preferably in the range 320 nm to 420 nm.
Optical Agents Intended to Limit the Propagation of Visible and
Infrared Light Towards the Photochromic Agent or Agents
[0336] Although the optical agents acting as a screen to UV
radiation serve to protect the non-developed zones, when using a
thermally stable photochromic composition capable of being
developed by UV irradiation, one or more optical agents that screen
in the visible may also be applied to the thermally stable
photochromic composition in order to protect the developed zones,
and it may be advantageous to combine the two, namely screening in
the UV and screening in the visible.
[0337] Many coloring agents or pigments may be used. In particular,
it is preferred to use coloring agents with a color close to that
of the skin, for example yellow coloring agents, orange coloring
agents or mixtures that enable yellow, orange, ochre, brown, or
chestnut hues to be produced or even red coloring agents that are
preferably used either in small quantities or else mixed with a
white or yellow diffusing agent, for example, to give the hue a
pastel appearance such as pink or beige-pink. It is preferable to
use coloring agent with a slightly pink hue for white skin, a
slightly yellow hue for white skin, and chestnut or brown hues for
skins that are termed black.
[0338] Alone or as a mixture, the coloring agents may have
chromaticity close to that of the skin. They preferably have chroma
C* (in the HVC* system) of less than 40.
[0339] The coloring agent or coloring agents may be selected from:
[0340] yellow pigments codified in the Color index with references
CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005;
[0341] orange pigments codified in the Color Index with references
CI 11725, 15510, 45370, 71105; and [0342] red pigments codified in
the Color Index with references CI 12085, 12120, 12370, 12420,
12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865,
15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470.
[0343] In the photoprotective composition, pigment pastes of
organic pigment may be used, such as the products sold by HOECHST
with trade names: [0344] JAUNE COSMENYL IOG: Pigment 5 t YELLOW 3
(CI 11710); [0345] JAUNE COSMENYL G: Pigment YELLOW 1 (CI 11680);
[0346] ORANGE COSMENYL GR: Pigment ORANGE 43 (CI 71105).
[0347] Lakes may be used, in particular those known by the
denominations D & C Red 21 (CI 45 380), D & C Orange 5 (CI
45370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45
425), D & C Red 3 (CI 45 430), D & C Red 7 (CI 15 850:1), D
& C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C
Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C
Yellow 10 (CI 77 002).
[0348] The coloring agents may be ionic or neutral.
[0349] Natural coloring agents and pigments are particularly
advantageous since they combine well with natural complexions and
some of them lose their color over time. They are, for example,
extracts from plants or natural molecules that have been
artificially reproduced, being selected, for example, from
melanine, anthocyans, polyphenols, porphyrins, and curcumin.
[0350] They may, for example, be pigments obtained by oxidation
polymerization of indole and/or phenol derivatives, such as those
described in the publication FR-2 679 771.
[0351] Coloring agents and pigments with an ionic nature that
complements UV screens are particularly advantageous, for example
coloring agents with an anionic function, such as certain food
coloring agents and cationic filters.
[0352] It is also possible to use IR filters or compounds that, on
reacting, become colored, for example DHA.
[0353] It is also possible to use a color-change colorant, for
example a coloring agent of color that develops over time, if
possible slowly, for example DHA or polyphenols, which tend to
become progressively colored in contact with air. This enables the
screening power of the photoprotective composition to develop
progressively.
Thermally Unstable Photochromic Agents
[0354] The optical agent used in the photoprotective composition
may be a thermally unstable photochromic coloration agent. This
does not serve to create the light-sensitive makeup look, but
rather to protect it in the event of exposure to too intense a
light, for example in very strong sunshine or an artificial effect
such as the illumination used in television studios, certain
medical treatments, certain cosmetic treatments such as tanning
booths, for example, flash photography, or certain festive
venues.
[0355] The thermally unstable photochromic agent takes on its color
during very intense illumination and, in a certain manner, it may
limit the visibility of the underlying light-sensitive makeup.
However, since the thermally unstable photochromic agent rapidly
regains its colorless form once the very intense illumination has
been stopped, this phenomenon is transient.
[0356] Preferably, thermally unstable photochromic agents are used
that lose at least half of their color in 60 seconds at 25.degree.
C. in darkness. In particular, inorganic thermally unstable
photochromic agents are preferred.
Optical Agents that are Capable of Reflecting Incident Light
[0357] The optical agent used, in particular in order to attenuate
UV or visible light, may be an optical agent forming a metal mirror
or an optical agent based on a multilayer interfering structure or
a diffraction grating.
[0358] The optical agents that are suitable for use alone or as a
complement to the optical agents listed above are optical agents
that are capable of reflecting incident light. The reflection
occurs at the interface between the reflective layer and the
propagation medium for the light wave. The material forming the
reflective layer may have a refractive index of more than 1.5, if
possible more than 1.8.
[0359] The optical agent may contain or be formed by a metal. As an
example, a layer of silver is formed on applying the
photoprotective composition by reducing a silver salt or by
applying a dispersion of silver nanoparticles.
[0360] The degree of reflection of the photoprotective composition
may be more than 5%, and if possible more than 10%. Preferably, it
is less than 50%, in order not to vitiate the light-sensitive
makeup results. As an example, the photoprotective composition may
comprise a dispersion, which is either aqueous or ethanolic, of
nanoparticles of silver, for example those from Nippon Paint that
have a dimension of 10 nm to 60 nm depending on the sample and that
are stabilized by a polymeric system. On drying, this stabilization
does not prevent the particles from coming into contact and by
means of these contacts of ensuring sufficient electrical
conductivity to provide the final material with a reflective power
close to that obtained with a silver mirror.
[0361] It is possible to use an optical agent comprising a
multilayer interference structure.
[0362] This interference structure filters light by means of a
phenomenon of destructive interference between the light waves
reflected by the various layers of the structure.
[0363] The multilayer structure is preferably selected so as to
have a high transmission factor in the visible, so that it does not
produce a marked color in the visible and so that it has the
desired transparency.
[0364] The multilayer structure may comprise alternating layers of
low and high refractive indices. By way of example, the refractive
index difference between the layers of high and low index is 0.1 or
more, preferably 0.15 or more, more preferably 0.6 or more.
[0365] The number of layers in the above-mentioned multi-layer
structure is preferably at least 2, more preferably 4 or 6, or even
at least 12, which facilitates the production of a structure that
is less sensitive to incident light and that presents the required
selectivity. The multilayer structure may optionally be symmetrical
and allow filtering of incident light irrespective of which is the
principal face for light to enter the structure, as
appropriate.
[0366] The material with a high refractive index may be mineral,
for example titanium dioxide in the anatase or rutile form, an iron
oxide, zirconium dioxide, zinc oxide, zinc sulfide, bismuth
oxychloride, and mixtures thereof, or organic, being selected, for
example, from: PEEK (polyetheretherketone), polyimide, PVN
(poly(2-vinylnaphthalene)), PVK (poly(N-vinyl carbazole)), PF
(phenolformaldehyde resin), PSU (polysulfone resin), PaMes
(poly(alpha-methylstyrene)), PVDC, (poly(vinylidene chloride)),
MeOS (poly(4-methoxystyrene)), PS (polystyrene), BPA, (bisphenol-A
polycarbonate), PC (polycarbonate resin), PVB (poly(vinyl
benzoate)), PET (poly(ethyleneterephthalate)), PDAP (poly(diallyl
phthalate)), PPhMA (poly(phenylmethacrylate)), SAN
(styrene/acrylonitrile copolymer), HDPE (high density
polyethylene), PVC (poly(vinyl chloride)), NYLON.RTM., POM
(poly(oxymethylene) or polyformaldehyde), PMA (poly(methyl
acrylate)), etc., and mixtures thereof.
[0367] The material with a low refractive index may be a mineral,
for example selected from silicon dioxide, magnesium fluoride,
aluminum oxide and mixtures thereof, or organic, for example
selected from polymers such as polymethyl methacrylate or
polystyrene, polyurethane and mixtures thereof.
[0368] In order produce the interference particles with a
multilayer structure, the skilled person will in particular make
reference to the many publications that deal with thin layer
deposition, for example the article "Overcoated Microspheres for
Specific Optical Powers" from the review Applied Optics, Vol. 41,
n.degree. 6 dated Jan. 6, 2002, incorporated herein by reference,
and to patents in the name of FLEXPRODUCTS.
[0369] The optical agent may comprise a diffracting structure, for
example at least one diffraction grating, which may be a grating
comprising a substantially repeating surface pattern so as to
diffract light.
[0370] The period of the grating, and possibly its depth, determine
the diffraction properties of the grating, inter alia. The mark
space ratio of the diffraction grating may be selected to be
unity.
[0371] Preferably, the period of the diffraction grating in at
least one direction is advantageously sufficiently low to reduce
the risk of creating colored effects in the photoprotective
composition. The period of the grating is then advantageously
selected so as not to diffract light in the visible region,
especially in the range from 400 nm to 780 nm.
[0372] The maximum period of the grating serving to avoid
diffraction orders in the visible may be determined at least
approximately by the relationship:
n 1 sin .theta. + m .lamda. .LAMBDA. = n 2 sin .PSI.
##EQU00004##
where .theta. is the angle of incidence measured relative to the
normal to the plane of the grating, .PSI. is the transmission
angle, .LAMBDA. is the period of the grating, m is diffraction
order, and n.sub.1 and n.sub.2 are the refractive indices of the
media in incidence and transmission respectively. n.sub.1 and
n.sub.2 may be taken to be 1.5 to a first approximation. For
.theta.=0.degree., the maximum period is .lamda./n.sub.1=400/1.5
i.e. approximately 267 nm. Without limitation to the angle of
incidence, the period is less than half. Thus, preferably, a period
for the grating of 270 nm or less is selected, preferably 140 nm or
less.
[0373] The depth d of the grating and its period .LAMBDA. may be
selected by successive tests in order to obtain a transmission
minimum in the UVA, for example. Computation of the characteristics
of the grating may be carried out vectorially, e.g. using the
GSOLVER software from the GRATING SOLVER DEVELOPMENT COMPANY.
[0374] The layer or various layers used to produce the diffraction
gratings may optionally be deposited on a substrate of an organic
or inorganic nature, which substrate may be used as is or may then
undergo a dissolution treatment.
[0375] The structure of the grating or gratings may thus be etched
either into the bulk of a material, or else after depositing a
material onto an organic or inorganic substrate that is spherical
or lamellar in shape.
[0376] Etching may be carried out so that diffraction of the light
in the visible region is minimized, in order to reduce color
effects. The periodicity of the etching and its thickness determine
the efficiency of the system in attenuating UV radiation.
[0377] The interference filter agent may optionally comprise two
diffraction gratings extending in non-parallel directions, for
example two substantially perpendicular directions, which gratings
may in particular increase absorption in the UV of circularly
polarized incident light and reduce the dependency of the screening
performance of the filter angle of incidence.
[0378] The two diffraction gratings may have periods .LAMBDA..sub.1
and .LAMBDA..sub.2 that are substantially equal; in particular,
both are 270 nm or less, preferably 140 nm or less.
[0379] The depths of the two diffraction gratings may also be
substantially equal when they have surface relief, and that relief
may create the periodic variation of the index of the grating.
[0380] The period of the grating may be constant or varying and the
depth may be constant or varying. The grating may extend in a
rectilinear or curvilinear direction.
[0381] The diffraction grating may comprise superimposed layers
having different refractive indices. The diffraction grating may be
produced at least partially from a dielectric material.
[0382] Various patterns may be used for the grating or gratings;
they may, for example, have rectangular or triangular crenellations
in section, or sinusoidal undulations, or stepped
crenellations.
[0383] The diffracting structure may be formed over at least a
portion of a principal face of the particle, preferably over the
two principal faces of the particle.
[0384] The diffracting structure may comprise a protective and
non-diffracting layer covering the grating or gratings.
[0385] Pigments having an interference effect and that are not
fastened to a substrate may also be mentioned, such as liquid
crystals (Helicones HC from Wacker), as well as interference
holographic flakes (Geometric Pigments or Spectra f/x from
Spectratrek).
[0386] The composition may comprise a mixture of interference
elements for screening UVA and/or UVB, for example particles having
diffraction gratings with different periods and/or depths.
Optical Agents Capable of Transforming the Wavelength of Incident
Light
[0387] The photoprotective composition may include a fluorescent
compound.
[0388] The term "fluorescent" compound means a compound that
absorbs light in the ultraviolet spectrum and possibly in the
visible and that transforms the absorbed energy into fluorescent
light with a longer wavelength emitted in the ultraviolet or
visible part of the spectrum.
[0389] The compound may be an optical brightener that may be
transparent and colorless, not absorbing visible light but only in
the UV and transforming the absorbed energy into fluorescent light
at a longer wavelength, for example 20 nm longer, or preferably 50
nm longer, or even 100 nm longer, that is emitted in the visible
part of the spectrum; the color impression generated by said
brighteners may thus be generated solely by predominantly blue
purely fluorescent light with wavelengths of 400 nm to 500 nm.
[0390] Said compounds may be in solution or particulate.
[0391] The fluorescent compound may be a diketopyrrolopyrrole with
formula:
##STR00012##
in which R.sub.1, R.sub.2, R.sub.3 and R.sub.4, independently of
each other, represent a hydrogen atom; a halogen atom; a
C.sub.6-C.sub.30 aryl group; a hydroxyl group; a cyano group; a
nitro group; a sulfo group; an amino group; an acylamino group; a
di (C.sub.1-C.sub.6)alkylamino group; a dihydroxy
(C.sub.1-C.sub.6)alkylamino group; a
(C.sub.1-C.sub.6)alkylhydroxy(C.sub.1-C.sub.6)alkylamino group; a
(C.sub.1-C.sub.6)alkoxy group; a (C.sub.1-C.sub.6) alkoxy carbonyl
group; a (C.sub.1-C.sub.6)carboxyalkoxy group; a piperidinosulfonyl
group; a pyrrolidino group; an (C.sub.1-C.sub.6)alkylhalogeno
(C.sub.1-C.sub.6)alkylamino group; a benzoyl(C.sub.1-C.sub.6)alkyl
group; a vinyl group; a formyl group; a C.sub.6-C.sub.30 aryl
radical that may be substituted with one or more groups selected
from hydroxyl, linear, branched or cyclic C.sub.1-C.sub.6 alkoxy,
linear, branched or cyclic alkyl containing 1 to 22 carbon atoms
itself optionally being substituted with one or more hydroxyl,
amino, C.sub.1-C.sub.6 alkoxy groups; a linear, branched or cyclic
alkyl radical containing 1 to 22 carbon atoms, optionally
substituted with one or more groups selected from hydroxyl, amino,
linear, branched or cyclic C.sub.1-C.sub.6 alkoxy groups,
optionally substituted aryl, carboxyl, sulfo groups, a halogen
atom, said alkyl radical possibly being interrupted by a
heteroatom.
[0392] The fluorescent compound may be a naphthalimide, with
formula:
##STR00013##
where
[0393] R.sub.1, R.sub.2, R.sub.3, independently of each other,
represent a hydrogen atom; a halogen atom; a C.sub.6-C.sub.30 aryl
group; a hydroxyl group; a cyano group; a nitro group; a sulfo
group; an amino group; an acylamino group; a
di(C.sub.1-C.sub.6)alkylamino group, a
dihydroxy(C.sub.1-C.sub.6)alkylamino group; a
(C.sub.1-C.sub.6)alkylhydroxy(C.sub.1-C.sub.6)alkylamino group; a
(C.sub.1-C.sub.6) alkoxy group; a (C.sub.1-C.sub.6)alkoxycarbonyl
group; a C.sub.1-C.sub.6 carboxyalkoxy group; a piperidinosulfonyl
group; a pyrrolidino group; a
(C.sub.1-C.sub.6)alkylhalogeno(C.sub.1-C.sub.6)alkylamino group; a
benzoyl(C.sub.1-C.sub.6)alkyl group; a vinyl group; a formyl group;
a C.sub.6-C.sub.30 aryl radical optionally substituted with one or
more groups selected from hydroxyl groups, linear, branched or
cyclic C.sub.1-C.sub.6 alkoxy, linear, branched or cyclic alkyl
containing 1 to 22 carbon atoms itself optionally being substituted
with one or more hydroxyl, amino, C.sub.1-C.sub.6 alkoxy groups; a
linear, branched or cyclic alkyl radical containing 1 to 22 carbon
atoms, optionally substituted with one or more groups selected from
hydroxyl, amino, linear, branched or cyclic C.sub.1-C.sub.6 alkoxy,
optionally substituted aryl, carboxy, sulfo, a halogen atom, these
5 alkyl radicals possibly being interrupted by a heteroatom; the
substituents R.sub.1, R.sub.2 and R.sub.3 with the carbon atoms to
which they are attached may form an aromatic or non-aromatic
C.sub.6-C.sub.30 or heterocyclic cycle comprising a total of 5 to
30 links and 1 to 5 heteroatoms; said cycles may optionally be
condensed, may optionally have a carbonyl group inserted, and being
substituted or not substituted with one or more groups selected
from C.sub.1-C.sub.4 alkyl groups,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl, amino, di
(C.sub.1-C.sub.4)alkylamino, halogen, phenyl, carboxy, and
tri(C.sub.1-C.sub.4)alkylammonio(C.sub.1-C.sub.4)alkyl.
[0394] The fluorescent compound may be a stilbene derivative such
as
##STR00014##
in which formula R represents a methyl or ethyl radical; R'
represents a methyl radical, X-- represents a chloride, iodide,
sulfate, methosulfate, acetate, perchlorate type anion.
[0395] An example of a compound of this type that may be mentioned
is Photosensitizing Dye NK-557 sold by UBICHEM, where R represents
an ethyl radical, R' a methyl radical and X-- an iodide.
[0396] The fluorescent compound may be a methyne derivative such
as:
##STR00015##
or an oxazine or thiazine derivative with general formula:
##STR00016##
[0397] It is also possible to mention dicyanopyrazine derivatives
(from Nippon Paint), naphtholactams, azalactone derivatives,
rhodamines, and xanthenes.
[0398] It is also possible to use mineral (MgO, TiO.sub.2, ZnO,
Ca(OH).sub.2, etc) or organic (latex, etc) pigments or particles
comprising said compounds at their core or on their surface.
[0399] The fluorescent compound may also be a semiconductor
compound that has a fluorescent effect, for example in the form of
small particles termed quantum dots.
[0400] Quantum dots are luminescent semiconductor nanoparticles
that, under light excitation, are capable of emitting radiation at
a Wavelength in the range 400 nm to 700 nm. These nanoparticles may
be fabricated in accordance with the methods described, for
example, in patents U.S. Pat. No. 6,225,198 or U.S. Pat. No.
5,990,479, in the publications cited therein, and also in the
following publications: Dabboussi B. O. et al "(CdSe)ZnS core-shell
quantum dots: synthesis and characterization of a size series of
highly luminescent nanocrystallites" Journal of Physical Chemistry
B, vol 101, 1997, pp 9463-9475, and Peng, Xiaogang et al,
"Epitaxial Growth of Highly Luminescent CdSe/CdS Core/shell
Nanocrystals with Photostability and Electronic Accessibility"
Journal of the American Chemical Society, vol 119, N.degree.30, pp
7019-7029.
[0401] Preferred fluorescent compounds are those emitting orangey
and yellow colors, for example.
[0402] Preferably, the fluorescent compound or compounds used as
optical agents in the invention have a maximum reflectance in the
wavelength range of 500 nm to 650 nm, preferably in the wavelength
range from 550 nanometers to 620 nanometers.
[0403] Examples of fluorescent compounds are those belonging to the
following families: naphthalimides; cationic or non-cationic
coumarins; xantheno-diquinolizines (such as sulforhodamines in
particular); azaxanthenes; naphtholactams; azlactones; oxazines;
thiazines; dioxazines; azo, azomethinic or methinic type
fluorescent polycationic coloring agents, used alone or as a
mixture.
[0404] More particularly, the following may be mentioned: [0405]
Jaune Brilliant B6GL sold by SANDOZ and with the following
structure:
[0405] ##STR00017## [0406] Basic Yellow 2, or Auramine O sold by
PROLABO, ALDRICH or CARLO ERBA, with the following structure:
##STR00018##
[0407] The fluorescent compounds used may be aminophenyl ethenyl
aryl compounds, in which the aryl is a pyridinium, which may
optionally be substituted, or another cationic group such as an
imidizolinium, which may optionally be substituted.
[0408] As an example, a fluorescent compound may be used such as
2-[2-(4-dialkylamino)phenyl ethenyl]-1 alkylpyridinium, in which
the alkyl radical of the pyridinium nucleus represents a methyl or
ethyl radical; while that of the benzene ring represents a methyl
radical.
[0409] An optical agent may contain several fluorescent groups on
the same molecule. Examples are dimers such as:
##STR00019##
where R.sub.1 and R.sub.2, which may be identical or different,
represent: [0410] a hydrogen atom; [0411] a linear or branched
alkyl radical containing 1 to 10 carbon atoms, preferably 1 to 4
carbon atoms, optionally interrupted and/or substituted with at
least one heteroatom and/or group comprising at least one
heteroatom and/or substituted with at least one halogen atom;
[0412] an aryl or arylalkyl radical, the aryl group containing 6
carbon atoms and the alkyl radical containing 1 to 4 carbon atoms;
the aryl radical optionally being substituted with one or more
linear or branched alkyl radicals containing 1 to 4 carbon atoms,
optionally interrupted and/or substituted with at least one
heteroatom and/or group comprising at least one heteroatom and/or
substituted with at least one halogen atom; [0413] R.sub.1 and
R.sub.2 may optionally be linked in order to form a heterocycle
with the nitrogen atom and comprise one or more other heteroatoms,
the heterocycle optionally being substituted with at least one
linear or branched alkyl radical preferably containing 1 to 4
carbon atoms and optionally being interrupted and/or substituted
with at least one heteroatom and/or group comprising at least one
heteroatom and/or substituted with at least one halogen atom;
[0414] R.sub.1 or R.sub.2 may optionally be engaged in a
heterocycle comprising the nitrogen atom and one of the carbon
atoms of the phenyl group carrying said nitrogen atom; [0415]
R.sub.3, R.sub.4, which may optionally be identical, represent a
hydrogen atom, or an alkyl radical containing 1 to 4 carbon atoms;
[0416] the R.sub.5 moieties, which may optionally be identical,
represent a hydrogen atom, a halogen atom, or a linear or branched
alkyl radical containing 1 to 4 carbon atoms, optionally
interrupted by at least one heteroatom; and [0417] the R.sub.6
moieties, which may optionally be identical, represent a hydrogen
atom; a halogen atom; a linear or branched alkyl radical containing
1 to 4 carbon atoms, optionally substituted with and/or interrupted
by at least one heteroatom and/or a group carrying at least one
heteroatom and/or substituted with at least one halogen atom.
[0418] X represents: [0419] a linear or branched alkyl radical
containing 1 to 14 carbon atoms, or an alkenyl radical containing 2
to 14 carbon atoms, optionally interrupted by and/or substituted
with at least one heteroatom and/or group comprising at least one
heteroatom and/or substituted with at least one halogen atom;
[0420] a heterocyclic radical comprising 5 or 6 links, optionally
substituted with at least one linear or branched alkyl radical
containing 1 to 14 carbon atoms, optionally substituted with at
least one heteroatom; with at least one linear or branched
aminoalkyl radical containing 1 to 4 carbon atoms, optionally
substituted with at least one heteroatom; or with at least one
halogen atom; [0421] an aromatic or diaromatic radical, which may
optionally be condensed, separated or not separated by an alkyl
radical containing 1 to 4 carbon atoms, the aryl radical or
radicals optionally being substituted with at least one halogen
atom or with at least one alkyl radical containing 1 to 10 carbon
atoms optionally substituted with and/or interrupted by at least
one heteroatom and/or group carrying at least one heteroatom;
[0422] a dicarbonyl radical; [0423] the group X possibly carrying
one or more cationic charges; and [0424] a being equal to 0 or
1.
[0425] The Y-- moieties, which may optionally be identical,
represent an organic or mineral anion, with n being a whole number
equal to at least 2 and at most the number of cationic charges
present in the fluorescent compound.
[0426] Other dimers are possible, such as those in which the
attachment point is formed between the two non-cationic groups or,
for example those in which the pyridinium group is replaced by
another arylcationic group such as an imidazolinium group.
[0427] The dicyanopyrazine family may also supply compounds that
fluoresce in the orange and are of interest to the invention.
[0428] Pigments that fluoresce in the orange may also be used. An
example is the Sunbrite-SG2515 yellow orange pigment sold by
SunChemical.
Application of the Photoprotective Composition
[0429] The user may apply the photoprotective composition to the
whole of the treated zone, spreading the layer of thermally stable
photochromic composition generously or, on the contrary, in a
localized manner over only certain zones, as illustrated in FIG.
12. In this figure, the light-sensitive makeup has been created
with a thermally stable photochromic composition PC completely
covered by the photoprotective composition PP. The photoprotective
composition may, for example, be localized to the edges of the zone
coated with the thermally stable photochromic composition, thereby
surrounding the light-sensitive makeup patterns when the
light-sensitive makeup is less extensive than the layer of
thermally stable photochromic composition.
[0430] The photoprotective composition layer may also take the form
of a flexible film to be bonded to the keratinous material, for
example the skin. The substance of the film may act as an optical
agent and/or the film may contain at least one optical agent
dispersed in the substance of the film. The film may also carry a
coating containing the optical agent, for example in the form of an
impression or a multilayer interference structure.
[0431] The user may apply said film over the whole of the thermally
stable photochromic composition layer, or could cut the film to
cover only the non-developed zones, not covering the developed
zones.
[0432] An automatic cutting system may be used that, starting from
the content of the light-sensitive makeup, e.g. its contour, cuts
the protective film to the suitable shape. The user then places the
cut protective film over the non-developed zones.
[0433] In another exemplary embodiment of the invention, the
photoprotective composition is deposited by transfer, by applying a
support sheet carrying at least one optical agent to the zone to be
treated. The user brings the sheet into contact with the keratinous
material coated with the thermally stable photochromic composition
and then uses friction or other means such as heat or a solvent to
cause the optical agent or agents to be transferred onto the
thermally stable photochromic composition layer.
[0434] In one exemplary embodiment of the invention, the
photoprotective composition layer is reversible, i.e. it is
possible for the user to remove it without removing the first layer
of thermally stable photochromic composition.
[0435] To this end, the first layer may be formulated so that it is
water-resistant or resistant to a mixture of water and surfactant,
and the second layer may be formulated so that it is not
water-resistant or resistant to a mixture of water and
surfactant.
[0436] It is also possible to produce a peelable second layer. To
this end, a second layer may be used, forming a cohesive coating
before or after application to the first layer. The second layer,
when it is peelable, comprises an elastomeric material, for
example.
[0437] In one exemplary embodiment of the invention, the second
layer is less adherent to the first layer, for example by the
thermally stable photochromic composition making use of low surface
tension compounds such as silicone or fluorinated compounds. In
another exemplary embodiment of the invention, an intermediate
non-stick layer is interposed between the first and the second
layer, facilitating removal of the photoprotective composition
layer.
[0438] Particularly when it is reversible, the photoprotective
composition layer may have a very high screening power F, for
example 20 or more.
[0439] A single layer containing the optical agent or agents or
several layers containing several different optical agents may be
deposited.
[0440] As an example, a single layer may be deposited that ensures
that the thermally stable photochromic layer is protected from UV
and visible light.
[0441] It is also possible to deposit a specific UV protective
layer and an additional layer for additional protection in the UV
and/or in the visible, said additional layer comprising a coloring
agent or a thermally unstable photochromic agent, for example.
[0442] It is also possible to use one UV protective layer and an
additional layer comprising a fluorescent compound ensuring
additional protection in the UV.
[0443] In a particular possibility, there is applied a multilayer
film, comprising a first layer of thermally stable photochromic
composition and a second layer that is photoprotective comprising
an optical agent forming a screen against the development radiation
for the thermally stable photochromic composition. This film may be
self-supporting or it may be applied by transfer.
[0444] The thermally stable photochromic composition may be applied
as is to the keratinous material, or it may be on a base layer, in
particular a base layer as defined below.
[0445] The second composition may be applied directly to the
thermally stable photochromic composition layer or to an
intermediate layer between the two, as mentioned above. The second
composition may itself be coated with an additional layer where
appropriate.
Choice of Ingredients for the Various Layers
[0446] In one exemplary embodiment of the invention, two
successively applied layers, for example the layer of thermally
stable photochromic composition and the layer of photoprotective
composition, or the base layer and the layer of thermally stable
photochromic composition, or the layer of thermally stable
photochromic and the layer intended to form a material protecting
the light-sensitive makeup, may be physically complementary,
allowing or facilitating the second layer to grip onto the first
and/or allowing or facilitating spreading of the second layer on
the first.
[0447] It may be advantageous for there to be ionic natures that
are complementary. Thus, for example, the first layer may contain
an anionic polymer and the second then contains a cationic
compound, for example a cationic filter, a cationic coloring agent
or a cationic fluorescent compound. The opposite is also
possible.
[0448] It may also be advantageous for the surface tensions to be
complementary. Thus, the first layer may have a first surface
tension of preferably more than 40 mN.m.sup.-1 [millinewton per
meter], for example by using at least one hydrophilic polymer. The
second layer may have a lower second surface tension than the
first, preferably less than 40, for example by using a mainly oily,
silicone, or fluorinated composition, or by using an aqueous
composition into which one or more surfactants has been
introduced.
[0449] The ingredients (solvents, adhesives, etc) for the second
layer may be selected so that they are not solvents of the
first.
[0450] As an example, an organic solvent (ethanol, acetone, alkyl
acetate, carbonaceous oils (for example isododecane), volatile
silicones) may be selected for the first layer and an aqueous or
hydroalcoholic solvent may be selected for the second layer, or
vice versa.
[0451] It is also possible to select two organic solvents or two
aqueous solvents for the two layers, provided that, on drying the
first layer, a transformation takes place. As an example, a first
layer containing a latex is used. On drying, the latex coalesces
and renders the first layer inert to application of the second
layer. It is also possible to use a first layer containing a low
hydrosolubility acrylic/acrylate copolymer rendered hydrosoluble by
neutralization with a volatile base such as ammonia. After drying
the first layer, the ammonia will evaporate and render the first
layer water-resistant.
Base Layer
[0452] A base layer of a photoprotective first composition may be
applied to the keratinous material, the base layer containing at
least one optical agent that is capable, at least temporarily, of
forming a screen at a wavelength .lamda., especially a wavelength
within the range 320 nm to 440 nm, and said base layer may have a
thermally stable photochromic second composition applied thereto
that is capable of being developed by exposure at least to
radiation of wavelength .lamda.; the optical agent or agents may be
selected from those indicated above.
[0453] By way of example, and at least while it is being applied,
the photoprotective composition applied as a base layer has a
screening power F against solar radiation of at least 2, preferably
5 or 10.
[0454] Using the base layer may reduce the risk of staining the
skin by rendering migration of the photochromic agent or agents of
the thermally stable photochromic composition towards the subjacent
keratinous material more difficult.
[0455] This migration may be further slowed or even prevented when
the first and second compositions are not miscible with each other,
one of the compositions being aqueous, for example, and the other
non aqueous, or vice versa, in order to form two phases.
[0456] Thus, it is possible to select the ingredients (solvents,
adhesives, etc) for the second composition that are not solvents
for the thermally stable photochromic composition and vice versa.
As an example, an organic solvent is selected from alcohols or
ketones, for example, in particular ethanol or acetone, alkyl
acetate, carbonaceous oils, in particular isododecane, or volatile
silicones for the photoprotective second composition and an aqueous
or hydroalcoholic solvent for the thermally stable photochromic
first composition, or vice versa.
[0457] It is also possible to select two organic solvents or two
aqueous solvents for the two compositions, such that a
transformation takes place on drying. As an example, a first
composition containing a latex may be used. On drying, this
composition coalesces and renders the layer inert to application of
the thermally stable photochromic composition.
[0458] The base layer may be formed on a surface that is more
extensive than the thermally stable photochromic composition. This
facilitates application of the thermally stable photochromic
composition, since the user no longer needs to worry about making
the outlines of the two applied compositions correspond
precisely.
[0459] When the thermally stable photochromic composition is
suitable for being developed by exposure to UV radiation, then the
optical agent contained in the base layer is preferably a
non-photostable sunscreen, with a photostability index of 80% or
less.
[0460] One resulting advantage is that when a base layer is applied
to the skin, the user is not completely prevented from tanning,
even if the extent of the base layer goes substantially beyond that
of the thermally stable photochromic composition. During exposure
to the sun, the base layer may then lose its capacity to screen UV,
which enables the user to tan progressively at least in the zone
not covered by the thermally stable photochromic composition. If
the sunscreen were photostable, users might fear applying the base
layer too extensively, for fear of leaving trace marks in their
tan.
[0461] In order to measure the photostability of a sunscreen, it is
diluted in a C.sub.12-C.sub.15 alkyl benzoate solvent with trade
name FINSOLV.RTM.. The screen Parsol 1789 is an example of a
non-photostable screen, having a photostability of the order of
30%, defined as being the ratio between the screening power after
one hour's exposure to UVA radiation produced by an irradiator from
SUNTEST divided by the initial screening power.
[0462] The base layer may be applied well before the
light-sensitive makeup, for example more than 15 minutes before,
which may have the effect of leaving the base layer time to dry and
to render it insoluble or nearly insoluble in the layer applied
over it, as mentioned above. Further, on drying, the base layer may
optionally form a relatively smooth surface, facilitating
application of a layer of thermally stable photochromic composition
with uniform thickness. The skin is thus smoothed, and so the
second layer may be thinner and there is a reduced risk of
non-uniform thickness, which might give rise to unattractive visual
effects following development.
[0463] If necessary, at least one intermediate layer may be applied
to the base layer in order to place it between the thermally stable
photochromic composition and the base layer.
[0464] This intermediate layer may have the effect of improving the
hold of the thermally stable photochromic composition on the base
layer or, on the contrary, of facilitating removal during makeup
removal, for example. The intermediate layer may be a layer of a
polymer or wax.
[0465] In particular, the intermediate layer need not function as a
screen at the wavelength .lamda. for developing the thermally
stable photochromic composition.
[0466] Further, a layer of another composition may be applied
beneath the base layer to facilitate its adhesion to the skin.
Thus, the base layer need not be directly in contact with the skin.
In a variation, the base layer is applied directly to the skin or
other keratinous material.
Mechanical Protection of Light-Sensitive Makeup
[0467] At least one layer of thermally stable photochromic
composition may be applied to the keratinous material, and by means
of a second composition or by means of added energy, it may form a
material that mechanically protects the light-sensitive makeup in
the layer of thermally stable photochromic composition.
[0468] It is also possible to deposit at least one covering layer
on the layer of thermally stable photochromic composition that
enables a material ensuring mechanical protection of the
light-sensitive makeup to be formed.
[0469] The light-sensitive makeup look may be created before or
after forming the material providing the light-sensitive makeup
with mechanical protection, by selectively developing the layer of
thermally stable photochromic composition.
[0470] Improving the mechanical hold of the light-sensitive makeup
may delay degradation of the image formed and the loss of sharpness
of the image over time is slowed.
[0471] Further, the light-sensitive makeup is rendered less
sensitive to rubbing and to movements. The risk of transferring
thermally stable photochromic composition onto clothing or other
regions of the body is also reduced.
[0472] Thus, a more durable light-sensitive makeup may be created
on zones such as zones covered with clothing, for example the back,
stomach, breasts, legs, or thighs.
[0473] Said material may be formed by solvent evaporation, or by a
polymerization or cross-linking reaction, which does not
necessarily need to be complete. Surface hardening, by
polymerization and/or cross-linking, may prove sufficient to
improve the hold.
[0474] The material providing mechanical protection of the
light-sensitive makeup is advantageously transparent.
[0475] When the material covers the layer of thermally stable
photochromic composition, the material forms a wear layer that, by
wearing bit by bit during the day, protects the light-sensitive
makeup.
[0476] When it covers the thermally stable photochromic composition
layer, the material may also contribute to the esthetics of the
light-sensitive makeup, by providing an additional optical effect,
for example a magnifying or coloration effect.
[0477] When the thermally stable photochromic composition offers
the possibility of erasing the light-sensitive makeup by
irradiating the layer of thermally stable photochromic composition
at a wavelength that differs from that used to develop the
thermally stable photochromic composition, the material may improve
its hold without in any way preventing the light-sensitive makeup
from being removed if that is desired; the user does not need to
remove the makeup completely for this purpose.
[0478] In order to form the material that provides the
light-sensitive makeup with mechanical protection, it is possible
to use polymerizable and/or cross-linkable compounds in the
thermally stable photochromic composition and/or in the covering
layer.
[0479] The thermally stable photochromic composition may contain
all of the polymerizable and/or cross-linkable compounds serving to
form the material. Optionally, the irradiation used to develop the
thermally stable photochromic composition serves for polymerization
and/or cross-linking.
[0480] The thermally stable photochromic composition may also
contain a first agent that may potentially polymerize and/or
cross-link. After or before development of the photochromic agents
of the thermally stable photochromic composition, a second compound
is applied that, by association with the first, may carry out the
polymerization or cross-linking. The irradiation may also possibly
serve to bring about polymerization and/or cross-linking.
[0481] In other exemplary embodiments, the second composition is
applied after applying the thermally stable photochromic
composition and creating the light-sensitive makeup look.
[0482] The covering layer may be applied either before or after
irradiation serving to develop the photochromic agent or agents.
Its mean thickness may be at least 2 .mu.m [micrometer], if
possible at least 5 .mu.m if the material is rather hard or
elastomeric, preferably at least 10 .mu.m if the material has a
rather soft elastic modulus.
[0483] When the keratinous material is covered by a single layer
that comprises the light-sensitive makeup, the thickness of said
layer is preferably more than 5 .mu.m, more preferably 10 .mu.m.
The thickness is preferably less than 1 mm.
[0484] When the thermally stable photochromic composition
incorporates all or some of the compounds that may potentially
cross-link, it is possible in a second stage, before or after
drying the first composition, to apply a second compound that
causes cross-linking or is necessary for cross-linking. The
thickness of the second layer (expressed after evaporation of any
solvents) is preferably equal to at least 20% of the thickness of
the first layer, preferably more than 50% of the thickness of the
first layer. The thickness of the second layer is preferably more
than 5 .mu.m.
[0485] When the thermally stable photochromic composition does not
include any potentially cross-linkable compounds, it is possible in
a second stage to apply a second composition containing the
compounds that produce cross-linking. The thickness of the second
layer (expressed after evaporating off any solvents) is preferably
equal to at least 10% of the thickness of the first layer, and
preferably more than 30% of the thickness of the first layer. The
thickness of the second layer is at least more than 5 .mu.m,
preferably less than 1 mm.
[0486] Polymerization and/or cross-linking allowing formation of
the material may be chemical or physical.
Chemical Polymerization and/or Cross-Linking
[0487] The term "chemical cross-linking" means that a compound,
whether alone, or by reaction with a second compound, or by the
action of radiation, or by the supply of energy, is capable of
creating covalent chemical bonds between the molecules. The result
is an increase in the cohesion of the material including said
compound.
[0488] The compound may be a simple molecule, or it may already be
the result of a combination of several molecules, for example
oligomers or polymers. The compound may carry one or more reactive
functions.
[0489] Preferred molecules are those that, after cross-linking,
provide a solid and/or deformable but elastomeric material.
[0490] The chemical functions may react with another function of
the same nature or that may react with another chemical
function.
Reaction with Another Function of the Same Nature
[0491] These are, for example, ethylenic functions, in particular
acrylates, acrylics, methacrylates, methacrylics, or styrene.
[0492] In order to react, these molecules generally require an
external form of activation, for example light, heat, the use of a
catalyst, or a combination with photoinitiators and possibly
photosensitizers intended to broaden the spectrum of action of the
photoinitiators. Photopolymerizable and/or photo-cross-linkable
compositions are described, for example, in patents CA-A-1 306 954
and U.S. Pat. No. 5,456,905.
[0493] It is possible to use polymeric compounds carrying ethylenic
functions as described in patent EP-A-1 247 515.
[0494] The ethylenic functions may be activated by an attracting
group in order to accelerate the reactions and render the supply of
any external activation redundant. This is typical of the
ethylcyanoacrylate monomer, for which the sole presence of a
catalyst such as water allows the reaction to occur.
[0495] The ethylenic functions may be moderately activated, for
example by an electron-attracting group. The advantage is that the
reaction requires an external activation, which is important when
controlling the initiation and the yield of the reaction, but does
not require a photoinitiator. For example, it may be a
cyanoacrylate monomer, in particular a cyanoacrylate monomer in
which the group carried by the ester function contains at least 2,
if possible 4 carbonaceous concatenations.
[0496] Molecules requiring external activation such as light but
not requiring a photoinitiator are preferred. Thus, molecules that
are capable of reacting by photodimerization, such as those
described in the patent EP-A-1 572 139, are particularly preferred,
in particular those carrying functions such as:
[0497] 1) stilbazoliums:
##STR00020##
where [0498] R represents a hydrogen atom, an alkyl or hydroxyalkyl
group; and [0499] R' represents a hydrogen atom or an alkyl
group;
[0500] 2) styrylazoliums:
##STR00021##
where
[0501] A designates a sulfur atom, an oxygen atom, or a NR' or
C(R').sub.2, group, R and R' being as defined above;
[0502] 3) chalcone;
[0503] 4) (thio)cinnamate and (thio)cinnamamide;
[0504] 5) maleimide;
[0505] 6) (thio)coumarin;
[0506] 7) thymine;
[0507] 8) uracil;
[0508] 9) butadiene;
[0509] 10) anthracene;
[0510] 11) pyridone;
[0511] 12) pyrrolizinone;
[0512] 13) acridizinium salts;
[0513] 14) furanone;
[0514] 15) phenylbenzoxazole;
[0515] 16) styrylpyrazine.
[0516] The reactions carried out on another function of the same
nature are not limited to reactions involving ethylenic
functions.
[0517] Compounds that may react by condensation are also preferred,
such as: [0518] siloxane groups, in particular dialkoxy- or
dihydroxy-silane functions, trialkoxy- or trihydroxy-silane
functions. It is possible to use molecules carrying
alkyltrialkoxysilane or dialkyltrialkoxysilane functions, in
particular alkylalkoxysilane functions where the alkyl group
carries a hydrosolubilizing function such as an amine, for example
a molecule such as aminotriethoxysilane or aminotriethoxysilane, or
molecules carrying such functions. In addition to small molecules
based on siloxanes (monomers or oligomers), compounds with a larger
mass may be used, in particular those described in patent FR-A-2
910 315; [0519] sol-gels based on titanium.
[0520] With these molecules, it is possible to control initiation
and reaction yield.
[0521] Compounds capable of reacting by oxidation are also
preferred, such as aromatic compounds carrying at least two
hydroxyl functions, or a hydroxyl function and an amine function,
or a hydroxyl function, for example cathecol or dihydroxyindole.
The oxidizing agent may be oxygen from the air or another oxidizing
agent such as hydrogen peroxide, for example.
Reaction with Another Function
[0522] The molecules that react in such circumstances have two
types of functions that are complementary. They may be systems in
which molecules carrying functions FA are brought into contact with
molecules carrying functions FB that are capable of reacting with
the functions FA.
[0523] They may also be molecules that carry one or more functions
FA and one or more functions FB on the same structure.
[0524] The function FA may be selected from the following, for
example: [0525] epoxide; [0526] aziridine; [0527] vinyl and
activated vinyl, in particular acrylonitrile, acrylic and
methacrylic esters; [0528] crotonic acid and esters, cinnamic acid
and esters, styrene and derivatives, butadiene; [0529] vinyl
ethers, vinylketone, maleic esters, vinylsulfones, maleimides;
[0530] carboxylic acid anhydride, chloride and esters; [0531]
aldehydes; [0532] acetals, hemi-acetals; [0533] aminals,
hemi-aminals; [0534] ketones, alpha-hydroxyketones,
alpha-haloketones; [0535] lactones, thiolactones; [0536]
isocyanate; [0537] thiocyanate; [0538] imines; [0539] imides, in
particular succinimide, glutimide; [0540] N-hydroxysuccinimide
esters; [0541] imidates; [0542] thiosulfate; [0543] oxazine and
oxazoline; [0544] oxazinium and oxazolinium; [0545] C.sub.1 to
C.sub.30 alkyl or C.sub.6 to C.sub.30 aryl or aralkyl halides with
formula RX, with X.dbd.I, Br, Cl; [0546] unsaturated, carbonaceous
or heterocyclic ring halides, in particular chlorotriazines; [0547]
chloropyrimidine, chloroquinoxaline, chlorobenzotriazole; [0548]
sulfonyl halide: RSO.sub.2--Cl or --F, R being a C.sub.1 to
C.sub.30 alkyl.
[0549] By way of illustration, the following molecules carrying
functions with a group FA may be mentioned: [0550] methylvinyl
ether and maleic anhydride copolymer, in particular sold by ISP
with the trade name Gantrez, for example; [0551] glycidyl
polymethacrylate, in particular sold by Polysciences; [0552]
glycidyl polydimethylsiloxane, in particular sold by Shinetsu
(reference X-2Z-173 FX or DX); [0553] epoxy polyamidoamine, for
example sold by Hercules with the trade name Delsette 101, Kymene
450 from Hercules; [0554] epoxy-dextran; and [0555] polyaldehyde
polysaccharides obtained by oxidation of polysaccharides using
NaIO.sub.4 (Bioconjugate Techniques; Hermanson GT, Academic Press,
1996).
[0556] The function FB may be selected from XHn functions with
X.dbd.O, N, S, COO and n=1 or 2, especially alcohols, amines,
thiols and carboxylic acids.
[0557] Examples of molecules that carry FB type functions are as
follows: [0558] PAMAM dendrimer, in particular sold by Dendritech,
DSM, Sigma-Aldrich (STARBURST, PAMAM DENDRIMER, G(2, O) from
DENDRITECH); [0559] dendrimer with hydroxyl functions, in
particular sold by Perstorp, DSM, (example: HBP TMP core 2
Generation PERSTORP); [0560] PEI (polyethylene-imine), in
particular sold by BASF, with the trade name Lupasol; [0561]
PEI-Thiol; [0562] polylysine, in particular sold by Chisso; [0563]
HP cellulose, such as KLUCELEF from AQUALON); [0564] amino-dextran,
for example sold by Carbomer; [0565] amino-cellulose, for example
those described in WO-01/25283 from BASF; [0566] PVA
(polyvinylacetal), for example AIRVOL 540 from AIRPRODUCTS
CHEMICAL; [0567] amino PVA, for example sold by Carbomer; and
[0568] chitosan.
[0569] This second case also includes molecules that may react by
hydrosilylation:
##STR00022##
(W represents a carbonaceous or silicon-containing chain, for
example).
[0570] Details of the two ingredients, the commercially available
molecules, the conditions for the catalysts and the conditions of
use are described in patent application FR-A-2 910 315.
[0571] In one particular possibility, a molecule that is already
present on the skin or excreted by the skin is used as a reagent or
catalytic agent. It is typically water, which may assist in the
cyanoacrylate reaction, for example, or in certain reactions
involving siloxanes.
[0572] In another particular possibility, a molecule is used as the
reagent or catalytic agent that is present in ambient air. It is
typically oxygen that is involved in the cross-linking reaction of
certain oils such as siccative oils, in particular siccative
vegetable oils such as linseed oil, China wood oil (or tung oil),
oiticica oil, vernonia oil, poppy-seed oil, pomegranate oil,
calendula oil or alkyd resins. The reactions may be accelerated by
using catalysts such as cobalt, manganese, calcium, zirconium,
zinc, strontium, lead, lithium, iron, cerium, barium, or tin salts
in the form of the octoate, linoleate or octanoate, for
example.
[0573] In another particular possibility, molecules are used that
bind with each other by rearranging. Thus, it is possible to use
molecules that carry an internal disulfide. By opening the internal
disulfide and reacting said disulfides, it is possible to create
new covalent bonds between the molecules.
[0574] Catalysts may be used to accelerate the reactions. As an
example, metal salts such as manganese, copper, iron, platinum,
titanates or enzymes such as oxidases or laccases may be used.
[0575] With chemical functions that react with another function of
the same or a different nature, several modes of application are
possible.
[0576] As an example, all of the ingredients that react are
incorporated in the thermally stable photochromic composition, or
all of the ingredients are incorporated in the thermally stable
photochromic composition with the exception of one or more
compounds, for example one of the compounds, or a catalyst. It may
be that none of the ingredients are incorporated in the thermally
stable photochromic composition; they are all applied at once or at
different times, after application of the thermally stable
photochromic composition and preferably after creating the
light-sensitive makeup look.
Physical Cross-Linking
[0577] Cross-linking may be physical when ingredients are used that
are capable of creating durable physical bonds between the
molecules and endowing the final material with water resistance.
These bonds, which are non-covalent, are of the ionic or hydrogen
type.
[0578] Examples that may be mentioned are mixtures with a di- or
poly-valent type salt, for example a calcium, zinc, strontium, or
aluminum salt.
[0579] As an example, a compound A such as an alginate derivative
and a compound B such as a calcium salt may be mixed. By way of
example, the alginate derivative is contained in the thermally
stable photochromic composition. In a second stage, an aqueous
solution of calcium chloride is applied in the form of a spray, for
example, in order to cause cross-linking.
[0580] Molecules that are capable of creating strong hydrogen bonds
may also be mentioned, such as polysiloxane and polyurea block
copolymers, and in particular those with formulae:
##STR00023##
where: [0581] R represents a monovalent hydrocarbon radical
containing 1 to 20 carbon atoms, which may be substituted with one
or more fluorine or chlorine atoms, [0582] X represents an alkylene
radical containing 1 to 20 carbon atoms, in which the
non-neighboring methylene units may be replaced by --O-- radicals;
[0583] A represents an oxygen atom or an amino radical --NR'--;
[0584] Z represents an oxygen atom or an amino radical --NR'--;
[0585] R' represents hydrogen or an alkyl radical containing 1 to
10 carbon atoms; [0586] Y represents a bivalent hydrocarbon
radical, if necessary substituted with fluorine or chlorine,
containing 1 to 20 carbon atoms; [0587] D represents an alkylene
radical, if necessary substituted with fluorine, chlorine,
C.sub.1-C.sub.6 alkyl, or C.sub.1-C.sub.6 alkyl ester, containing 1
to 700 carbon atoms, in which the non neighboring methylene units
may be replaced by the radicals --O--, --COO--, --COO-- or
--OCOO--; [0588] n is a number from 1 to 4000; [0589] a is a number
that is at least 1; [0590] b is a number from 0 to 40; [0591] c is
a number from 0 to 30; and [0592] d is a number greater than 0.
[0593] Details of the functions, commercially available molecules,
and the implementation conditions are given in patent EP-A-0 759
812.
Cross-Linking Compounds Leading to the Formation of a Particularly
Resistant Coating
[0594] Irrespective of whether the cross-linking is chemical or
physical, the cross-linking compounds may be selected so that they
provide the best possible resistance, in particular to water and
moisture.
[0595] Thus, it is possible to produce highly hydrophobic coatings,
in particular to treat the parts of the body that perspire the
most, such as the bust or the armpits, for example.
[0596] As an example, a first reactive ingredient FA of the polyol
type may be used, such as a cellulose derivative, and a second
reactive ingredient FB of the perfluoro-alkyltriethoxysilane type.
Under such circumstances, the application is carried out in two
stages. The polyol is introduced into the thermally stable
photochromic composition. A coating composition containing the
ingredient FB is applied to the thermally stable photochromic
composition.
[0597] In another example, a system is employed that is capable of
producing a cross-linked coating; it also contains hydrophobic
particles. An illustration of these combinations is the combination
of hydrophobic particles with condensation techniques or
hydrosilylation techniques such as those described in patent FR-A-2
910 315. The solid particles that may be used may be of mineral or
organic origin, porous or non porous, colored or not colored. They
may have any morphology, preferably spherical. The particles may be
naturally hydrophobic, which is the case with PTFE powder, for
example, or they may be rendered hydrophobic by coatings, in
particular of hydrocarbons, silicones, fluoro compounds or
fluorosilicones.
[0598] It is also possible to produce coatings that provide better
resistance to sebum and to fats, based on oxide or zinc salts, for
example, or coatings that are rendered more resistant to elongation
or to tearing. These improvements may be of use in applications to
parts of the body that move the most, such as the lips, the hands,
the armpits, the neck, or any zones close to joints.
[0599] The elongation strength may be acquired by using
cross-linking ingredients that, for example, produce a material
with an elastomeric nature. It is also possible to integrate non
reactive compounds into the composition or compositions, providing
an elastomeric nature, for example an elastomeric polymer such as a
deproteined natural latex or fibers.
[0600] One particular possibility is to impregnate a woven or
nonwoven fabric with cross-linking ingredients. A woven or nonwoven
fabric may be applied to the skin before or during or after
application of the light-sensitive makeup composition. Impregnating
the composition into the fabric provides mechanical strength.
[0601] It is also possible to combine the fabric and the
light-sensitive makeup composition then, once produced, to apply it
to the skin with or without using an adhesive.
[0602] Lubricating active ingredients may be incorporated in the
compositions, in particular solid lubricants such as boron nitride
or aluminum, for example.
[0603] It is also possible to integrate solid fillers, in
particular fillers that are hydrophilic or rendered hydrophilic,
such as metal oxide particles, metal hydroxide particles, metal
carbonate particles, or organic particles. These fillers may
provide additional abrasion resistance.
Covering Layer Forming Wear Layer
[0604] The coating layer may form a mechanical protective material
above the thermally stable photochromic composition layer and act
as a wear layer.
[0605] The coating layer is then advantageously cohesive, after
evaporating off any solvents, and it may be applied before or after
irradiation.
[0606] The term "cohesive" means that the layer is resistant on
contact. As an example, if a flat probe with a surface area of 1
cm.sup.2 [square centimeter] is brought towards the coating layer,
so that it comes into contact with a pressure of 10 N/cm.sup.2
[newton per square centimeter], then the probe is withdrawn after a
contact time of 5 seconds, it must not entrain matter. Thus, oily
compounds are excluded.
[0607] The coating layer is not sticky once the solvents have been
evaporated off. The term "not sticky" means that the layer offers
no resistance to withdrawal. As an example, if a flat probe with a
surface area of 1 cm.sup.2 is brought towards the layer so that it
comes into contact with a pressure of 10 N/cm.sup.2, and then it is
withdrawn after a contact time of 5 seconds, it must not require a
resistive force to achieve that withdrawal. Thus, compounds known
as PSA (pressure sensitive adhesive) are excluded.
[0608] The material forming the coating layer may have an elastic
modulus of less than 500 MPa [megapascal] and more than 100 kPa
[kilopascal], preferably in the range 200 MPa to 1 MPa.
[0609] Its mean thickness is at least 1 .mu.m, if possible at least
2 .mu.m if the material has an elastic modulus of more than 10 MPa.
Its mean thickness is at least 2 .mu.m, if possible at least 5
.mu.m if the material has an elastic modulus of less than 10
MPa.
[0610] When the material forming the coating layer is elastomeric,
i.e. has a maximum deformation of at least 400% before rupture and
has an elastic recovery of at least 90% after waiting for 1 minute,
the mean thickness is preferably at least 1 .mu.m, even if the
elastic modulus is less than 10 MPa.
[0611] The term "elastic recovery" means the degree of return to
the initial length of a specimen after 40% tensile deformation then
release of the load. Thus, if the initial length of the specimen is
L0, and the length after 40% tensile deformation and release of the
load is L(t), the recovery R(t) at time t from the release is equal
to:
100.times.(1-(L(t)-L0)/L0)/0.4).
[0612] Thus, if L(t)=L0, then R(t)=100.
[0613] If L(t)=1.4.times.L0, then R(t)=0
[0614] The recovery test is carried out by initially preparing a
specimen approximately 200 .mu.m thick, 6 cm in length, and 1 cm
wide. If necessary, the specimen is optionally produced on a
support film; its mechanical impact is judged to be small compared
with the mechanical properties of the specimen.
[0615] The specimen is subjected to a tensile deformation of 40% of
its length at a rate of 0.1 mm/s [millimeter per second]. Next, the
load is released and 1 minute is allowed to pass.
[0616] Preferably, the coating layer is applied with a solvent that
is very different from that used for the thermally stable
photochromic composition layer. However, this condition may be
circumvented, in particular when using cross-linking or coalescent
compounds for the thermally stable photochromic composition
layer.
[0617] As an example, if the thermally stable photochromic
composition layer contains a latex with a glass transition
temperature, Tg of <40.degree. C. and water, for example, the
coating layer may also be water-based.
[0618] If the thermally stable photochromic composition layer
contains a solvent and a compound that is capable of cross-linking,
such as those described above, for example, the coating layer may
contain the same solvent.
[0619] In order to assist in producing the coating layer properly,
prior to its application, light or heat may be supplied, for
example. It is also possible to deposit an intermediate layer
produced, for example, from a resin or any other product that aids
adhesion, such as an adhesive or certain powders, in particular
those that assist the upper layer in gripping because of their
grain size.
[0620] After application of the coating layer, light or heat may be
supplied.
[0621] The coating layer may be eliminated progressively. Thus, the
light-sensitive makeup layer is not altered over time and precision
of the light-sensitive makeup is fully retained.
Ingredients in the Coating Layer Forming the Wear Layer
[0622] The compounds that may be used in forming said coating layer
are polymers, for example poly(meth-)acrylics,
poly(meth-)acrylates, polyurethanes, polyesters, polystyrenes or
copolymers in the soluble or dispersed form, for example selected
from Mexomer, ultrahold Strong DR 25, 28-29-30, Gantrez, Amerhold
DR 25, amphomer, Luviset Si Pur, AQ 38, or AQ 48.
[0623] The polymers may carry side or terminal groups in order to
adjust their hardness. As an example, the material forming the
coating layer may comprise acrylate polymers with silicone
functions, such as VS 80, for example.
[0624] The polymers may be natural polymers or modified natural
polymers, for example polyosic polymers, such as guar gums, carouba
gums, or cellulose derivatives, such as HPMCP
[hydroxypropylmethylcellulose phthalate] or proteins.
[0625] The polymers may be hydrocarbon polymers.
[0626] The polymers may be silicones such as silicone gums, for
example.
[0627] Since the intrinsic qualities of the majority of polymers
cannot always provide the required hardness, it may be useful to
add a plasticizer.
[0628] In addition to the normally used plasticizers, for example
glycol ether (tripropylene glycol monomethyl ether (known as PPG3
methyl ether, from DOW CHEMICAL) or glycerin, certain non-volatile
solvents may be included, such as propylene carbonate, alcohols,
silicone or carbonaceous oils.
[0629] The quantities of plasticizers are calculated as a function
of the polymer and its intrinsic qualities. Typical values are as
follows (% relative to the weight of polymer):
TABLE-US-00001 Glycol ether Glycerin Ultrahold Strong DR 25 (BASF)
5% 10% Mexomer (Chimex) 4% 8% AQ 48 (Eastman Chemicals) 1% 2%
Luviset Si Pur (BASF) 3% 5% VS 80 (3M) 5% 10%
[0630] Mineral or organic particles may be included in the
composition, which may prolong the service life of the wear layer
without, however, causing it to lose its qualities. The particles
do not cause tightness in the skin but may, however, cause the
phenomena of flaking or balling. Thus, preferably a concentration
by weight of 40% of particles is not exceeded (particles capable of
coalescing not included).
[0631] Rheological agents that aid application may be included.
[0632] It is also possible to include spreading agents such as
surfactants or certain solvents with a boiling point in the range
80.degree. C. to 200.degree. C. These solvents have the advantage
of slowing down caking of the composition while being eliminated
over time.
Concentrations and Thicknesses after Drying
[0633] The concentrations of the various ingredients may be
adjusted so that the thicknesses after drying are, taking into
account the quantities applied, in agreement with the
specifications given above.
[0634] As an example, assuming that 20 mg/cm.sup.2 of fluid
composition for spreading is applied, and that the composition
contains 10% dry matter, then it is possible to deposit
approximately 2 mg/cm.sup.2. If the density is approximately 1,
this corresponds to a thickness of approximately 20 .mu.m.
[0635] In another example, if it assumed that spraying of an
aerosol composition comprising 20% dry matter is carried out 30 cm
from the face for 4 seconds, then approximately 0.4 g [grams] be
deposited over 400 cm.sup.2, i.e. 1 mg per cm.sup.2. If the
relative density is approximately 1, then the thickness of the
deposited layer will be approximately 10 .mu.m.
[0636] Thus, depending on the modes of application and the
galenical forms, the dry matter concentrations may be from 1% to
50%.
[0637] The coating composition may be dry.
Other Ingredients
[0638] In addition to the ingredients mentioned above, each
composition may contain ingredients that make the following
possible or easier: distributing over the keratinous material, more
particularly the skin; providing skin care, comfort, for example
odor or softness; aiding in elimination on washing, for example one
or more surfactants; limiting penetration of the ingredients into
the skin, for example astringents; or supplying other cosmetic
functions, for example moisturizing, color, shine, and/or limiting
the impact of ultraviolet screening, for example a self-tanning
agent or a vitamin D activator.
Makeup Removal
[0639] When removing makeup, the user may leave traces of the
non-developed thermally stable photochromic composition. However,
these traces may be caused to be developed subsequently, for
example after a few hours have passed in ambient light. At that
time, it may be difficult for the user to start removing the makeup
again.
[0640] In order to overcome this problem, it may be advantageous
during or after makeup removal to apply at least one optical agent
that forms a screen at least at a wavelength .lamda. and that acts
to develop the thermally stable photochromic composition.
[0641] Said optical agent may be re-applied several times, where
appropriate.
[0642] The optical agent may be part of a makeup removal
composition.
[0643] The term "forming a screen at the wavelength .lamda." means
that the optical agent attenuates radiation with a wavelength
.lamda. by a factor of at least 2, the measurement being carried
out using apparatus that may measure the absorption spectrum by
restricting the irradiating light to a zone with a wavelength
centered around wavelength .lamda., as detailed above. Applying the
optical agent during, and preferably after, makeup removal prevents
traces of photochromic agent from being developed and reduces the
risk of staining the keratinous material or clothing.
[0644] The keratinous material should not be washed during the hour
following application of the optical agent. Later, when the user
washes, the non-developed traces of photochromic agent protected by
the optical agent can be eliminated.
[0645] Another advantage linked to application of the optical agent
is that, when a fresh light-sensitive makeup look is created, it
prevents certain non-developed parts of the preceding
light-sensitive makeup that are still present from being developed
during exposure to the radiation used to create the fresh
light-sensitive makeup look.
[0646] The optical agent may be applied after removing the makeup.
The optical agent may also form part of the formulation of a makeup
removal composition used for makeup removal.
[0647] The wavelength .lamda. may fall within the UV or near UV
spectrum (290 nm to 400 nm), in particular in the range from 320 nm
to 440 nm.
[0648] The makeup removal composition may be a conventional makeup
removal product based on surfactants or a particular makeup removal
product adapted to compounds from the thermally stable photochromic
composition, and may include a solvent, for example ethyl or butyl
acetate, acetone, ethanol or mixtures thereof, and more generally
any solvent selected from cosmetically acceptable organic solvents
(acceptable tolerance, toxicology, and feel). These organic
solvents may represent 0% to 98% of the total composition weight.
They may be selected from the group constituted by hydrophilic
organic solvents, lipophilic organic solvents, amphiphilic
solvents, and mixtures thereof. Examples of hydrophilic organic
solvents that may be mentioned are linear or branched lower mono
alcohols containing 1 to 8 carbon atoms such as ethanol, propanol,
butanol, isopropanol, or isobutanol; polyethylene glycols
containing 6 to 80 ethylene oxide moieties; polyols such as
propylene glycol, isoprene glycol, butylene glycol, glycerol, or
sorbitol; mono- or di-alkyl isosorbides of alkyl groups that
contain 1 to 5 carbon atoms; glycol ethers such as diethylene
glycol mono-methyl or mono-ethyl ether, and propylene glycol ethers
such as dipropylene glycol methyl ether.
[0649] Examples of amphiphilic organic solvents that may be
mentioned are polyols such as derivatives of polypropylene glycol
(PPG), such as the esters of polypropylene glycol and fatty acid,
or PPG and fatty acid such as PPG-23 oleyl ether or PPG-36 oleate.
Examples of lipophilic organic solvents that may be mentioned are
fatty esters such as diisopropyl adipate, dioctyl adipate, alkyl
benzoates, isopropyl myristate, isopropyl palmitate, butyl
stearate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl
palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate,
2-octyldodecyl myristate, di-(2-ethylhexyl) succinate, diisostearyl
malate, 2-octyldodecyl lactate, glycerin triisostearate, or
diglycerin triisostearate.
[0650] The makeup removal composition may also comprise: [0651] an
oil, for example in the form of a microemulsion; [0652] a pH agent
if the compound or compounds used to maintain the photochromic
agent or agents on the skin are pH-sensitive, as is carbopol, for
example; or [0653] an ionic liquid.
[0654] Examples of anionic surfactants that may be used alone or as
a mixture in the makeup removal composition that may in particular
be mentioned are alkaline salts, ammonium salts, amine salts or
amino alcohol salts of the following compounds: alkoylsulfates,
alkoylether sulfates, alkoylamide sulfates and ether sulfates,
alkoylarylpolyethersulfates, monoglyceride sulfates,
alkoylsulfonates, alkoylamide sulfonates, alkoylarylsulfonates,
.alpha.-olefin sulfonates, paraffin sulfonates,
alkoylsulfosuccinates, alkoylethersulfosuccinates, alkoylamide
sulfosuccinates, alkoylsulfosuccinamates, alkoylsulfoacetates,
alkoylpolyglycerol carboxylates,
alkoylphosphates/alkoyletherphosphates, acylsarcosinates,
alkoylpolypeptidates, alkoylamidopolypeptidates, acylisethionates
and alkoyllaurates.
[0655] The alkoyl or acyl radical in all of these compounds
generally designates a chain containing 12 to 18 carbon atoms.
[0656] It is also possible to mention soaps and fatty acid salts
such as oleic, ricinoleic, palmitic, stearic acids, coprah oil
acids or hydrogenated coprah oil acids and in particular salts of
amines such as amine stearates; acyl lactylates of acyl radical
that contains 8-20 carbon atoms; and carboxylic acids of
polyglycolic ethers with formula:
Alk-(OCH.sub.2--CH.sub.2).sub.n--OCH.sub.2--COOH
in the acid or salt form, in which the substituent Alk corresponds
to a straight chain containing 12 to 18 carbon atoms and in which n
is a whole number in the range 5 to 15.
[0657] Examples of non-ionic surfactants that may be used alone or
as a mixture and that may be mentioned in particular are: alcohols,
alkoylphenols and polyethoxylated, polypropoxylated or
polyglycerolated fatty acids with a fatty chain containing 8 to 18
carbon atoms; copolymers of ethylene oxide and propylene oxide,
condensates of ethylene oxide and propylene oxide on fatty
alcohols, polyethoxylated fatty amides, polyethoxylated fatty
amines, ethanolamides, esters of fatty acids with glycol, esters of
fatty acids with sorbitan, which may optionally be oxyethylenated,
esters of fatty acids with saccharose, esters of fatty acids with
polyethylene glycol, phosphoric triesters, esters of fatty acids
with glucose derivatives; alkylpolyglycosides and alkylamides of
aminated sugars; the condensation products of an .alpha.-diol, a
monoalcohol, an alkoylphenol, an amide or a diglycolamide with
glycidol, or a precursor of glycidol.
[0658] The makeup removal composition that contains the optical
agent may be formulated so as to allow the optical agent to be
deposited on rinsing, for example by coacervation effect, this
effect being capable of being obtained, for example, by using
surfactants and polymers with complementary ionic natures, for
example PC/PA, TC/TA, TC/PA, TA/PC, possibly with amphoteric and
non-ionic surfactants to facilitate deposition. PCs are typically
compounds such as cationic guar gums (Jaguar C13S, for example) or
artificial compounds such as JR 400 or ionene. TCs are typically
quaternary chain compounds (in particular trimethylammonium groups)
and fatty chain compounds (C.sub.6 to C.sub.30). PAs may be
multianionic polymers such as acrylate or methacrylate polymers or
copolymers or polymers containing sulfonic groups. TAs are anionic
surfactants such as carboxylic or sulfate or sulfonic surfactants
(LES, LS).
[0659] The makeup removal composition may be applied using any
suitable support, in particular one that is capable of absorbing,
for example a fibrous makeup removal disk, for example woven or
nonwoven, felt, cotton-wool, flocked film, sponge, or towelette;
the support used for makeup removal is advantageously eliminated
after the makeup removal operation.
[0660] The makeup removal composition may be contained in a
receptacle and withdrawn each time the makeup is to be removed. In
a variation, the makeup removal composition impregnates the support
used for makeup removal, the support then possibly being packaged,
for example in sealed packaging. After using the makeup removal
composition, the keratinous material does not need to be rinsed. In
a variation, it may be rinsed. Rinsing may be carried out using
running water, for example, without adding soap.
Examples proposed (the proportions expressed are by weight)
Photochromic composition A
TABLE-US-00002 Diarylethene * 0.8%
(1,2-BIS(2,4-DIMETHYL-5-PHENYL-3-THIENYL)-
3,3,4,4,5,5-HEXAFLUOROCYCLOPENTENE) Cellulose 4% Acetone qs 100%
##STR00024##
Photoprotective composition I:
TABLE-US-00003 Parsol 1789 5% Ethyl acetate qs 100% The mixture was
introduced in an aerosol, pressurized with DME (65/35)
Photoprotective composition II:
TABLE-US-00004 Fluorescent agent 0.4% 2-[2-(4-dimethylamino)phenyl
ethenyl]-1 methyl pyridinium Ethanol 20% Water qs 100%
Photoprotective composition III:
TABLE-US-00005 Thermally unstable photochromic mineral (AgCl +
copper 0.3% sulfate) Oil/water emulsion qs 100%
Photoprotective composition IV:
TABLE-US-00006 Fluorescent orange 0.5% Photosensitizing Dye NK-557
(Ubikem) Ethanol 20% Water qs 100%
Negative
[0661] A negative may be created for the light-sensitive makeup as
follows. A PowerPoint.RTM. file is produced representing a grid in
which each square has a side of approximately 3 mm. This file is
then printed onto a transparency using a laser printer. Where it is
not printed, the transparency allows UV to pass through in the UVA
activation band, at about 365 nm.
Irradiator
[0662] The UV irradiator used is, for example, a Wood lamp sold by
Bioblock Scientific with reference VL 6L, which delivers
approximately 6 W over approximately 75 cm.sup.2, at about 365 nm.
The power received, measured using a wattmeter, is 2.25 mW per
cm.sup.2 at 3 cm from the apparatus.
Support
[0663] The support used is a white polyurethane material
representing the texture of the skin, sold by Beaulax under the
trade name Bioskin ref #white 061031-2.
Tests
[0664] The tests were carried out in ambient light in a closed
room.
[0665] The compositions were applied to the above support and were
allowed to dry for 1 minute.
[0666] The negative was placed on the support, holding it with the
hand, and the irradiator was brought to approximately 3 cm from the
surface. Irradiation was carried out for t seconds, corresponding
to an energy of approximately 2.25 t mJ/cm.sup.2 [millijoule per
square centimeter].
[0667] The quality of the light-sensitive makeup was evaluated by
eye, taking care to observe the quality of the grid pattern.
Test 1:
[0668] A first light-sensitive makeup was created by applying
photochromic composition A to the support, allowing it to dry for 1
minute, illuminating with the UV irradiator while the negative was
on the support. Irradiation lasted 10 seconds and delivered 22.5
mJ/cm.sup.2.
Test 2:
[0669] A second light-sensitive makeup was created identical to the
first, with the difference that the photoprotective composition I
was sprayed on the layer of photochromic composition A. The two
light-sensitive makeups were allowed to age in daylight and the
sharpness of the colors were observed visually. After a few hours,
a much sharper color was obtained for test 2.
Test 3:
[0670] A light-sensitive makeup look was created by applying
photochromic composition A to the support, allowing it to dry for 1
minute and illuminating with the UV irradiator while the negative
was on the support. Irradiation lasted approximately 10 seconds and
delivered 22.5 mJ/cm.sup.2.
[0671] The photoprotective composition II was applied in the form
of spray. The light-sensitive makeup was compared with that
obtained by the procedure in test 1. They were quite comparable.
However, after 2 hours in daylight, the sharpness of the colors was
better for test 3 than for test 1.
Test 4:
[0672] A light-sensitive makeup was created by applying the
photochromic composition A to the skin, allowing it to dry for 1
minute, illuminating the zone with the UV irradiator while the
negative was on the skin. Irradiation took about 10 seconds and
delivered 22.5 mJ/cm.sup.2.
[0673] Photoprotective composition III was applied in the form of
spray. The light-sensitive makeup was compared with that obtained
in test 1.
[0674] The results were quite comparable. After 2 hours, the two
light-sensitive makeups were put into a chamber that was strongly
illuminated corresponding to the lighting in a television studio.
After turning off the illumination, the sharpness of the colors was
better for test 4 than for test 1.
Test 5:
[0675] A light-sensitive makeup was created by applying the
photochromic composition A to the support, allowing it to dry for 1
minute, illuminating the support with the UV irradiator while the
negative representing the pattern was on the support. Irradiation
took about 10 seconds and delivered 22.5 mJ/cm.sup.2.
[0676] The photoprotective composition IV was applied in the form
of spray.
[0677] The light-sensitive makeup was compared with that obtained
in test 1.
[0678] The results were quite different. The color differences
between developed and non-developed zones were less than in test 1.
However, after 4 hours, the light-sensitive makeup turned out to be
much more contrasted than for test 1.
Test 6:
[0679] Photochromic composition A was applied to the support,
allowing it to dry for 1 minute. The photoprotective composition I
having a screening power F of about 10 was applied. The negative
was placed on the support. The irradiator was brought to
approximately 3 cm, and irradiation was carried out for 100 s
[second] in order to deliver 225 mJ/cm.sup.2. A light-sensitive
makeup was observed equivalent to that in test 1.
[0680] The invention is not limited to the examples described.
[0681] For example, as photoprotective layer, it is possible to use
a garment that is transparent, at least in part, e.g. tights or
stockings that are very fine, but that are able to screen UV.
[0682] However, the layer of photoprotective composition or the
above-mentioned garment need not be present permanently on the
layer of photochromic composition. For example, the person may
remove or reduce the protection when the conditions in which the
person is situated are considered to have a lower level of UV. To
this end, a system may alert the person about the level of the UV
irradiation.
[0683] Zones of the body other than the face may be treated. All of
the examples referring to treatment of the face are equally valid
for the treatment of other regions.
[0684] The expression "comprising a" should be construed as being
synonymous with "comprising at least one".
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