Specification
PHOTOPROTECTIVE COMPOSITIONS AND FILMS, AND A PREPARATION
METHOD
The present invention relates to compositions and to
methods for photoprotecting various materials using
particles of photonic material, in particular particles
having a polymeric multilayer interference structure
obtained from photonic gels.
Furthermore, the present invention relates to
compositions and to methods of treating human keratinous
material.
Prior art
Current photoprotective compositions use
combinations of various screening agents, especially
soluble or insoluble organic screens. The absorption
spectrum of each of said screens is rarely broad enough
to cover the whole UV spectrum, and combinations are
necessary.
Further, a large number of soluble organic screens
may cause compatibility problems with the ingredients
usually contained in them, especially as a result of
interactions with other organic screens or with active
molecules such as antioxidants or vitamins, and their
photcstability may not be encirely satisfactory. Many
patents are concerned with solving this problem - an
indication that this problem crops up repeatedly.
Many non-cosmetic industry sectors also use uv
screens to photoprotect various materials against the
effects of UV radiation, in particular solar radiation.
This is particularly true of paint, ink, or
protective coating formulations for applying to
substances that are permanently exposed to uv radiation,
such as construction materials, materials used in the
automobile industry, or plastics packaging materials. In
particular, UV screens are being developed for colorant
formulations that need to be transparent, photostable,
compatible with the usual ingredients contained in said
formulations, and effective in providing the looked-for
color with resistance to light.
Similar considerations apply with polymer
compositions used in particular in the manufacture of
plastics materials that are stable on storage; they need
UV light screens to be developed that are particularly-
adapted to the methods of manufacturing and transforming
polymers, and in particular they need to he able to
tolerate the high temperatures used in extrusion.
In the natural fiber and/or artificial fibyr and/or
synthetic fiber industry, broad spectrum photostable UV
screens are being developed that are compatible with
methods of manufacturing said fibers, in particular in
the context of the manufacture of fibers made of
polyamide such as nylon, which are resistant to high
temperatures and can incorporate UV protection during
extrusion. Further, UV screens are being developed that
have good affinity, good adhesion to fibers, and thus in
particular can provide good resistance upon frequent
washing. The UV screens being developed must also
provide both good protection of the textile fibers and
also of the skin and other human keratinous material in
contact with said fibers.
The mineral or organic glass industry, in particular
for glass used in ophthalmology, is developing UV screens
that need to have a broad spectrum (active in the UVA and
in the UV3 regions), and that are photostable,
transparent, and compatible with the various techniques
for treating glass, such as methods of keying onto the
glass matrix or applying a photoprotective coating, for
example with polycarbonate glass.
Interference materials constituted by a multilayer
structure may be used as screening agents. With films
having a polymeric multilayer interference structure, the
layers may number up to several hundred, for example.
Such films may be produced by extrusion, are usually
transparent, and are several hundred µm [micrometer]
thick.
The use of a metal layer, for example of TiO2 or ZnO,
can produce greater differences in refractive index and
can reduce the number of layers constituting the film.
However, films using that technology nay become opaque to
visible light and may also prove to be fairly rigid.
In a variation, when the films are thick and have a
large number of layers, their efficiency may be
significantly reduced when they are fragmented into
particles. Because of the great, thickness of the films,
"edge effects" may very substantially reduce the
production of interference.
The use of holographic pigments in order to produce
a reflection in the UV spectrum is known from application
FR 2 921 559.
Application FR 2 888 491 discloses a photoprotective
composition comprising a screening agent having a
multilayer interference structure, the screening agent
comprising alternating high refractive index layers and
low refractive index layers.
"Photonic materials" or "photonic crystals" are
known from application US 2009/0086208 that are
constituted by a periodic arrangement of at lease two
polymeric portions having different dielectric constants.
In particular, those polymeric photonic materials contain
at least one polymeric portion that is capable, under the
influence of an altering stimulus, of producing a change
in at least one physical, chemical, or dielectric
characteristic including the dimension, shape, dielectric
constant, refractive index, color, or other parameter.
That change results in modifying a wavelength of
electromagnetic radiation diffracted by the photonic
material.
A photonic gel is a film having a polymeric
multilayer structure that may comprise a block polymer
that spontaneously forms a periodic lamellar structure
during deposition onto a support. Such a material may
have interference properties, for example when it is
brought into contact with a swelling agent.
Photonic gels are known from publications by
B. Thomas: Nat Mat Vol 6, 957-96 0, 2008 and J Am Cham soc
2009, 131, 7538 - 7539.
There is a need to benefit from novel UV light
screening systems adapted to photoprotecting materials
such as those mentioned above.
There is a need to benefit from non-soluble
screening materials that can be used to cover the UVA
and/or UVB spectrum, that are completely harmless, inert
as regards the environment, are photostable and not
photoreactive, that do not have compatibility problems
with the other constituents of the compositions
containing their., and that do not modify the mechanical
properties of the materials of packaging materials in a
negative manner.
There is a need to benefit from coloring effect
materials that are completely harmless, inert as regards
the environment, photostable, and not photoreactive, that
do not have compatibility problems with the other
constituents of the compositions containing them, and
that do not modify the mechanical properties of packaging
materials in a negative manner,
There is also a need to have available polymeric
films with a multi-portion structure, in particular
having a polymeric multilayer interference structure,
with optical properties that are only slightly affected
or are unaffected when they are fragmented into
particles.
The invention, which is intended to satisfy same or
all of the needs mentioned above, provides the use of
particles of photonic material, in particular particles
having a polymeric multilayer interference structure
obtained from photonic materials, in particular photonic
gels.
Summary
"Photoprotective™ application
Photoprotective compositions ana films
In first exemplary embodiments the inven.tion
provides a photoprotective composition, in particular a
cosmetic, including particles of photonic material.
The particles o£ photonic material may in particular
be particles having a polymeric multilayer interference
structure with at least two layers comprising a polymer.
Said polymer may be an amphophilic polymer defining at
least two layers of said structure. In other words, at
least two layers of said structure may be formed by an
amphophilic polymer.
In the context of the invention, the term
"photoprotective composition" is used to mean a
composition that is capable of protecting any material,
in particular human keratinous materials, against UV
radiation. In particular it has a transmission factor,
measured before application to said material, that is
less than or equal to 70%, 60%, 50%, 40%, 30%, 20%, 10%,
5%, or even more preferably less than or equal to 1%, for
at least one wavelength in the range 2 50 nm no 400 nm,
more preferably over the whole of said range. Screening
is much better when the transmission factor over the
range 250 ran to 400 nm is low.
In the context of the invention, the term "photonic
material" is used for a polymeric material comprising a
plurality of different portions arranged in a periodic
manner, capable of interfering with electromagnetic
radiation and of modifying it, with at least a first and
a second portion each having a respective dielectric
constant and a respective abiliry to modify the
electromagnetic radiation dimensionally by at least 5 nm
such that the portions define a ratio of dielectric
constants of at least 1 for a continuous wavelength range
from 10 nm to 10 micrometers when subjected to an
altering stimulus.
In the context of the invention, the term "polymeric
multilayer interference structure" is used for a stack of
at least two layers of polymer, preferably more than two
layers, the stack being capable of producing
interference, for example in order to screen UV, and for
example to provide protection against UVA, thereby
limiting browning of the skin, and/or to produce a color
and/or to lighten the complexion and/or to modify the
spectral reflectance, depending on the application.
The interference may provide the polymeric
multilayer interference structure with a transmission
spectrum including one or more transmission minima or a
reflection spectrum including one or more reflection
peaks in the wavelength range 250 nm to 800 nm.
The term "amphiphilic polymer" should be understood
to mean a polymer comprising a hydrophilic group and a
hydrophobic group. An amphophilic polymer may, for
example, be a block copolymer comprising at least one
hydrcphilic block and at least one hydrophobic block.
According to other exemplary embodiments the
invention provides a composition, in particular a
cosmetic composition, including particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, comprising a polymer
having a UV screen within it. The polymer is, for
example, an amphophilic polymer, for example as defined
above,
The term "polymer having a UV screen within it"
should be understood to mean that particles having UV
screening properties and that are distinct from the
groups forming said polymer are imprisoned in the
structure formed by said polymer. In other words, the UV
screen is present in addition to said polymer in the
structure formed thereby.
According to other exemplary embodiments the
invention provides a film that photoprotects against
solar UV radiation, for application to a material, in
particular to human keratinous materials, the film
including a photonic material, in particular a multilayer
interference structure screening solar UV radiation, in
which at least two layers comprise an amphophilic
polymer.
The amphophilic polymer may define at least two
layers of the polymeric multilayer interference structure
screening solar UV radiation. In other words, as with
the particles, at least two layers of the structure may
be formed by an amphophilic polymer.
According to other exemplary embodiments the
invention provides a photoprotective film for application
to a material, in particular to human keratinous
materials, comprising a photonic material, more
particularly a polymeric multilayer interference
structure, comprising a polymer having a UV screen within
it for example as defined above.
The photoprotective films described above may be
applied to a material, for example selected from
materials manufactured from at least one synthetic or
natural polymer, organic or mineral glasses, and
materials comprising at least natural fibers and/or
artificial fibers and/or synthetic fibers such as
textiles or papers.
The formulations for the photoprotective films are
selected in such a manner that they have a transmission
factor, measured before application to the material of
interest, in particular to keratinous materials, that is
less than or equal to 70%, 60%, 50%, 40%, 30%, 20%, 10%,
5%, or even better preferably less than or equal to 1%,
for at least one wavelength in the range 2 50 nm to
400 nm, more preferably over the whole of said range.
Screening is even better when the transmission factor
over the range 25 0 run to 400 nm is low.
Preparation methods
In other exemplary embodiments, the invention
provides a method of preparing a photoprotective
composition as described above, said method comprising:
a) a step of bringing a swelling agent into contact
with a photonic material, in particular having a
polymeric multilayer structure with at least two layers
comprising an amphophilic polymer;
b) a step of fragmenting a film of photonic
material, in particular a film having a polymeric
multilayer structure in which at least two layers
comprise an amphiphilic polymer, into particles of
photonic material, in particular into particles having a
polymeric multilayer structure with a largest dimension
of 100 µm or less and/or with a smallest dimension of
100 nm or more; and
c) a step of dispersing the particles of photonic
material, in particular particles having a polymeric
multilayer interference structure obtained after carrying
out steps a) and b) , in. a suitable medium;
step b) being carried out before or after step a) .
According to other exemplary embodiments, the
invention provides a method of preparing a
photoprotective composition as described above, said
method comprising:
a) a step of bringing a swelling agent including a
dissolved UV screen into contact with a photonic
material, in particular a photonic material having a
polymeric multilayer structure;
b) a step of fragmenting a film o£ photonic
material, in particular a film having a polymeric
multilayer structure, into particles of photonic
material, in particular into particles having a polymeric
multilayer structure with a largest dimension of 10 0 µm
or less and/or with a smallest dimension of 100 nm or
mere; and
c) a step of dispersing the particles of photonic
material, in particular particles having a polymeric
multilayer interference structure obtained after carrying
out steps a} and b), in a suitable medium;
step b) being carried out before or after step a).
The photoprotective compositions prepared by the
methods described above may bs photoprotective and
cosmetic compositions, the dispersion of step c) then
being carried out in a cosmetically acceptable medium.
Uses of photoprotective compositions and films
According to other exemplary embodiments the
invention provides a method of photoprotecting a material
against solar UV radiation, the method comprising the
steps consisting in:
- treating said material with a photoprotective
composition including particles of photonic material,
more particularly particles having a polymeric multilayer
interference structure, at least two layers of said
structure comprising an amphiphilic polymer; or
- integrating at least said composition into said
material
According to other exemplary embodiments the
invention provides a non-therapeutic and in particular a
cosmetic method of photoprotecting human keratinous
materials against solar UV radiation, the method
comprising the step consisting in applying to the human
keratinous materials a photoprotective cosmetic
composition including particles of photonic material,
more particularly particles having a polymeric multilayer
interference structure, at least two layers of said
structure comprising ar. amphiphilic polymer.
Other exemplary embodiments of the invention also
provide a physiologically acceptable, in particular a
cosmetic composition, for use in a method of
phoroprotection of human keratinous material against
solar UV radiation, in particular in a method for
reducing the risk of apparition of a skin cancer,
Wherein said composition includes particles of photonic
material, more particularly particles having a polymeric
multilayer interference structure, at least two layers of
said structure comprising an amphiphilic polymer.
Unless, otherwise specified, said composition may present
all the features of the cosmetic compositions according
-o the present invention.
According to other exemplary embodiments the
invention provides a method of photopratecting an ink, a
paint, or a coating, the rnethod comprising the step of
incorporating into said ink or said painc or said coating
at. least one composition including particles of photonic
material, more particularly particles having a polymeric
multilayer interference structure, at least two layers of
said structure comprising an amphiphilic polymer.
According to other exemplary embodiments the
invention provides a method of photoprotecting a material
manufactured from at least one synthetic or natural
polymer, the method comprising the step of:
- treating said polymer with a composition including
particles of photonic material, more particularly
particles having a polymeric multilayer interference
structure, at least two layers of said structure
comprising an amphiphilic polymer; or integrating said
composition into said material.
According to other exemplary embodiments the
invention provides a method of photoprotecting an organic
or mineral glass comprising the step of:
- treating said glass with at least one composition
including particles of photonic material, more
particularly particles having a polymeric multilayer
interference structure, at least two layers of said
structure comprising 3n amphiphilic polymer; or
integrating said composition into said glass.
According to ocher exemplary embodiments the
invention provides a method of photoprotecting a material
comprising at least natural fibers and/or artificial
fibers and/or synthetic fibers such as textiles or
papers, the method comprising the step of:
- creating said material with at least one
composition including particles of photonic material,
more particularly particles having a polymeric multilayer
interference structure, at least two layers of said
structure comprising an amphophilic polymer; or
integrating said composition into said material.
According to other exemplary embodiments the
invention, provides a method of photoprotecting a material
against solar UV radiation, the method comprising the
step consisting of:
- treating said material winh a photoprotective
composition including particles cf photonic material,
more particularly particles having a polymeric multilayer
interference structure, comprising a polymer having a UV
screen within it, for example an amphophilic polymer as
defined above; or
- integrating at least said composition into said
material.
According to other exemplary embodiments the
invention provides a non-therapeutic, and in particular a
cosmetic, method of photoprotecting human keratinous
materials against sola.r UV radiation, the method
comprising the step consisting in applying to human
keratinous materials a photoprotective cosmetic
composition including particles of photonic material,
more particularly particles having a polymeric multilayer
interference structure, comprising a polymer having a UV
screen within it, for example an amphophilic polymer as
defined above.
Other exemplary embodiments of the invention also
provide a physiologically acceptable, in particular a
cosmetic composition, for use in & method of
photoprotection of human. keratinous material against
solar UV radiation, in particular in a method for
reducing the risk of apparition of a skin cancer.
Wherein said composition particles of photonic material,
more particularly particles having a polymeric multilayer
interference structure, comprising a polymer having a UV
screen within it, for example an amphiphilic polymer as
defined above.
Unless, otherwise specified, said composition may present
all the features of the cosmetic compositions according
to the present invention.
According to other exemplary embodiments the
invention provides a method of photoprotecting an ink, a
paint or a coating, the method comprising the step of
incorporating into said ink or paint or said coating at
least one composition including particles of photonic
material, more particularly particles having a polymeric
multilayer interference structure, comprising a polymer
having a UV screen within it, for example an amphiphilic
polymer as defined above.
According to other exemplary embodiments the
invention provides a method of photoprotecting a material
manufactured from at least one synthetic or natural
polymer, the method comprising the step of:
- treating said polymer with a composition including
particles of photonic material, more particularly
particles having a polymeric multilayer interference
structure, comprising a polymer having a uv screen within
it, for example an amphiphilic polymer as defined above;
or integrating said composition into said material.
According to other exemplary embodiments the
invention provides a method of photoprotecting an organic
or mineral glass comprising the step of:
- treating said glass with at least one composition
including particles of photonic material, more
particularly particles having a polymeric multilayer
interference structure, comprising a polymer having a UV
screen within it, for example an amphiphilic polymer as
defined above; or integrating said composition into said
glass.
According to other exemplary embodiments the
invention provides a method of photoprotecting a material
comprising at least natural fibers and/or artificial
fibers and/or synthetic fibers such as textiles or
papers, the method comprising the step of:
- treating said material with at least one
composition including particles of photonic material,
more particularly particles having a polymeric multilayer
interference structure, comprising a polymer having a UV
screen within it, for example an amphiphilic polymer as
defined above-, or integrating said composition in~o said
material.
By wayr of example, the compositions and films used
in the photoprotection methods of the invention have an
SPF index, measured before application to the keratinous
materials, of at least 10, more preferably 15, more
preferably at least 30, 45, or 60. The SPF (Sun Screen
Protection Factor) index is defined in the article "A new
substrate to measure sunscreen protection factors
throughout the ultraviolet spectrum", J Soc Cosmet Chem,
40, 127 - 133 (May/June 1969).
'Fluorescence" application
Compositions and films
In other exemplary embodiments the invention
provides a cosmetic composition including particles, of
photonic material, more particularly particles having a
polymeric multilayer interference structure, comprising a
polymer having a fluorescent agent within it, for example
as defined above. The polymer may, for example, be an
amphiphilic polymer.
The term "polymer having a fluorescent agent within
it" is used to mean that particles having fluorescent
properties and that are distinct from the groups forming
said polymer are imprisoned in the structure formed by
said polymer. In other words, the particles having
fluorescent properties are present in addition to said
polymer in the structure formed thereby.
Preparation method
In other exemplary embodiments the invention
provides a method of preparing a cosmetic composition
including particles of photonic material, in particular
particles having a polymeric multilayer interference
structure, comprising a polymer having a fluorescent
agent within it, for example as defined above, said
method comprising:
a) a step of bringing a swelling agent includinging
a dissolved fluorescent agent into contact with a
photonic material, in particular having a polymeric
multilayer structure;
b) a step of fragmenting a film of photonic
material, in particular a film having said polymeric
multilayer structure, into particles of photonic
material, in particular into particles having a polymeric
multilayer structure with a largest dimension of 100 urn
or less and/or with a smallest dimension of 10 0 ran or
more; and
c) a s~ep of dispersing the particles of photonic
material, in particular particles having a polymeric
multilayer interference structure obtained after carrying
out steps a) and b), in a cosmetically acceptable medium;
step b) being carried out before or after step a).
Uses of compositions and films
In other exemplary embodiments the invention
provides a method of lightening human karatinous
materials, -he raerhod comprising the step consisting in
applying a cosmetic composition including particles of
photonic material, more particularly particles having a
polymeric multilayer interference structure, comprising a
polymer having a fluorescent agent within it, for example
as defined above.
According to other exemplary embodiments the
invention provides a film for lightening the complexion,
for application to human keratinous materials, comprising
a photonic material, more particularly a polymeric
multilayer interference structure, comprising a polymer
having a fluorescent agent within it, for example as
defined above.
"Coloring1 applica t i on
Compositions and films
In other exemplary embodiments the invention
provides a cosmetic composition including particles of
photonic material, more particularly particles having a
polymeric multilayer interference structure, producing a
visible color.
According to other exemplary embodiments the
invention provides a cosmetic composition including
particles of photonic material, more particularly
particles having a polymeric multilayer interference
structure, comprising a polymer having a coloring agent
within it, for example as defined above.
The term "polymer having a coloring agent within it"
is used to mean that a coloring agent that is distinct
from the groups forming said polymer is imprisoned in the
structure formed by said polymer. In other words, the
coloring agent is present in addition to said polymer in
the structure formed thereby.
According to other exemplary embodiments the
invention provides a. film for makeup, for example to even
out the complexion, for application to human keratinous
materials, the film including particles of photonic
material, more particularly particles having a polymeric
multilayer interference structure, producing a visible
color.
According to other exemplary embodiments the
invention provides a film for makeup, for example to even
out the complexion, for application to human keratinous
materials, the film including a photonic material
structure, in particular a polymeric multilayer
interference structure, comprising a polymer having a
coloring agent within it.
The particles having a polymeric muirilayer
interference structure may include an amphiphilic polymer
as defined above.
Preparation wet hods
in other exemplary embodiments the invention
provides a method of preparing a cosmetic composition
including particles of photonic material, in particular
particles having a polymeric multilayer interference
structure, for example comprising an amphiphilic polymer,
producing a visible color, said method comprising:
a) a step of bringing a swelling agent into contact
with a photonic material, in particular having a
polymeric multilayer structure;
b) a step of fragmenting a film of photonic
material, in particular a film having a polymeric
multilayer structure, into particles of photonic
material, in particular into particles having a polymeric
multilayer structure with a largest dimension of 10D urn
or less and/or with a smallest- dimension of 100 ran or
more; and
c) a step of dispersing said particles obtained
after carrying out steps a) and b) in a cosmetically
acceptable medium;
step b) being carried out before or afrer step a).
According to other exemplary embodiments zhe
invention provides a method of preparing a cosmetic
composition including particles of photonic material, in
particular parricles having a polymeric multilayer
interference structure, comprising a polymer having a
coloring agenc within it, for example as defined above,
said method comprising:
a) a step of bringing a photonic material, in
particular having a polymeric multilayer structure, into
contact with a swelling agent comprising a dissolved
coloring agent;
b) a step of fragmenting a film of photonic
material, in particular a film having a polymeric
multilayer structure, into particles of photonic
material, in particular into particles having a polymeric
multilayer structure with a largest dimension of 100 µm
or less and/or with a smallest dimension of 100 nm or
more; and
c) a step of dispersing said particles obtained
after carrying out steps a) and b} in a cosmetically
acceptable medium;
step b) being carried out before or afcer step a).
Uses of compositions and films
In other exemplary embodiments the invention-
provides a method of making up, for example to even out
the complexion, the method comprising the step consisting
in applying to human keratinous materials a cosmetic
composition including particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, for example comprising an
amphophilic polymer as defined above, producing a visible
color, said method possibly further comprising a step of
selecting a composition, as a function of the color and/or
the spectral reflectance of the keratinous materials to
be created.
According to other exemplary embodiments che
invention provides a method of making up, for example tc
even out the complexion, the method comprising the suep
consisting in applying to human keratinous materials a
cosmetic composition including particles of photonic
material, more particularly particles having a polymeric
multilayer interference structure, comprising a polymer
having a coloring agent within it, for example an
amphiphilic polymer as defined above, sa^id method
possibly further comprising a step of selecting the
composition as a function of the color and/or the
spectral reflectance of the keratinous materials to be
treated.
Photonic materials and polymeric multilayer interference
structures
The particular structural arrangement of the various
portions of the material and the dielectric constants of
said portions may result in reflection, in at least one
direction, of electromagnetic radiation of a particular
frequency directed onto the material. The structural
arrangement of the various portions of material and the
dielectric constants of said portions may form photonic
materials that diffract or reflect light about a
particular frequency or frequencies. In particular, the
polymeric photonic materials contain at least one
polymeric portion that is capable of producing a change
in at least one physical, chemical, or dielectric
characteristic including the dimension, shape, dielectric
constant, refractive index, color, or other parameters by
means of an altering stimulus. This change has the
result of modifying a wavelength of electromagnetic
radiation diffracted by the photonic material. As an
example, a change in dimension (i.e. volume change) may
be produced by swelling of one of the portions of the
photonic material my means of a solvent type swelling
agent. The dimensional change may modify the structural
arrangement of the photonic material and as a result the
dielectric constant of one of the portions of the
material, or it may modify the electromagnetic radiation
reflected hy the photonic material. As an example, a
modification of the optical properties nay in particular
be due to a periodic type spacing between similar
portions. The photonic material may comprise a firs::
portion that is reactive to an altering stimulus
producing a change in volume or another dimension and a
second portion that is non reactive or that is reactive
to another type of stimulation.
Photonic materials or photonic crystals are capable
of diffracting and/or reflecting electromagnetic
radiation over a wide range of wavelengths including the
visible, ultraviolet, infrared, and microwave
wavelengths. In some circumstances, they may diffract
electromagnetic radiation with a wavelength lying in the
range 100 run to 1600 run. In other circumstances,
photonic materials are capable of exhibiting spectacular
wavelength shifts of the order of 600% under the action
of an external stimulus.
In a particular embodiment of the invention, the
dimension of the electromagnetic radiation of at least
one of the portions changes relative to another portion
such that one wavelength of diffracted electromagnetic
radiation is modified by at least 10 nmr at least 25 nm,
at least 50 nm, at least 150 nm, at least 2 00 nm, or at
least 250 run under the influence of an altering stimulus
(i.e. swelling agent}.
The photonic materials of the invention may also
produce changes in the wavelength of the diffracted
electromagnetic radiation of at least 50%, at least 25%
or at least 10%. As an example, a photonic material of
the invention may diffract electromagnetic radiation of
more than 700 nm (infrared, microwave) , when in the
presence of an altering stimulus, the dimension of -he
electromagnetic radiation of at least one of the portions
may change relative no the other portion such that one
wavelength of electromagnetic radiation diffracted by the
photonic material is modified by at least 1%, 5%, 10%,
25% cr more. The percentage change in said diffracted
wavelength may be calculated using the following
equation:
[ Ui -A0) /A0j X 100
in which Ao corresponds to the peak of the diffracted
wavelength before contact with, or in the absence of, an
altering stimulus, and A3. corresponds to the peak of the
wavelength diffracted during contact with the altering
stimulus.
Photonic materials in accordance with the invention
are described in application US 2009/0086208 and they are
prepared using the methods indicated in that document.
Photonic material films and particles, in particular
having a__polymeric multilayer__interference structure
In the context of" the invention, the terms "photonic
naterials" and in particular the "polymeric multilayer
interference structures" encompass films and particles of
photonic materials, in particular having a polymeric
multilayer interference structure.
In the context of the invention, particles of
photonic material, in particular particles having a
polymeric multilayer interference structure, may be
present within a cosmetic composition.
The weight content, relative to the total
composition weight, of the particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, may be in the range
0.1% to 50%, for example in the range 1% to 20%, for
example in the range 5% to 15%.
It is also possible to use photonic material films,
in particular films having a polymeric multilayer
interference structure, said films possibly being applied
to keratinous materials as well as to materials such as
those mentioned above.
Said films may be deposited locally on a portion of
the external surface of the keratinous materials, for
example for protection from solar UV radiation, or to
lighten the complexion or for making up, for example to
even out the complexion.
Sa^ci films may be cut into any format and may, for
example, be used to conceal skin imperfections: spots,
wrinkles, vitiligo, etc
The films of the invention may optionally be
adhesive. The films may be adhesive, for example when
intended for application to keratinous materials, for
example the skin. The films of the invention may be
formed in situ on the keratinous materials.
Size and form of the polymeric multilayer interference
Structures
Figure 1 shows a particle having a polymeric
multilayer interference structure according to the
invention.
In the absence or in the presence of a swelling
agent, the length Li and the width r..2 of the particle may-
be in the range 1 pm to 100 pi.
The thickness L3 of particle iTiay be in the range
0.1 µm to 50 µm in the absence of a swelling agent, and
in the range 0,1 p to 100 µm in the presence of a
swe11i ng agen t.
in the absence or in the presence of a swelling
agent, the particles having a polymeric multilayer
interference structure may have a largest dimension of
100 urn or less-
In the absence of a swelling agent, -he pax'ticles
may have a largest dimension of 100 µm or less, for
example 7 5 urn or less, for example 50 µm or less.
In the absence or in the presence of a swelling
agent, the particles having a polymeric multilayer
interference structure may have a smallest dimension cf
0.1 µm or more, for example 1 pa or more.
The film having a polymeric multilayer interference
structure iray have a largest dimension in the range 1 irt.
to 5 0 cm.
The polymeric multilayer interference structures may
have a form factor in the range 1 to 1000.
The term "form factor" means the ratio of the
largest dimension of the polymeric multilayer
interference structure to its smallest dimension.
The polymeric multilayer interference structures may
be plate-like, i.e. have a form factor at least equal to
3, for example at least equal to 10.
The polymeric multilayer interference structures may
have a lamellar structure, linked to the presence of an
amphophilic polymer, for example. The amphophilic
polymer may have a lamellar structure.
The polymeric multilayer interference structures may
comprise at least three layers, for example at least 5,
10 or 50,
The polymeric multilayer interference structures may
comprise fewer than 100 layers.
Method for preparing the polymeric multilayer
interference structure
As mentioned above, the particles having a polymeric
multilayer interference structure may be obtained from a
photonic gel, which may be produced as described in the
publications by E. Thomas: Nat Ma- Vol 6, 957-960, 2006
and J Am Chem Soc 2009, 131, 7538 - 7539.
Figure 2 shows an example of a method of fabricating
films and particles having a polymeric multilayer
interference structure of the invention.
A pho-onic gel is obtained in the form of a film
(step i! , for exair.ple by spreading with a film puller, by
dip-coating or by spin-coating and by any printing
method, for example by ink jet printing a solution of
amphophilic block polymer in a solvent. When deposited
on a support, it organizes itself spontaneously into a
multilayer polymeric structure, for example a lamellar
structure. The photonic gel then comprises alternating
hydrophiiic and hydrophobic layers.
The number of layers of the multilayer structure of
the photonic gel nay be 100 or less and its thickness
after drying may be 15um or less.
After deposition and in the absence of a swelling
agent, the photonic gel need not have an interference
property in the wavelength range 250 ran to 800 nm.
The photonic gel may be quaternized, for example by
contact with 1-broruoethane, as described in the
publication Nat Mat Vol 6, 957-960, 2008.
Contact with a swelling agent (step III) , of nature
that is given in detail below, may cause the photonic gel
to swell, for example in. its hydrophilic or hydrophobic
layers, and thus produce a polymeric multilayer
interference structure.
As is detailed below, ~he step of contact with the
swelling agent may be used advantageously in order to
introduce one or more UV screens and/or one or more
fluorescent agents and/or one or more coloring agents
into the polymeric multilayer structure.
The interference wavelength may vary as a function
of the concentration, the difference in refractive index
between the various layers, the pH of the swelling agent,
the molecular weight and the degree of cross-linking cf
the polymers present in the polymeric multilayer
interference structure. By varying these parameters, it
is possible, for example, to cover the whole UVA or UVB
spectrum.
In Figures 3 and 4, for the purposes of clarity, the
relative proportions of the various elements shown have
not necessarily been maintained.
Figure 3 diagrammatically and partially shows a
photonic gel 1 deposited on a support S before contacc
with a swelling agent.
This photonic gel 1 comprises a polymeric multilayer
structure that may, for example and as illustrated, be
constituted by alternating hydrophilic 10 and hydrophobic
2 0 lamellar layers.
In the embodiment shown "in Figure 3, the photonic
gel is transparent to radiation R having, for example, a
wavelength in the range 250 mu to 80 0 nm.
The term "transparent" means that the photonic gel
has no band gap in the wavelength range 450 nm to 8 00 nm.
As an example, the photonic gel may have a transmission
factor of 80% or more, for example 90% in the wavelength
range under consideration.
Figure 4 shows the photonic gel 1 of Figure 3 after
contact with a swelling agent. In the example of
Figure 4, only rhe hydrophobic layers 20 are sensitive to
the swelling agent.
In a variation, it is possible for only the
hydrophilic layers 10 to be sensitive to the swelling
agent.
As shown, contact with a swelling agent may allow a
photonic gel 1 to reflect the radiation R and, for
example, provide photoprot-active properties as regards
solar UV radiation and/or produce a visible color. The
films of the invention may be used once the swelling step
has been carried out.
A coagulation step (step IV} of coagulating the
photonic gel may be carried out after bringing the
polymeric multilayer structure into contact with the
swelling agent, preferably before or after the
fragmentation step. It may comprise bringing the
polymeric multilayer structure into contact with a
coagulation agent that may be an inorganic material such
as silica or its precursors, for example TEOS, or a
glycol, for example glycerol, dipropylene glycol,
sorbitol, butylene glycol, PEGs having molecular weights
in the range 4 00 g/moi to 50000 g/mol. A coagulation
step employing a silica precursor, TEOS, in a sol-gel
method is described in the publication J Am Cherr. Soc
2G0S, 131, 7533 - 7539.
Carrying out a coagulation step may mean that the
particles can retain their physico-chemical properties,
especially their interference properties, after
dispersing them in a cosmetically acceptable medium.
The compositions including particles having a
polymeric multilayer interference structure comprising a
coagulation agent may retain their interfereuce
properties during application and for at least 2 hours,
for example 3 hours after applying the composition to the
keratinous materials.
The films having a polymeric multilayer interference
structure comprising a coagulation agent may retain their
interference properties during application and for at
least 2 hours, for example 3 hours after applying the
composition to the keratinous materials.
Fragmentation step (V) tor fragmenting the polymeric
multilayer structure of the photonic gel may be carried
out, as illustrated in Figure 2, after the step of making
contact with a swelling agenu. and after any step of
making contact with a coagulation agent. In a variation,
it is possible to carry out the fragmentation step before
the step of making contact with a swelling agent, and
then to carry out any coagulation step.
Fragmentation may, for example, be carried out by
laser cutting or milling with an air jet, cryorniiiing,
ball milling, or wet milling.
Swelling agent
In some exemplary embodiments, the photonic
material, in particular the polymeric multilayer
interference structure, may further include a swelling
agent (in particular a non-vclatile swelling agent) in 3
quantity that can swell one or both portions of said
material. The swelling agent may, for example, be a
mineral oil when the photonic material comprises a
polybutadiene / styrene block copolymer in order to swell
the polybutadiene portion.
Any appropriate solvent may be used as the swelling
agent, such as aqueous or organic solvents, for example.
In some particular embodiments of the invention, an
acidic, neutral, or basic solvent may be used.
in the context of the invention, the particles of
photonic material, in particular par-ides having a
polymeric multilayer interference structure, may include
a swelling agent.
The swelling agent may be hydrcphilic or hydrophobic
depending on the nature of the photonic material
portions, in particular the layers of the polymeric
multilayer interference structure, which are caused to
swell.
The swelling agent may include at least one
dissolved optically active material, for example a UV
screen, a fluorescent agent, a coloring agent and
mixtures thereof,
The optically active material may, for example, be
hydrophobic ox~ hydrophilic.
The swelling agent may, for example, comprise a
mixture of op-ically active materials, for example a
mixture of a UV screen and a fluorescent agent, a mixture
of a UV screen and a coloring agent, a mixture of a
fluorescent agent and a coloring agent or indeed a
mixture of a UV screen, a fluorescent agent and a
coloring agent.
It is possible to use water as the swelling agent,
as well as organic or inorganic saline solutions with a
concentration in the range C. 01 M to 5 M, for example
solutions of sodium, magnesium, potassium, calcium or
copper salts, solutions of phosphates, or ammonium salt
solutions.
It is also possible to use as the swelling agent,
either alone, as a mixture, or in aqueous solution ar.d in
any proportions, glycerol, PEGs having a molecular weight
in the range 400 g/mel to 50000 g/'mol, mono-, di- and
cligo-saccharides thar are soluble in water in a
proportion of at least 1% by weight, sorbitol, propylene
glycol, diprcpylene glycol, ethylene glycol, butylene
glycol, water-soluble polyols, lower alcohols tha: are
rtiiscible in water, for example methanol, ethanol or
isopropanol, or 1-butanol.
The term "lower alcohol" means an alcohol having
fewer than 6 carbon atoms-
Examples of other suitable solvents that may be
mentioned are benzene, acetone, p-methylbutyric acid, oc-
ethylbutyric acid, 2,2,2,-trifluoroethanol, 1-butanol,
1,4-butanediol, chloroform, bromoethane, methyl acetate,
ethyl acetate, dimethylformamide, butan-2-one,
divinylbenzene, propylene glycol monomethylether acetate
(PGHSA), and acetic acid solutions.
The swelling agent may further comprise or even
consist of a UV screen solution, for example organic,
neutralized or not neutralized. The following solutions
may be mentioned: terephthalylidene dicamphor SULFONIC
ACID, lor example Mexoryl SX or PHENYLBEtfZIMIDAZOLE
SULFONIC ACID, for example Eusolex 232.
Using a solution of non-neutralized organic UV
screen(s) would mean that the pH could be varied and thus
the swelling of the photonic material, especially the
polymeric multilayer structure, for example the
amphophilic polymer, can also be varied.
The swelling agent may also be selected from polar
oils such as lauroyl isopropyl sarcosinate,
octyldodecanol, a C12-Ci5 alkylbensoate {Finsolv TN) ,
imaecane and tridecane, for example, as well as oily
solutions of organic screens, for example when the
particles of photonic material, in particular particles
having a polymeric multilayer interference structure, for
example the amphiphilic polymer, comprise at least a
portion, in particular a layer, which is hydrophobic and
sensitive to the swelling agent.
The pH of the swelling agent may be in the range 1
to 12 . it may be modified by contact with acids and
bases selected, for example, from acetic, lactic,
hydrochloric, nitric, sulfuric, maleic, and succinic
acid, and bases such as sodium hydroxide, potassium
hydroxide, triethanolamine, or solutiong of lysine and
arginine.
Fixing agent
The particles of photonic material, in particular
particles having a polymeric multilayer interference
structure, may include a fixing agent.
A fixing agent may be selected from inorganic
compounds, for example silica and its precursors, for
example TEOS, or glycols, for example glycerol,
dipropylene glycol, sorbitol, butylene glycol, or PEGs
having molecular weights in the range 400 g/mol to
50000 g/mol.
The difference in the refractive index of the fixing
agent and the layers of the polymeric multilayer
interference structure may be in the range 0.05 to 1.5.
Polymers of photonic materials and o£ polymeric
multilayer interference structures
The photonic materials, in particular the polymeric
multilayer interference structures, of the invention may
include homopolymers, copolymers, block copolymers,
mixtures of homopolymers, mixtures of block copolymers,
mixtures of homopolymers and block copolymers, polymeric
materials associated with additives such as colorants, or
inorganic compounds.
In some exemplary embodiments, the photonic
materials may comprise mixtures of polymers or mixtures
of polymers and nor—polymers or others, and may include
at least two portions with different compositions and/or
having different chemical. physical, or dielectric
properties.
Furthermore, the photonic materials of the invention
may contain other polymeric, or . non-polymeric additives
that may be used to modify the dimension, the chemical or
the physical properties of at least one of the portions.
In addition, a non-polymeric additive present in the
structure of the photonic material may constitute a
region separating two portions within the periodic
structure. As an example, the size of the separated
polymeric portions may be controlled by modifying a
fraction of the volume of the portion, for example by
incorporating auxiliary nanoparticles, auxiliary
horaopoiymers, auxiliary monomers, or cross-linkable
compounds ~hat are polymerized, grafted, and/or cross-
linked in situ. The additives such as those mentioned
above nay be used to modify the number/type of the
portion and/or the dimensions of the portion but will noi:
influence the behavior of rhe photonic material under the
influence of an altering stimulus.
Block copolymer
The block copolymers present in the photonic
materials of the invention may result in one-, two- or
three-dimensional periodic structures arranged in
separate portions characterized by different compositions
and/or different physical properties.
The term "periodic structure" is used to mean a
structure arranged such that a straight line in at least
one direction passes through said structure and
intersects at least two separate portions at regular'
intervals. As an example, a "one-dimensional structure"
is a structure that may be oriented in an orthogonal
system of coordinates in three dimensions {components in
the X, Y, 2 directions) such that a straight line in a
single direction passes through said structure and
intersects an lease two separated portions at regular
integrals. A "twc-dimsnsional structure" is a structure
that may be oriented in a 3-dimensional coordinate system
such that straight lines in. two directions pass through-
said structure and intersect at least two separate
portions at regular intervals. A "three-dimensional
structure" is a structure that may be orier.ted in a 3-
dimensional coordinate system such that a straight liny
in any of the three directions passes through said
structure and intersects at least two separate portions
at regular intervals. In addition, the term "periodic
structure" refers to a material with portions having a
regular periodicity characterized ay similar portions
having similar dimensions and spacings in the photonic
material. The term "portion" defines a distinct region
of the photonic material characterized by a particular
composition and/or particular physical properries that
distinguish it from those of adjacent or surrounding
portions.
The polymer constituting the photonic material, in
particular the polymeric multilayer interference
structure, may bo amphiphilic and may comprise or, for
example, may be a block copolymer, for example a:
- diblock copolymer with the form A-B where A is a
hydrophobic block selected, for example, from;
polystyrene, polymethyl methacrylate, polycyclohexyi
methacrylate, polyisobornyl acrylate, polyisobornyl
methacrylate, polyisobutyl methacrylate, polyethyl
methacrylate, poly N-tert butyl acrylamide, and
polyisoprcpyi methacrylate, and B is a:
• hydrophilic and cationic block, for example
selected from: poly(2-vinyl pyridine), poly(4-vinyl
pyridine), poly(dimethyl amino ethyl methacrylate),
poly(diethyl amino ethyl methacrylate), poly(dimethyl
amino propyl methacrylamide), and poly(N-vinyl
pyrrolidone);
• hydrophilic and anionic block, for example
selected from: poly(acrylic acid), poly(methacrylic
acid), poiyfmaleic acid), poly(itaconic acid),
poly(fumaric acid), poly(crotonic acid), poly(acrylamido
glycolic acid), and poly(acrylamido 2-methylpropane
sulfonic acid] ,• or
• hydrophilic and ncn-ionic block, for example
selected from: poly(PEG methacrylate);
- triblock copolymer with the form A-B-C where:
• A and C are different hydrophobic blocks, for
example selected from: polystyrene, polymethyl
methacrylate, polycyclohexyl methacrylate, polyisobornyl
acrylate, polyisobornyl methacrylate, polyisobutyl
methacrylate, polyethyl methacrylate, poly N-tert butyl
acrylandde, and polyisopropyl methacrylate, and B is a:
c hydrophilic and cationic block, for example
selected from: poly(2-vinyl pyridine), poly{4-vinyl
pyridine), poly(dimethyl amino ethyl methacrylate},
poly(diethyl amino ethyl methacrylate), poly(dimethyl
amino propyl methacrylamide), and poly, Neocryl
A-1070®, Neocryl A-109G®, Neocryl 3T-62®, Neocryl
A-107 9® and Neocryl A-523® by the supplier AVECIA-
NEORESINS, Dow Latex 432® by the supplier DOW CHEMICAL,
Daitosol 5000 AD© or Daitosol 5000 SJ® by the supplier
DAITO KASSY KOGYO, Syntran 5760® by the supplier
interpoiymer, Allianz OPT by the supplier ROHM & HAAS,
aqueous dispersions of acrylic or styrene/acrylic
polymers sold under the trade name JONCRYL® by the
supplier JOHNSON POLYMER, or aqueous dispersions of
polyurethane sold under the names Neorez R-981® and
Neorez R-974® by the supplier AVECIA-NSQRESINS, Avalure
UR-4C5®, Avalure UR-410®, Avalure UR-425®, Avalure
UR-450®, Sancure 375®, Sancure 861©, Sancure 878® and
sancure 206 0® by the supplier GOODRICH, Impranil 85® by
the supplier BAYER, Aquamere H-1511® by the supplier
HYDROMER, sul£opolyesters sold under the trade name
Eastman AQ® by the supplier Eastman Chemical Products,
vinyl dispersions such as Mexomere PAM® from the supplier
CHIMEX and mixtures thereof.
The term "amphophilic or associative polymers" means
polymers comprising one or more hydrophilic portions that
render then partially soluble in water and one or more
hydrophobic portions via which the polymers associate or
interact. The following associative polymers may be
used: Nuvis FX1100® from Elementis, Aculyn 22®, Aculyn
44®, Aculyn 46® from Rohm&Haas, and Viscophobe DB1Q00®
from AMERCHOL. Diblock copolymers constituted by a
hydrophilic block (polyacrylate, polyethylene glycol) and
a hydrophobic block (polystyrene, polysiloxane) may also
be used.
The composition may comprise an oily phase and the
film-forming polymer may be present in said oily phase.
The polymer may then be in dispersion or in solution.
NAD type polymers or microgels (for example KSGs) nay be
used, as well as polymers of the PS-PA type or copolymers
based on styrene (Kratoa, Regalite).
Examples of non-aqueous dispersions of polymer
particles in one or more silicone and/or hydrocarbon oils
that can be stabilized at their surface by at least one
stabilizing agent, in particular a block, graft or random
polymer, that may be mentioned are acrylic dispersions in
isododecane, such as Mexcmere PAP® from the supplier
CHIMEX, and dispersions of particles of a graft ethylenic
polymer, preferably acrylic, in a liquid fatty phase, the
ethylenic polymer advantageously being dispersed in the
absence of an additional particle surface stabilizer such
as that described in particular in the document
WO 04/055081.
Film-forming polymers that may be used in the
composition of the present invention that may be
mentioned are synthetic polymers of the radical or
polycondensation type, polymers of natural origin, and
mixtures thereof.
In particular, the radical type film-forming
polymers may be polymers or copolymers, which are vinyls,
especially acrylic polymers.
Vinyl film-forming polymers may result from
polymerizing monomers containing an etliylenically
unsaturated bond having at least one acid group and/or
esters of said acid monomers and/or amides of said acid
monomers, such as unsaturated a,p-ethylenically
unsaturated carboxylic acids, for example acrylic acid,
methacrylic acid, crotonic acid, maleic acid or itaconic
acid.
Polymers of natural origin, optionally modified, may
be selected from shellac resin, sandarac gum, dammars,
elemis, copals, and cellulose polymers such as
nitrocellulose, ethylcelluiose or nitrocellulose esters
selected, for example, from cellulose acetate, cellulose
acetobutyrate, cellulose acetopropionate, and mixtures
thereof.
The film-forming polymer may be present in the form
of solid particles in aqueous or oily dispersion,
generally known as a latex or pseudclatex. The film-
forming polymer may comprise one or more suable
dispersions of particles of generally spherical polymers
of one or more polymers, in a physiologically acceptable,
liquid fatty phase. These dispersions are generally
termed polymer NADs, as opposed to latexes that are
aqueous polymer dispersions. These dispersions may in
particular be in the form of nanoparticles of polymers in
stable dispersion in said fatty phase. The nanoparticle
size is preferably in the range 5 ran to 600 nm. The
techniques for preparing said dispersions are well known
to the skilled person.
The composition may comprise at least one film-
forming polymer that is a linear block ethylenic film-
forming polymer. Said polymer may comprise at least one
first sequence {block} and at least one second sequence
having different glass transition temperatures (Tg), said
first and second sequences being connected together via
an intermediate sequence comprising at least one
constitutive monomer of the first sequence and at least
one constitutive monomer of the second sequence. As an
example, the first and second sequences and the block
polymer are incompatible with each other. Such polymers,
for example, are described in the documents EP 1 411 069
or WO 04/028483, which are herewith incorporated by-
reference.
Aqueous phase
The compositions of the invention may include at
least one aqueous phase.
The compositions of the invention, may include an
aqueous phase that may include particles of photonic
material, in particular particles having a polymeric
multilayer interference structure.
The water content of the aqueous phase is, for
example, greater than or equal to 30% by weight, more
preferably 40% by weight, highly preferably 50% by
weight.
The aqueous phase may also include a mixture of
water and (an) organic solvent (s) raiseible with wa:er
{miscibility in water greater than 50% by weight at 25°C)
such as lower monoalcohols containing 1 to 5 carbon atoms
such as ethanol, isopropanol, glycols containing 2 to 8
carbon atoms such, as propylene glycol, ethylene glycol,
1,3-butylene glycol, dipropylene glycol, C3-C1 ketones,
and C2-C4 aldehydes.
The aqueous phase may be present in an amount in the
range 1% to 99% by weight, in particular in the range 3%
to 80% by weight, and more particularly in the range 5%
to 60% by weight relative to the total weight of the
composition under consideration.
Fatty Phase
In all of the embodiments under consideration, the
compositions of the invention may include a fatty phase.
The fatty phase may, for example, be free of
particles of photonic material, in particular particles
having a polymeric multilayer interference structure.
The composition may comprise an oil such as, for
example, synthesized esters or ethers, linear or branched
hydrocarbons of mineral or synthetic origin, fatty
alcohols containing 8 to 26 carbon atoms, partially
fluorinated hydrocarbon and/or silicone oils, silicone
oils such as polymethylsiloxanes (PDMS) , which may
optionally be volatile, with a linear or cyclic silicone
chain, which may be liquid or pasty at ambient
-ernperature, and mixtures thereof; other examples are
given bslow.
A composition in accordance with the invention may
thus comprise at least one volatile oil.
Volatile oils
In the context of the present invention, the term
"volatile oil" means an oil (or non-aqueous medium} that
is capable of evaporating on contact with skin in less
than one hour, at ambient temperature and at atmospheric
pressure.
The volatile oil is a volatile cosmetic oil, liquit
at. ambient temperature, in particular having a r.on-zen
vapor pressure, at ambient temperature and atmospheric
pressure, in particular having a vapor pressure in th<
range 0.13 Pa to 40000 Pa (10~3mmHg to 300 iraiHg), i]
particular in the range 1.3 Pa to 13C00 Pa (0.01 mnHg t(
100 mmHg) , and more particularly in the range 1.3 Pa t<
1300 Pa (0.01 mmHg to 10 mmHg) .
The volatile hydrocarbon oils may be selected froi
hydrocarbon oils of animal or vegetable origin containing
8 to 16 carbon atoms, and in particular branched Ce-Ca
elkanes (also termed isoparaffins) , such as isododecan.
(also termed 2,2,4,4,6-pentamethylheptane), isodecane
isohexadecane and, for example, oils sold under the trad*
names isopars® or Permethyis®.
Examples of volatile oils that may also be used ar<
volatile silicones, for example linear or cyclic volatile
silicone oils, especially those with a viscosity
of 10.
The esters may he in particular be selected frorr.
esters, in particular of fatty acids, such as, for
example:
• cetostearyl octanoate, esiers of isopropyl
alcohol such as isopropyl myristate, isopropyl palmitate,
ethyl palmitate, 2-ethylhexyl palmitate, isopropyl
stearate or isostearate, isostearyl isostearate, octyl
stearate, hydroxy1 esters such as isostearyl lactate,
octyl hydroxystearate, diisopropyl adipate, heptanoates,
in particular isostearyl heptanoate, octanoates,
decanoates or ricinoleates of alcohols or polyalcohols,
such as propylene glycol dioctanoate, cetyl octanoate,
tridecyl octanoate, 2-ethylhexyl 4-diheptanoate and
palmitate, alkyl benzoate, polyethylene glycol
diheptanoate, propylene glycol 2-diethyl hexanoa~e and
mixtures thereof, Ci2-c:5 alcohol benzoates, hexyl laurate,
neopentanoic acid esters such as isodecyl neopentanoaue,
isotridecyl neopentanoate, isostearyl neopentanoaze,
octyldodecyl neopentanoate, isononanoic acid esters such
as isononyl isononanoate, isotridecyl isononanoate, octyl
isononanoate, or hydroxyl esters such as isostearyl
lactate, or di-isosr.earyl malate;
• esters of polyols, and penraetrythritol
esters, such as diper.taerythritol cetrahydroxystearate /
tetraisos tearate;
• esters of diol dimers and diacid dimers, such
as Lusplan DD-DA5® and Lusplan DD-DA7®, sold by the
supplier NIPPON FINE CHEMICAL and described in
application FR 03 0280S;
• fatty alcohols that are liquid at ambient
temperature having a branched and/or unsaturated carbon
chain containing 3 2 to 26 carbon atoms, such as 2-
octyldodecanol, isostearyl alcohol, oleic alcohol, 2-
hexyldecanol, 2-butyloctanol, or 2-undecylpentadecanol;
• higher fatty acids such as oleic acid,
linoleic acid, linolenic acid and mixtures thereof; and
• dialkyl carbonates, the 2 alkyl chains
possibly being identical or different, such as dicaprylyl
carbonate sold under the name Cetiol CC®, by Cognis;
• non-volatile silicone oils such as, for
example, non-volatile polydimethylsiloxanes (PDMS),
polydimethylsiloxanes comprising pendant alkyl cr alkoxy
groups and/or with silicone chain ends, the groups each
containing 2 to 24 carbon atoms r phenyl silicones such as
phenyl trimethicones, phenyl dimethicones, phenyl
trimethylsiloxy dipiienylsiloxan.es, diphenyl dimethicones,
diphenyl methyldiphenyl trisiloxanes, or 2~phenylethy±
trimethylsiloxysilicates, or dimethicones or
phenyl^rirr.ethicone with a viscosity less than or equal to
10G cSt, and mixtures thereof,-
- and mixtures thereof.
Surfactants
The composition of the invention may further contain
emulsifying and co-emulsifying surfactants present, for
example, in a proportion in the range 0.1% to 30% by
weigh- relative to the total composition weight.
Said surfactants may be selected from anionic or
non-ionic surfactants. Reference should be made to the
document "The Encyclopedia of Chemical Technology, KIRK-
OTHKER, volume 22, pp 333 - 432, third edition, 1979,
WILZY, for a definition of the properties and functions
of the surfactants, in particular pp 347 - 377 of said
reference, for the anionic and non-ionic surfactants.
Examples of surfactants that may be employed in the
invention and are suitable for producing a W/0 emulsion
that may be mentioned are dimethicone copolyols such as
the mixture of cyclomethicone and dimethicone copolyol
sold under the name DC 522 b C by the supplier Dow
corning, and dimethicone copolyols such as
laurylmethicone copolyol sold, under the name Dow Corning
520 0 Formulation Aid by the supplier Dow Corning and
cetyl dimethicone copolyol sold under the name ABIL EH
90R by the supplier GOLDSCKMIDT, or the polygiyceryl-4
isostearate / cetyl dimethicone copolyol / hexyllaurate
mixture sold under the name ABIL WE 09 by the supplier
GOLDSCHMIDT.
In is possible to add thereto one or more co-
emulsifying agents that may, for example, be selected
from the group comprising alkylated polyol esters.
Particular examples of alkylated polyol esters that may
be mentioned are esters of glycerol and/or sorbitan, for
example polyglycerol isostearate, such as the composition
sold under the name isolan GI 34 by the supplier
GOLDSCHMIDT, sorbitan isostearate, such as the
composition sold under the name ARLACEL- 9 87 by the
supplier ICI, sorbitan and glycerol isostearate, such as
the composition sold under the name ARLACEL 9 86 by the
supplier ici, and mixtures thereof.
Polyisobutylene surfactants containing esterified
succinic end groups, such as those sold under the names
Lubrizol 5603 and Chemcinnate 2 00C hy the suppliers
Lubrizol and Cheirror., may also be used as emulsifiers
suitable for obtaining a W/0 emulsion.
Surfactants for w/0 emulsions that may also be used
include a solid cross-linked elastomeric
organopoiysiloxane comprising a~ least one oxyalkylene
group, such as those obtained according to the procedure
of Examples 3, 4 and S of document: US-A-5 412 004 and cf
the examples of document US-A-5 611 487, especially the
product of Example 3 (synthesis example) of patent
US-A-5 412 004, and such as the product sold under the
reference KSG 21 by the supplier Shin-Etsu.
Examples of surfactants that may be used in the
invention that are suitable for obtaining an O/W emulsion
that may be mentioned are non-ionic surfactants, and
especially esters of polyols and of fatty acids with a
saturated or unsaturated chain containing, for example, 8
to 24 carbon atoms and more preferably 12 to 22 carbon
atoms, and their oxyalkylenated derivatives, i.e.
derivatives containing oxyethylenated and/or
oxypropylenatad units, such as the glyceryl esters of Cg-
C24 fatty acids, and their oxyalkylenated derivatives;
polyethylene glycol esters of C8-C24 fatty acids, and
their oxyalkylenated derivatives; sorbitol esters of Cg-
C2i fatty acids, and their oxyalkylenated derivatives;
sugar (sucrose, glucose or alkylglucose) esters of Cs-C2i
fatty acids, and their oxyalkylenated derivatives; ethers
of fatty alcohols; sugar ethers of C8-C24 fatty alcohols;
oxyethylenated fatty acid ethers of glucose or
alkylglucose; and mixtures thereof.
Glyceryl esters of fatty acids that may in
particular be mentioned include glyceryl stearate
(glyceryl mono-, di- and/or tristearate) (CTFA name:
glyceryl stearate) or glyceryl ricinoleate, and mixtures
thereof.
Polyethylene glycol esters of fatty acids that may
in particular be mentioned include polyethylene glycol
stearate (polyethylene glycol mono-, di- and/or
tristearate) and more especially polyethylene glycol 50
OH monosteara-e (CTFA name: PEG-50 stearate),
polyethylene glycol 100 oe monostearate [CTFA name:
FEG-100 stearate) and mixtures thereof.
It is also possible to use mixtures of these
surfactants, such as the product containing glyceryl
stearate and PEG-100 stearate, sold under the name
ARLACEL 155 by the supplier Uniqema, and the product
containing glyceryl stearate (glyceryl mono-d.istearate)
and potassium stearate, sold under the name TEGIN by the
supplier GCLDSCHMIDT (CTFA name: glyceryl stearate SE).
Fatty acid esters of glucose or of alkylglucose that
may in particular be mentioned include glucose palmitate,
alkylglucose sesquistearates, such as methyl glucose
sesquistearate, alkylglucose palmitates, such as
methylglucose or ethylglucose palmitate, fatty esters of
methylglucoside and more especially the diester of
methylglucoside and of oleic acid (CTFA name: Methyl
glucose dioleate) ,- the mixed ester of methylglucoside and
of the oleic acid / hydroxystearic acid mixture (CTFA
name: Methyl glucose dioleate / hydroxystearate); the
ester of methylglucoside and isostearic acid (CTFA name:
Methyl glucose isostearate); the ester of methylglucoside
and lauric acid (CTFA name: Methyl glucose laurate); the
mixture of the monoester and diester of methylglucoside
and isostearic acid (CTFA name: Methyl glucose sesqui-
isostearate); the mixture of the monoester and diester of
methylglucoside and stearic acid {CTFA name: Methyl
glucose sesquistearate) and in particular the product
sold under the name Glucate SS by the supplier AMERCHOL,
and mixtures thereof.
Examples of oxyethylenated ethers of a fatty acid
and glucose or alkylglucose that may be mentioned include
the oxyethylenated ethers of a fatty acid and
methylglucose, for example the polyethylene glycol ether
of the diester cf methyl glucose and stearic acid
containing approximately 20 moi of ethylene oxide (CTFA
name: PBG-20 methyl glucose distearate), such as the
product sold under ~he name Giucam E-2 0 distearate by the
supplier AKERCHOL; the polyethylene glycol ether of the
mixture of the monoester and diester cf mezhylgiucose and
stearic acid containing about 2 0 moi of ethylene oxide
(CTFA name: PEG-2C methyl glucose sesquistearate}, for
example the produce sold under the name Giucamate SSE-2 0
by the supplier AMERCHOL, and the product sold, under the
name Grillccose PSE-20 by the supplier GOLDSCKMIDT, and
mixtures thereof.
Examples of sucrose esters that may be mentioned
include saccharose palmitostearate, saccharose stearate
and saccharose monolaurate. Examples of ethers of fatty
alcohols that may be mentioned include polyethylene
glycol ethers of fatty alcohols containing 8 to 30 carbon
atoms and especially 10 to 22 carbon atoms, such as
polyethylene glycol ethers of cetyl alcohol, stearyl
alcohol or cetearyl alcohol {mixture of cetyl and stearyl
alcohol). Examples that may be mentioned include ethers
comprising 1 to 2 00 and preferably 2 to 100
oxyethylene groups, such as those with CTFA name
Ceteareth-2C and Ceteareth-30, and mixtures thereof.
Sugar ethers that may in particular be mentioned are
alkyIpolyglucosides, for example decylglucoside, such as
the product sold under the name MYDQL 10 by the supplier
Kao Chemicals, the product sold under the name PLAWTAREN
2 000 by the supplier Henkel, and the product sold under
the name ORAMIX HS 10 by the supplier SEPPIC; caprylyl /
capryl glucoside, such as the product sold under the name
ORAMIX CG 110 by the supplier SEPPIC or under the name
L'JTEMSOL GD 70 by the supplier BASF; laurylglucoside,
such as the products sold under the names PLANTAREN
1200 W and PLANTACARE 1200 by the supplier Henkel;
cocoglucoside, such as the product sold under the name
PLANTACARE 818/UP by the supplier Henkel; cetostearyl
glucoside optionally as a mixture with cetostearyl
alcohol, sold, for example, under the name MONTANOV 68 by
the supplier SEPPIC, under the name TEGO-CARE CG90 by the
supplier GOLDSCHMIDT and under the name EMULGADE KE3302
by the supplier Henkel; arachidyl glucoside, for example
in the form of the mixture of arachidyl alcohol and
behenyl alcohol and arachidyl glucoside, sold "under the
name MONTANOV 202 by the supplier SEPPIC;
cocoylethylglucoside, for example in the form of a
mixture (35/65) with cetyl and stearyl alcohol, sold
under the name MOKTTANOV 82 by the supplier SSPPIC, and
mixtures thereof.
The composition according to the invention may also
contain amphiphilic polymers as enuzlsifiers or co-
emulsifiers.
The term "amphiphilic polymer" means any polymer
comprising both a hydrophilic portion and a hydrophobic
portion separating two liquids of different polarity and
thus allowing liquid-liquid dispersions of a direct,
inverse or multiple type to be stabilized.
The amphiphilic polymer may reduce the water/oil
interfacial tension to 10 mN/rn, irrespective of the oil.
These polymers are ionic (anionic or cationic) or
amphoteric.
The amphiphilic polymers in accordance with the
invention generally have a number average molecular
weight in the range 1000 g/mol to 20000000 g/mol,
preferably in the range 20000 to 8000000, for example in
the range 100000 g/mol to 700000 g/mol. The quantity of
amphiphilic polymer used in accordance with the invention
may be in the range 0.01% to 20% by weight, preferably
0.1% to 10% by weight, for example 0.2% to 5% by weight.
Particular examples that may be used are acrylate /
C10-C3Q- alkylacrylate copolymers such as the products sold
under the names PEMULEN TRl, PEMULEN TR2 and CARBOPOL
1382 by the supplier GOODRICH, or mixtures thereof. it
is also possible to use acrylate / steareth-20 itaconate
copolymers and acrylate / ceteth-2 0 itaconate copolymers
sold under the names STRUCTURE 20C1 and STRUCTURE 3001 by
the supplier NATIONAL STARCH. Particularly suitable
cross-linked or non cross-linked amphiphilic polymers are
the products sold under the names ARISTOFLBX LNC,
ARISTOFLEX SKC, and ARISTOFLEX EMS by the supplier
CLARIANT.
An example of a terpolymer that may be mentioned is
the methacrylic acid / methyl acrylate / behenyl
dimethyl-m- isopropenylbenzylisocyanate terpolymer
ethoxylated with 40 EO units, sold by the supplier
AMERCHOL under the names VISCOPHOBE DB 1000 NP3-NP4.
It is also possible to mention cross-linked
terpoiymers of methacrylic acid, ethyl aerylate,
polyethylene glycol stearyl ether (10 EO) (Steareth 10) ,
such as those sold by the supplier allied Colloids under
the name SALCARE SC 80.
Examples of anionic polymers for use in the
invention are polymers of i soph thai ic acid or
sulfoisophthalic acid, in particular copolymers of
phthalate / sulfoisophthalate / glycol (for example
diethylene glycol / phthalate / isophthalate / 1,4-
cyclohexanediitiethanol) sold under the name "Eastman AQ
Polymer" (AQ 35S, AQ 38S, AQ 55S and AQ 48 Ultra) by the
supplier Eastman Chemical.
Additives
The composition comprising the particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, may comprise at least
one additive selected from adjuvants that are normal in
the cosmetics field, such as fillers, softening agents,
coloring agents, surfactants, hydrophilic or lipophilic
gelling agents, active ingredients, either hydrosoluble
or liposoluble, preservatives, moisturizers such as
polyols and in particular glycerin, sequestrating agents,
antioxidants, solvents, fragrances, physical and chemical
sunscreens, especially against TJVA and/or UVB, odor
absorbers, pH adjusting agents (acids or bases), and
mixtures thereof.
The composition may contain at least one active
ingredient having a complementary activity in the solar
protection field, such as antioxidants, whitening agents
in the context of anti-pigmentation and depigmentation,
or anti-ageing active ingredients.
The additive or additives may be selected from those
cited in the CTFA Cosmetic Ingredient Handbook, 10th
Edition, Cosmetic and Fragrance Assn., inc, Washington DC
(2004), herev?ith incorporated by reference.
Galenical dosage forms
The particles of photonic material, in particular
particles having a polymeric multilayer interference
structure, may be used in lotions, creams, milks, balms,
pommades, gels, emulsions, films, patches, sticks, for
example lipsticks, powders, or pastes, for the skin, the
lips, the hair or the nails.
The particles of the invention may, for example, be
incorporated into any type of cosmetic composition, for
example of the gloes, lipstick, eye-liner, mascara,
foundation, eyeshadow, nail polish etc type.
The photonic material films, in particular films
having a polymeric multilayer interference structure of
the invention, may bs applied by transfer. Before
application to the keratinous materials, said films may
be attached to an adhesive layer.
When the cosmetic composition of the invention is
used to protect the hair against solar UV radiation, it
may be in the form of a shampoo, lotion, gel, emulsion,
or non-ionic vesicular dispersion, and may, for example,
constitute a rinse-out composition, a composition for
application before or after shampooing, before or after
coloring or stripping, before, during or after penning or
straightening, as a setting or treatment lotion, a lotion
or gel for blow drying or setting, a perming or
straightening composition, or for coloring or stripping
the hair.
Modes of application
The composition including parricles of photonic
material, in particular particles having a polymeric
multilayer interference structure, may be applied, with
the hand or using an applicator.
Application may also be accomplished by spraying or
projection using a piezoelectric device, for example, or
by transfer of a layer of composition that has been
deposited on an intermediate support.
Packaging
The composition may toe packaged in any packaging
device, especially formed from thermoplastic material, or
on any support provided for that purpose.
The packaging device may be a bottle, a pump bottle,
an aerosol bottle, a tube, a sachet, or a pot.
Examples
Example 1
A gel of polystyrene-poly<2-vinylpyridine)
quaternised diblock copolymer (PS-D-Q-P2VP) (190K/19QK)
with a thickness of 3 urn (dry) was obtained by dip
coating, on a rigid surface, from a 5% by weight PS-b-Q-
P2VP solution in propylene glycol monomethyl ether
acetate. The gel was then swollen using an agueous 2.5 M
NH4CI solution. A photonic gel interfering in the
wavelength range 340 ran to 385 nir. was obtained. This
photonic gel film was suitable for use as a
photoprotective agent for keratinous materials.
Example 2
The gel from Example 1 was detached from the rigid
support then fragmented before swelling into particles
with a largest dimension of less than 50 uir. using a dry
bail mill. The particles thus obtained were then
dispersed in an aqueous 2.5 M NHjCI solution.
After separating by filtration, particles having a
polymeric multilayer interference structure interfering
ir. the TJV range (between 340 nm and 385 rim) were
obtained.
Example 3
A 3 pm thick (dry) ?S-b-Q-P2VP (190K/19CK) gel was
spread over a rigid support then fragmented before
gwelling into particles with a largest dimension of less
than 5C urn using a dry ball mill. The particles thus
obtained were then dispersed in a mixture containing 50%
by weight of glycerol and 50% by weight of an aqueous
2.5 M NH4Cl solution. After separating, particles having
a polymeric multilayer interference structure interfering
in the wavelength range 340 nm to 385 nm were obtained.
Introducing glycerol had the effect of preserving
the interference properties of the photonic gel after
drying.
Example 4: Photoprotective cosmetic composition based on
photonic gel particles
Fatty phase
ARISTOFLEX LNC {CLARIANT) 1%
Cyclopentasiloxane 6%
Oc-ylpaliaitate 6%
Aqueous phase
Particles of phoconic gel produced
in Example 3 10%
Glycerol 5%
Preservative 0.3%
Water qsp 100%
Example 5: Production of photonic gel particles
coagulated with silica
A 3 µm thick (dry) PS-b-Q~F2VP (190K/19DK) gel was
obtained by dip coating, on a rigid surface, from a 5%
P£-b-Q-?2v? solution in propylene glycol monomethyl ether
acetate. The gel was then fragmented, before swelling
into particles with a largest dimension of less than
50 µm using a dry ball mill. The particles obtained were
then dispersed and swollen in methanol.
An aqueous solution of TEOS (tetraethoxysilane) with
a concentration 0.45 M was then added. An aqueous 2.5 M
WHaCl solution was added with vigorous stirring.
Particles having a polymeric multilayer interference
structure interfering in the wavelength range 340 nm to
385 nm and insensitive to the dispersion medium were
obtained.
Example 6: Photonic gel swollen with an aqueous sunscreen
solution
A 3 µm thick (dry) PS-D-Q-P2VP (19OK/19OK) gel was
obtained by dip coating, on a rigid surface, from a 5%
PS-b-Q-P2VP solution in propylene glycol monomethyl ether
acetate. This gel was then swollen with an aqueous 3%
solution of Mexcryl SX (Chimex) (TEREPHTHALYLIDENE
DICAMPHOR SULFONIC ACID, 33% in water), A phoconic gel
interfering in the wavelength range 33 0 nm to 3B5 nm with
a significantly reduced goniochroinatic effect was thus
obtained.
Said photonic gel film was suitable for use as a
phoroprotective agent for keratinous materials.
Example 7: Photonic gel swollen with an aqueous sunscreen
solution
A 3 µm thick (dry) PS-b-Q-?2VF (190K/190K) gel was
obtained by dip coating, on a rigid surface, from a 5%
PS-b-Q-P2VP solution ir. propylene glycol monomethyl ether
acetate. This gel was swollen with an aqueous D.5%
solution of 2usolex 232 (Merck) (PHENYLBEKZIMIDAZCLE
SULFONIC ACID). A photonic gel interfering in the
wavelength range 230 nm to 385 nm was thus obtained.
Said photonic gel film was suitable for use as a
photoprotective agent for keratinous materials.
Example 3:____Photoprotective____cosmetic composition
comprising two types of particles with polymeric
multilayer interference structures that interfere
differently and in a complementary manner with UV
Fatty phase
ARISTOFLEX LATC (CLARIANT) 1%
Cyclopentasiloxane 6%
Octylpalmitate 6%
Aqueous phase
Particles having a polymeric multilayer interference
structure obtained by ball milling a photonic gel from
Example 6 5%
Particles having a polymeric multilayer interference
structure obtained by ball milling a photonic gel from
Example 7 5%
Glycerol 5%
Preservative 0.3%
Water qsp 100%
Example 9.-____Fhotoprotective cosmetic composition
comprising two types of particles with polymeric
multilayer interference structures that interfere
-differently and in a complementary manner with UV
Fatty phase
ARISTOFLEX LNC (CLARIANT) 1%
Cyclopentasiloxane 6%
Octylpalmitate 6%
Aqueous phase
Particles having a polymeric multilayer interference
structure from Example 2 5%
Particles having a polymeric rmilnilayer interference
structure similar to those of Example 1 but swollen with
a 1 M solution of NH4CI obtained, using the method of
Example 2 5%
Glycerol 5%
Preservative 0.3%
Water qsp 100%
Example 10: Photonic gel swollen with an optical
brightener solution
A 3 urn thick (dry) PS-b-Q-P2vp (190K/190K) gel was
obtained by dip coating, on a rigid surface, from a 5%
PS-b-Q-P2v? solution in propylene glycol monomethyl ether
acetate. Said gel was then swollen with an aqueous 0.5%
solution of Tinopal CBS X (CIBA) (MSODIUK
DISTYK.YLBI PHENYL DlSULFONATE). A photonic gel
interfering in the UV region and colored blue 'was
obtained that was suitable, once fragmented, for use in
lightening human kerarinous materials, for example the
skin.
Example 11: Colored photonic gel
A 3 urn thick (dry) PS-b-Q-P2VP (190K/190K) gel was
obtained by dip coating, on a rigid surface, from a 5%
?S-b-Q-P2VP solution in propylene glycol monomethyl ether
acetate. Said gel was then swollen with an aqueous 1.5 M
NH4CI solution. The reflected wavelength corresponding to
the transmission minimum was approximately 550 mi, i.e. a
yellow color.
The film was suitable, for example, for use to even
out the complexion either before or after fragmentation.
Example 12: Colored photonic gel
A 3 mm thick (dry) ?S-b-Q-?2VP {19CK/190K) gel was
obtained by dip coating, on a rigid surface, from a 5%
PS-b-Q~P2VP solution in propylene glycol rncnomethyl ether
acetate. Said gel was swollen with an aqueous 0.5 M NE^Cl
solution. The reflected wavelength corresponding to the
transmission minimum was approximately 410-420 nm, i.e. a
violet color.
The film was suitable, for example, for use to even
out the complexion either before or after fragmentation.
example 13: Colored photonic gel
A 3 µm thick (dry) PS-b-Q-P2VP (19 0K/190K) gel was
obtained by dip coating, on a rigid surface, from a 5%
PS-b-Q-P2VP solution in propylene glycol monomethy]. ether
acetate. Said gel was then swollen with an aqueous 1 M
NH4Cl solution. The reflected wavelength corresponding ,to
the transmission minimum was approximately 600 nm, i.e. a
yellow-orange color. The film was suitable, for example,
for use to even out the complexion either before or after
fragmentation.
The photonic gels described in Examples 11 to 13
could be fragmented using the method of Example 2.
The photonic gels described above, for example the
colored photonic gels of Examples 11 to 13, could be
coagulated by the action of a silica precursor (TEOS) or
with glycerol, as in Example 3.
Example 14: Reflection spectrum of a photonic gel
Figure 5 shows two absorption spectra of a PS-P2VP
photonic gel from the publication Wat Mat. Vol 6,
957-960, 2008.
The absorption peaks measured correspond to the
transmission minima and to the reflection peaks of the
photonic gel.
In the absence of a swelling agent, the absorption
spectrum had no peak and the photonic gel did not have
interference properties.
in contrast, when the photonic gel was swollen with
pure water, the absorption spectrum could, as shown, have
5 reflection bands each corresponding to a distinct order
of interference. The peak in the UV in this example
corresponds to an order of interference of 5.
Unless otherwise specified, the expression
"comprising a" should be construed as meaning "comprising
at least one".
CLAIMS
1. A photoprotective cosmetic composition including
particles having a polymeric multilayer interference
structure, at least two layers of said structure
comprising an amphiphilic polymer.
2. A composition according to claim 1, wherein the
particles having a polymeric multilayer interference
structure have a reflection spectrum including a
reflection peak in the wavelength range 2 50 nm to
400 nm.
3. A composition according to claim 1 or 2, wherein the
amphiphilic polymer includes a swelling agent.
4. A composition according to any preceding claim,
comprising a fatty phase and an agueous phase, the
aqueous phase including particles having a polymeric
multilayer interference structure.
5. A composition according to any preceding claim,
wherein the particles having a polymeric multilayer
interference structure include a fixing agent selected
from inorganic materials, for example silica and its
precursors for example TEOS, glycols, for example
glycerol, dipropylene glycol, sorbitol, butylene
glycol, and PEGs having a molecular weight in the
range 400 g/mol to 50000 g/mol.
6. A composition according to any preceding claim,
including at least two different types of particles
having a polymeric multilayer interference structure,
each particle type having a different transmission
spectrum in the wavelength range 250 nm to 400 nm.
7. A composition according to any preceding claim,
wherein the amphophilic polymer has a lamellar
structure.
8. A composition according to any preceding claim,
wherein the amphiphilic polymer comprises a block
copolymer.
9. A composition according to the preceding claim,
wherein the amphiphilic polymer comprises, in
particular consists of, a:
- dibiock copolymer with the form A-B where A is a
hydrophobic block selected, for example, from:
polystyrene, polymethyl methacrylate, polycyclohexyl
methacrylate, polyisobornyl acrylate, polyisobornyl
methacrylate, polyiscbutyl mcthacrylate, polyethyl
methacrylate, poly N-tert butyl acrylamide and
polyisopropyl methacrylate, and B is a:
• hydrophilic and cationic block, for example
selected from: poly(2-vinyl pyridine), poly(4-vinyl
pyridine), poly(dimethyl amino ethyl methacrylate),
polyfdiethyl amino ethyl methacrylate), poly(dimethyl
amino propyl methacrylamide), and poly(N-vinyl
pyrrolldone);
• hydrophilic and anionic block, for example
selected from: poly(acrylic acid), poly(methacrylic
acid), poly(maleic acid), poly(itaconic acid),
poly(fumaric acid), poly{crotonic acid),
poly(acrylamico glycolic acid) , and poly (acrylainido 2-
methyipropane sulfonic acid); or
• hydrophilic and non-ionic block, for example
selected from: polyJPSG methacrylate);
- triblock copolymer with the form A-B-C where:
• A and C are different hydrophobic blocks, for
example selected from: polystyrene, polymethyl
methacrylate, polycyclohexyl methacrylate,
polyisobornyl acrylate, polyisobornyl methacrylate.
polyisobutyl methacrylate, polyethyl nethacrylate,
poly N-tert butyl acrylamide, and polyisopropyl
methacrylate, and B is at
o hydrophilic and cationic block, for
example selected from: poly(2-vinyl pyridine), poly(4~
vinyl pyridine), poly (dimethyl amino ethyl
methacrylate), poiy(diethyl amino ethyl methacrylate),
poly(dimethyl amino propyl methacrylamide), and
poly(N-vinyl pyrrolidone);
o hydrophilic and anionic block, for
example selected from: poly(acrylic acid),
poly(methacrylic acid), poly(maleic acid),
poly(itaconic acid), poly(fumaric acid), poly(crotonic
acid), poly(aerylamido glycolic acid), and
poly(acrylamido 2-methylpropane sulfonic acid); or
o hydrophilic and non-ionic block, tor
example selected from: poly(PEG methacrylate); or
* B is a hydrophobic block, for example
selected from: polystyrene, polymethyl methacrylate,
polycyclohexyl methacrylate, polyisobornyl aerylate,
polyisobornyl methacrylate, polyisobutyl methacrylate,
polyethyl methacrylate, poly N-tert butyl acrylamide
and polyisopropyl methacrylate and A and C are
different and selected from:
o hydrophilic and cationic blocks, for
example selected from: poly{2-vinyl pyridine), poly(4-
vinyl pyridine), poly(dimethyl amino ethyl
methacrylate), poly(diethyl amino ethyl methacrylate) ,
poly(dimethyl amino propyl methacrylamide) , and
poly(N-vinyl pyrrolidone);
o hydrophilic and anionic blocks, for
example selected from: poly(acrylic acid),
pcly(methacrylic acid), polyfmaleic acid),
poly(icaconic acid), poly{fumaric acid), poly(crotonic
acid), poly(acrylamido glycolic acid) and
poly(acrylamido 2-methylpropane sulfonic acid); or
o hydrophilic and non-ionic blocks, for
example selected from: poly(PEG methacrylatej .
10. A composition according to the preceding claim,
wherein the amphiphilic polymer comprises, in
particular consists of, adiblock copolymer with the
form A-B where A is polystyrene and B is poly(2-vinyl
pyridine).
11. A composition according to any preceding claim,
wherein the particles having a polymeric multilayer
interference structure are plate-like.
12. A composition according to any one of claims 1 to 11,
wherein the particles having a polymeric multilayer
interference structure include another optically-
active material, for example within the amphiphilic
polymer.
13. A composition, according to any one of claims 3 to 12,
wherein the swelling agent is selected from:
- water and organic or inorganic saline solutions
with a concentration in the range 0.01 M to 5 M, for
example solutions of sodium, magnesium, potassium,
calcium or copper salts, solutions of phosphates and
solutions of ammonium salts;
- the following compounds alone, as a mixture or in
aqueous solution:
o glycerol, PEGs having a molecular weight in
the range 400 g/mol to 50000 g/mol, mono-, di- and
oligc-saccharides that are soluble in water at at
least 1% by weight, sorbitol, propylene glycol,
dipropylene glycol, butylene glycol, water-soluble
polyols, water-irascible lower alcohols, for example
methanol, ethanol or isopropanol;
o neutralised or non-neutralised solutions of
JV screens; and
o polar oils, for example lauroyl isopropyl
sarcosinate, octyldodecanol, undecane and tridecane as
well as oily solutions of organic screens.
14.A method of preparing a cosmetic composition according
to any one of claims 3 to 13, comprising:
a) a step of bringing a swelling agent into contact
with a polymeric multilayer structure having at least
two layers comprising ail amphiphilic polymer;
b) a step of fragmenting a film having a polymeric
multilayer structure wherein at least two layers
comprise an amphiphilic polymer into particles having
a polymeric multilayer structure with a largest
dimension of less than 100 pin and with a smallest
dimension of 100 nm or more; and
c) a step of dispersing the particles wich the
polymeric multilayer interference structure obtained
after carrying out steps a) and b) in a cosmetically
acceptable medium;
step b) being carried out before or after step a).
15.A non-therapeutic and in particular cosmetic method of
photoprotecting human keratinous materials against,
solar UV radiation, the method comprising applying a
cosmetic composition according to any one of claims 1
to 13 to the human keratinous materials.
16.A photoprotective film against solar UV radiation, for
application to human keratinous materials, the film
including a multilayer interference structure
screening solar UV radiation in which at least two
layers comprise an amphiphilic polymer.
17. A photoprotective composition including particles of
photonic material, in particular particles having a
polymeric multilayer interference structure, at least
two layers of said structure comprising an amphiphilic
polymer.
18.A composition according to claim 17, wherein the
particles of photor.ic material , in particular
particles having a polymeric multilayer interference
structure, have a reflection spectrum including a
reflection peak in the wavelength range 250 nm to
400 nra.
19. A composition according to any one of claims 17 and
18, wherein the photonic material includes at least
one swelling agent.
20.A composition according to any one of claims 17 to 19,
comprising a fatty phase and an aqueous phase, the
aqueous phase including particles of photonic
material, in particular particles having a polymeric
multilayer interference structure.
21.A composition according to any one of claims 17 to 20,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, include a fixing agent
selected from inorganic materials, for example silica
and its precursors, for example TEOS, glycols, for
example glycerol, dipropylene glycol, sorbitol,
butylene glycol, and PEGs having a molecular weight in
the range 400 g/mol to 500 00 g/mol.
22. A composition according to any one cf claims 17 to 21,
comprising at least two different types of pho-onic
material particles, in particular particles having a
polymeric multilayer interference structure, each
particle type having a different transmission spectrum
in the wavelength range 250 mn to 400 nm.
23. A composition according to any preceding claim,
wherein the amphophilic polymer has a lamellar
structure.
24.A composition according to any preceding claim,
wherein the amphiphilic polymer comprises, in
particular consists of, a block copolymer.
25. A composition according to the preceding claim,
wherein the amphiphilic polymer comprises, in
particular consists of, a:
- difalock copolymer with the form A-B where A is a
hydrophobic block selected, for example, from:
polystyrene, polymethyl methacrylate, polycyclohexyl
methacrylate, polyisobornyl acrylate, polyisobornyl
methacrylate, polyisobutyl methacrylate, polyethyl
methacrylate, poly N-tert butyl acrylamide, and
polyisopropyl methacrylate, and B is a:
• hydrophilic and cationic block, for example
selected from: poly(2-vinyl pyridine), poly(4-vinyl
pyridine), poly(dimethyl amino ethyl methacrylate),
poly{diethyl amino ethyl methacrylate}, poly(dimethyl
amino propyl methacrylamide), and poly(N-vinyl
pyrrolidone);
• hydrophilic and anionic block, for example
selected from: poly(acrylic acid}, poly(methacrylic
acid), poly(maleic acid), poly(itaconic acid),
poIy(fumaric acid), polyfcrotonic acid),
polyfacrylamido glycolic acid), and poly(acrylanido 2-
methylpropane sulfonic acid); or
• hydrophilic and non-ionic block, for example
selected from: poly(PEG methacrylate)?
- triblock copolymer with the form A-3-C where:
• A and C are different hydrophobic blocks, for
example selected from: polystyrene!, polymethyl
methacrylate, polycyclohexyl methacrylate,
polyisobornyl acrylate, polyisobornyl methacrylate,
polyisobutyl methacrylate, polyethyl methacrylate,
poly N-tert butyl acrylamide and polyisopropyl
methacrylate, and B is a:
o hydrophilic and cationic block, for
example selected from: poly(2-vinyl pyridine), poly(4-
vinyl pyridine), poly (dimethyl amino ethyl
methacrylate), poly(diethyl amino ethyl methacrylate),
poly(dimethyl amino propyl methacrylamide), and
poly(N-vinyl pyrrclidone);
o hydrophilic and anionic block, for
example selected from: poly(acrylic acid),
poly(methacrylic acid), poly(maleic acid),
poiy(itaconic acid), poly(fumaric acid), poly(crotonic
acid), poly(acrylamido glycolic acid), and
poly(acrylamido 2-methylpropane sulfonic acid); or
o hydrophilic and non-ionic block, for
example selected from: poly (PEG methacrylate) ,- or
• B is a hydrophobic block, for example
selected from: polystyrene, polymethyl methacrylate,
polycyclohexyl methacrylate, polyisobornyl acrylate,
polyisobornyl me-hacryiats, polyisobutyl methacrylate,
polyethyl methacrylate, poly N-tert butyl acrylamide,
and polyisopropyl methacrylate and A and C are
different and selected from:
o hydrophilic and cationic blocks, for
example selected from: poly(2-vinyl pyridine}, poly{4-
vinyl pyridine), poly(dimethyl amino ethyl
methacrylate), poly(diethyl amino ethyl methacrylate),
poly(dimethyl amino propyl methacrylamide), and
poly(N-vinyl pyrrolidone);
o hydrophilic and anionic blocks, for
example selected from: poly(acrylic acid),
poly(methacrylic acid), poly(maleic acid),
poly(itaconic acid), poly(fumaric acid), poly(crotonic
acid), poly(acrylamido glycolic acid), and
poly(acrylamido 2-me-hyipropane sulfonic acid); or
o hydrophilic and non-ionic blocks, for
example selected from: poly(PEG methacrylate).
26. A composition according to the preceding claim,
wherein the amphophilic polymer comprises, in
particular consists of, a diblock copolymer with the
form A-B where A is polystyrene and B is poly (2-vinyl
pyridine).
27.A composition according to any one of claims 17 to 2 6,
wherein the particles having a polymeric multilayer
interference structure are plate-like.
28.A composition according to any one of claims 17 to 27,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, include another optically
active material, for example within the amphiphilic
polymer.
29.A composition according to any one of claims 19 to 28,
wherein the swelling agent is selected from:
- water and organic or inorganic saline solutions
with a concentration in the range 0.01 M to 5 M, for
example solutions of sodium, magnesium, potassium,
calcium or copper salts, solutions of phosphates and
solutions of ammonium salts;
- zhe following compounds alone, as a mixture or in
agueous solution:
o glycerol, PEGS having a molecular weight in
the range 400 g/mol to 50000 g/mol, mono-, di- and
oligc-saccharides that are soluble in water at at
least 1% by weight, sorbitol, propylene glycol,
dipropylene glycol, butylene glycol, rater-soluble
polyols, water-miscible lower alcohols, for example
methanol, ethanol or isopropanol, benzene, acetone, ß-
me-hylbutyric acid, a-ethylbutyric acid, 2,2,2,-
trifluoroethanol, 1-butanol, 1,4-butanediol,
chloroform, bromoethane, methyl acetate, ethyl
acetate, dimethylformamide, butan-2-one,
divinylbenzene, propylene glycol monomethylether
acetate (PGMEA), and acetic acid solutions;
o neutralized or non-neutralized solutions of
UV screens; and
o polar oils, for example lauroyl isopropyl
sarcosinate, octyldodecanol, a C12-C15 alkylbenzoate,
undecane and tridecane as well as oily solutions of
organic screens.
30. A cosmetic composition comprising, in a cosmetically
acceptable medium, at least particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, as defined in any
one of claims 17 to 29.
31. A method of preparing a composition according to any
one of claims 19 to 30, comprising:
a) a step of bringing a swelling agent into contact
with a photonic material, in particular with a
polymeric multilayer structure having at least two
layers comprising an amphophilic polymer,-
b) a step of fragmenting a film of photonic
material, in particular a film having a polymeric
multilayer structure wherein at least two layers
comprise an amphiphilic polymer, into particles of
photonic material, in particular into particles having
a polymeric multilayer structure, with a largest
dimension of less than 100 urn and with a smallest
dimension of 103 nm or more; and
c) a step of dispersing the particles of photonic
material, in. particular particles having a polymeric
multilayer interference structure, obtained after
carrying out steps a) and b) , in a suitable medium;
step b) being carried cut before or after step a).
32. A method of photoprotecting a material against solar
UV radiation, the method comprising at least treating
said material with a photoprotective composition
according to any one of claims 17 to 30 or integrating
at least said composition into said material.
33.A non-therapeutic and in particular cosmetic method of
photoprotecting human keratinous materials against
solar UV radiation, the method comprising at least
applying a cosmetic composition according to claim 30
to human keratinous materials.
34. A method of photoprotecting an ink, a paint, or a
coating, the method comprising incorporating at least
one composition as defined in any one of claims 17 to
29 into said ink or said paint or said coating.
35. A method of photoprotecting a material manufactured
from at least one synthetic or natural polymer, the
method comprising at least treating said polymer with
at least one composition as defined in any one of
claims 17 to 29 or integrating at least said
composition into said material.
36.A method of photoprotecting an organic or mineral
glass, the method comprising at least treating said
glass with at least one composition as defined in any
one of claims 17 to 2 9 or integrating at least said
composition into said glass.
37, a method of photoprotecting a material comprising at
least sarural fibers and/or artificial fibers and/or
synthetic fibers sue." as textiles or papers, the
method comprising at least treating said material with
at least one composition as defined in any one of
claims 17 to 29 or integrating at least said
composition into said material.
3 8.A film for photoprotecting against solar UV radiation,
the film including a photonic material, in particular
a multilayer interference structure, screening solar
UV radiation wherein at least two layers comprise an
amphiphilic polymer.
35.A cosmetic composition including particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, comprising an
amphiphilic polymer and producing a visible color.
40. A composition according to claim 39 having, before
application to keratinous materials, a reflection
spectrum including a reflection peak in the wavelength
range 400 nm to 8 00 nm.
41. A composition according to claim 39 or claim 40,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, include a swelling agent.
42.A composition according to any one of claims 39 to 41,
further including an additional coloring agent.
43. A composition according to the preceding claim,
wherein the additional coloring agent is in the free
state in the composition.
44.A composition according to any one of claims 41 to 43,
wherein the swelling agent is selected from:
- water and organic or inorganic saline solutions
with a concentration in the range 0.01 M to 5 M, for
example sodium, magnesium, potassium, calcium, or
copper salts, solutions of phosphates and solutions of
ammonium salts;
- the following compounds alone, as a mixture or in
aqueous solution:
o glycerol, PEGs having a molecular weight in
the range 400 g/mol to 50000 g/mol, mono-, di- and
oligo-sacch.arid.es that are soluble in water at at
least 1% by weight, sorbitol, propylene glycol,
dipropylene glycol, butylene glycol, water-soluble
polyols, water-miscible lower alcohols, for example
methanol, ethanol or isopropanol, benzene, acetone, ß-
methylbutyric acid, a-ethylbutyric acid, 2,2,2,-
trifluoroethanol, 1-butan.ol, 1,4-butanediol,
chloroform, bromoethane, methyl acetate, ethyl
acetate, dimethylformamide, butan-2-one,
divinylbenzene, propylene glycol monomethy1ether
acetate (PGMSA), and acetic acid solutions;
o neutralized or non-neutralized solutions of
UV screens; and
o polar oils, for example lauroyl isopropyl
sarcosinate, octyldodecanol, undecane and tridecane as
well as oily solutions of organic screens.
45.A composition according to any one of claims 39 to 44,
wherein the coloring agent is selected from:
i. liposoluble coloring agents, for example DC Red
17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC
Violet 2, DC Orange 5, Sudan red, carotenes such as ß-
carotene or lycopene, xanthophylls such as capsanthin,
capsombin or lutein, palm oil, Sudan brown, quinoline
yellow, roucou, curcumin;
ii. hydrosoluble coloring agents, for example FDC
Red 4, DC Red 5, DC Red 22, DC Red 28, DC Red 30, DC
Red 33, DC Orange 4, DC Yellow 5, DC Yellow 5, DC
Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1,
betanin, carmine, chlorophyllin copper, methylene
blue, anthocyanins, riboflavin.
46.A composition according to any one of claims 39 to 45,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, have a lamellar structure.
47. A composition according to any one of claims 39 to 46,
wherein the amphiphilic polymer comprises a copolymer,
in particular a block copolymer.
48. A composition according to the preceding claim,
wherein the amphiphilic polymer comprises, in
particular consists of, a:
- diblock copolymer with the form a-b where A is a
hydrophobic block selected, for example, from:
polystyrene, polymethyl methacrylate, polycyclohexyl
methacrylate, polyisobornyl acrylate, polyisobornyl
methacrylate, polyisobutyl methacrylate, polyethyl
methacrylate, poly N-tert butyl acrylamide, and
polyisopropyl methacrylate, and E is a:
• hydrophilic and cationic block, for example
selected from: poly(2-vinyl pyridine), poly(4-vinyl
pyridine) , poly(dimethyl amino ethyl methacrylate),
poly(diethyl amino ethyl methacrylate), poly(dimethyl
amino propyl methacrylamide), and poly(N-vinyl
pyrrolldone);
• hydrophilic and anionic block, for example
selected from: poly(acrylic acid), poly(methacrylic
acid), poly(maleic acid), poly(itaconic acid),
poly(fumaric acid), poly(crotonic acid),
poly(acrylamido glycolic acid), and poly(acrylamido 2-
methylpropane sulfonic acid) ,- or
•hydrophilic and non-ionic block, for example
selected from: poly(peg methacrylate) ;
- triblock copolymer with the form A-B-e where:
• A. and C are different hydrophobic blocks
selected from: polystyrene, polymethyl methacrylate,
polycyclohexyl methacrylate, polyisobornyl acrylate,
polyisobornyl methacrylate, polyisobutyl methacrylate,
polyethyi methacrylate, poly N-tert butyl acrylamide,
and polyisopropyl methacrylate, and B is a:
o hyd.ropb.ilic and cationic block, for
example selected from: poly(2-vinyl pyridine}, poly (4-
vinyl pyridine), poly(dimethyl amino ethyl
methacrylate), poly(diethyl amino ethyl methacrylate),
poly(dimethyl amino propyl methacxylamide), and
poly(N-vinyl pyrrclidone);
o hydrophilic and anionic block, for
example selected from: poly(acrylic acid),
polytmethacrylic acid), poly(maleic acid),
poly(itaconic acid), poly{fumaric acid), poly(crotonic
acid), poly{acrylamido glycolic acid), and
poly(aerylamido 2-methylpropane sulfonic acid); or
o hydrophilic and non-ionic block, for
example selected from; poly(PEG methacrylate); or
• D is a hydrophobic block selected from:
polystyrene, polymethyl methacrylate, polycyclohexyl
methacrylate, polyisobornyl acrylate, polyisobornyl
methacrylate, polyisobutyl methacrylate, polyethyi
methacrylate, poly N-tert butyl acrylamide and
polyisopropyl methacrylate and A and C are different
and selected from:
o hydrophilic and cationic blocks, for
example selected from: poly(2-vinyl pyridine), poly{4-
vinyl pyridine), poly (dimethyl amine ethyl
methacrylate), poly(diethyl amino ethyl methacrylate) ,
poly (dimethyl amino propyl methacrylsirdde) , and
poly (N-vinyl pyrrolidone);
o hydrophilic and anionic blocks, for
example selected from: poly(acrylic acid),
poiyimethacrylic acid), polylmaieic acid),
poiy(itaconic acid), poly(£umaric acid), poly(crotonic
acid) , poly(acrylamido glycolic acid!, and
poly(acrylamido 2-methylpropane sulfonic acid); or
o hydrophiiic and non-ionic blocks, for
example selected from: poly(PEG methacrylate).
49. A composition according to the preceding claim,
wherein the amphophilic polymer comprises, in
particular consists of, a ctibiock copolymer with the
form A-B where A is polystyrene and B is poly (2-vinyl
pyridine).
50.A composition according to any one of claims 39 to 49,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, are plate-like in form.
51. A method of making up, for example to make the
complexion uniform, the method comprising applying a
composition according to any one of claims 39 to 50 to
human keratinous materials.
52. A film for making up; for example to make the
complexion uniform, for application to human
keratinous materials, the film including a photonic
material, in particular a polymeric multilayer
interference structure, comprising an amphiphilic
polymer and producing a visible color.
53.A method of preparing a cosmetic composition according
to any one of claims 41 to 5C comprising:
a) a step of bringing a swelling agent into contact
with a photonic material, in particular with a
polymeric multilayer structure, comprising an
amphiphilic polymer;
b) a step of fragmenting a film of photonic
material, in particular a film having a polymeric
multilayer structure, into particles of photonic
material, in particular into particles having a
polymeric multilayer structure, with a largest
dimension of less than 100 µm and with a smallest
dimension of 100 rim or more; and
c) a step of dispersing the particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, comprising an
amphiphilic polymer and producing a visible color
obtained after carrying out steps a) and b) in a
cosmetically acceptable medium,-
step b} being carried out before or after step a).
54.A cosmetic composition including particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, including a polymer
having a fluorescent agent within it.
55.A composition according to claim 54, wherein the
particles of photonic material, in particular
particles having a polymeric multilayer interference
structure, have a reflection spectrum including a
reflection peak in the wavelength range 250 nm to
800 nm.
5 6. A composition according to claim 54 or claim 55,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, include a swelling agent.
57. A composition according to the preceding claim,
wherein the fluorescent agent is dissolved in the
swelling agent.
58.A composition according to any one of claims 55 to 57,
having, before application to the keratinous
materials, a transmission spectrum including two
minima in the wavelength range 250 nm to 8C0 nm.
59. A composition according to the preceding claim,
wherein the minima are separated by at least 50 ran.
50. A composition according to claim 58 or claim 59,
wherein at least one minimum is located in the
wavelength range 250 nm to 400 nm arid at least one
minimum is located in the wavelength range 400 run to
800 nm, for example in the range 4G0 nm tc 550 nm.
61. A composition according to any one of claims 54 to 60,
wherein the fluorescent agent is an optical brightener
selected from solutions of stilbene derivatives, in
particular polystyry1stiibenes and triazinstiibenes,
coumarin derivatives, in particular hydroxycoumarins
and aminocoumarins, oxazole, benzoxazole, imidazole,
triazole or pyrazoline derivatives, pyrene derivatives
and porphyrin derivatives and/or mixtures thereof, and
aqueous solutions of disodium distyrylbiphenyl
disuifonate.
62.A composition according, to any one of claims 54 to 61,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, are plate-like.
63.A composition according to any one of claims 54 to 62,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, have a lamellar structure.
64.A composition according to any one of claims 54 to 63,
wherein said amphiphilic polymer comprises a
copolymer, for example a block copolymer.
65-A composition according to the preceding claim,
v/herein said polymer comprises, in particular consists
of, an amphiphilic polymer selected from:
- diblock copolymers wi~h the form A-B where A is a
hydrophobic block selected, for example, from:
polystyrene, polymethyl methacrylate, polycyclohexyl
methacrylate, polyisobornyl acrylate, polyisobornyl
methacrylate, polyisobutyl methacrylate, polyethyl
methacrylate, poly N-tert butyl acrylamide, and
polyisopropyl methacrylate, and B is a:
• hydrophilic' and cationic block, for example
selected from: poly(2-vinyl pyridine), poly(4-vinyl
pyridine), poly(dimethyl amino ethyl methacrylate),
poly(diethyl amino ethyl methacrylate), poly(dimethyl
amino propyl methacrylamide), and poly(N-vinyl
pyrrolidone) ,-
• hydrophilic and anionic block, for example
selected from: po!y(acrylic acid), poly(methacrylic
acid), polyfmaleic acid), poly(itaconic acid),
poly(fumaric acid), poly(crotonic acid),
poly(acrylamido glycolic acid), and poly(acrylamido 2-
methylpropane sulfonic acid) ,- or
• hydrophilic and non-ionic block, for example
selected from: poly(PEG methacrylate);
- triblock copolymers with the form A-B-C where:
• A and C are different hydrophobic blocks, for
example selected from: polystyrene, polymethyl
methacrylate, polycyclohexyl methacrylate,
polyisobornyl acrylate, polyisobornyl methacrylate,
polyisobutyl methacrylace, polyethyl methacrylate,
poly N-tert bury I acrylamide and polyisopropyl
methacrylate, and B is a:
o hydrophilic and cationic block, for
example selected from; poiy(2-vinyl pyridine) , poly(4-
vinyl pyridine), poly(dimethyl amino ethyl
methacrylate) , poly(diethyl amino ethyl methacrylate) ,
poly(dimethyl amino propyl raethacrylamide), and
poly(N-vinyl pyrrolidone];
o hydrophilic and anionic block, for
example selected from: poly(acrylic acid) ,
poly(methacrylic acid) , polyfrraleic acid) ,
poly(itaconic acid), poly (f µmaric acid), poly{crotonic
acid), poly[aery1amido glycolic acid), and
polyfacrylamido 2-methylpropane sulfonic acid); or
o hydxophilic and noil-ionic block, for
example poly (PEG methacryiate); or
• B is a hydrophobic block, for example
selected from: polystyrene, polymethyl methacryiate,
polycyclohexyl methacryiate, polyisobornyl acrylate,
polyisobornyl methacryiate, polyisobutyl methacryiate,
polysthyl methacryiate, poly N-tert butyl acrylamido,
and polyisopropyl methacryiate and A and C are
different and selected from:
o hydrophilic and cationic blocks, for
example selected from: poly(2-vinyl pyridine), poly{4-
vinyl pyridine), poly (dimethyl amino ethyl
methacryiate) , poly(diethyl amino ethyl methacryiate),
poly(dimethyl amino propyl methacrylamide), and
poly(N-vinyl pyrrol idone) ,-
o hydrophilic and anionic blocks, for
example selected from: poly(acrylic acid),
poly(methacrylic acid), poly(maleic acid),
poly(itaconic acid), poly(fumaric acid), poly(crotonic
acid;, polyfacrylamido glycolic acid), and
polyfacrylamido 2-methylpropane sulfonic acid); or
o hydrophilic and non-ionic blocks, for
example poly(PEG methacryiate).
66. A composition according to the preceding claim,
wherein the amphophilic polymer comprises, in
particular consists c£, a diblock copolymer with the
form A-B where A is polystyrene and B is poly(2-vinyl
pyridine}.
67 . A method of lightening human kera.tinous materials, the
method comprising applying a cosmetic composition
according to any one of claims 54 to 66.
68. A filir. for lightening the complexion, for application
to human keratinous materials, the film including a
photonic material, in particular a polymeric
multilayer interference structure, comprising a
polymer having a fluorescent agenc within it.
69.A method of preparing a cosmetic composition according
to any one of claims 57 to 68, comprising:
a) a step of bringing a swelling agent including a
dissolved fluorescent agent into contact with a
photonic material, in particular with a polymeric
multilayer structure;
b) a step of fragmenting a film of photonic
material, in particular a film having said polymeric
multilayer structure, into particles of photonic
material, in particular into particles having a
polymeric multilayer structure, with a largest
dimension of less than or equal to lOOum and a
smallest dimension greater than 100 nm; and
c} a step of dispersing the particles of photonic
material, in particular the particles having a
polymeric multilayer interference structure, obtained
after carrying out steps a) and b) in a cosmetically
acceptable medium;
step b) being carried out before or after step a).
70. A photoprotective composition, in particular a
cosmetic composition, including particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, comprising a
polymer having a UV screen within it.
71.A composition according to claim 70, wherein the
particles of photonic material, in particular the
particles having a polymeric multilayer interference
structure, have a reflection spectrum including a
reflection peak in the wavelength range 250 nm to
400 nm.
72.A composition according to claim 70 or claim 71
having, before application to the keratinous
materials, a transmission spectrum including two
minima in the wavelength range 250 nm to 400 nm, the
minima being separated by at least 50 nm,
73.A composition according to any one of claims 7 0 to 72,
having a SPF greater than or equal to 10.
74.A composition according to any one o£ claims 7 0 to 73,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, have a lamellar structure.
75.A composition according to any one of claims 70 to 74,
wherein said polymer comprises a copolymer, in
particular a block copolymer.
76.A composition according to the preceding claim,
wherein said polymer comprises, in particular consists
of, a:
- dibiock copolymer with the form A-B where A is a
hydrophobic block selected, for example, from:
polystyrene, polymethyl methacrylate, polycyclohexyl
methacrylate, polyisobomyl acrylate, polyisobornyl
methacrylate, polyisobutyl methacrylate, polyethyl
methacrylate, poly N- tert butyl acrylamide, and
polyisopropyl methacrylate, and B is a:
» hydrophilic and cationic block, for example
selected from: poly{2-vinyl pyridine), poly{4-vinyl
pyridine) , poly(dimethyl amino ethyl methacrylate) ,
poly(diethyl amino ethyl methacrylate), poly(dimethyl
amino propyl methacryiamide), and poly(N-vinyl
pyrrolidonel;
• hydrophilic and anionic block, for example
selected from: poly (acrylic acid), poly (raethacrylic
acid), poiy(maleic acid), poly(itaconic acid),
poly(fumaric acid), poly (crotonic acid),
poly(acrylamido glycolic acid), and poly(acrylamido 2-
methylpropane sulfonic acid); or
• hydrophilic and non-ionic block, for example
selected from: poly(PEG methacrylate);
- triblock copolymer with the form A-B-C where:
• A and C are different hydrophobic blocks, for
example selected from: polystyrene, polymethyl
methacrylate, polycyclohexyl methacrylate,
polyisobornyl acrylate, polyisobornyl methacrylate,
polyisobutyl methacrylate, polyethyl methacrylate,
poly N-tert butyl acrylamide and polyisopropyl
methacrylate, and B is a:
o hydrophilic and cationic block, for
example selected from,- poly(2-vinyl pyridine), poly(4-
vinyl pyridine), poly{dimethyl amino ethyl
methacrylate) , poly(diethyl amino ethyl methacrylate) ,
poly (dimethyl amino propyl metbacrylamide) , and
poly(N-vinyl pyrrolidone);
o hydrophilic and anionic block, for
example selected from: polyiacrylic acid),
poly(methacrylic acid), poly(maleic acid),
poly (itaconic acid), poly(fnmaric acid), poly(crotonic
acid), poly(acrylamido glycolic acid), and
poly (acrylamido 2-methylpropane sulfonic acid); or
o hydrophilic and non-ionic block, fcr
example poly(PEG methacrylate); cr
• B is a hydrophobic block, for example
selected from: polystyrene, polymethyl methacrylate,
polycyclohexyl methacrylate, polyisobornyl acrylate,
polyisobornyl methacrylate, polyisobutyl methacrylate,
polyethyl methacrylate, poly N-tert butyl acrylamide
and polyisopropyl methacrylate and A and C are
different and selectee from:
o hydrophilic and cationic blocks, for
example selected from: poly(2-vinyl pyridine), poly(4-
vinyl pyridine), poly (dimethyl amino ethyl
methacrylate) , poly(diethyl amino ethyl methacrylate),
poly (dimethyl amino propyl -nethacrylamide) , and
poly(N-vinyl pyrrolidone) ,-
o hydrophilic and anionic blocks, for
example selected from: poly(acrylic acid),
poly{methacrylic acid), polyimaleic acid),
poly(itaconic acid), polylfumaric acid), poly(crctonic
acid), poly(acrylamido glycolic acid), and
poly(acrylamido 2-metnylpropane sulfonic acid); or
o hydrophilic and non-ionic blocks, for
example poly(PEG methacrylate) .
77. A composition according to the preceding claim,
wherein the amphiphilic polymer comprises, in
particular consists of, a diblock copolymer with the
form. A-3 where A is polystyrene and 3 is poly(2-vinyl .
pyridine).
78.A composition according to any one of claims 70 to 77,
wherein the particles of photonic material, in
. particular particles having a polymeric multilayer
interference structure, include a swelling agent.
79. A composition according to the preceding claim,
wherein the UV screen is dissolved in the swelling
agent.
SO. A composition according to any preceding claim,
wherein the UV screen is selected from:
- hydrophobic screens, for example: dibenzoylmethane
derivatives, aminobenzophenones, anthranilic
derivatives, 4,4-diarylbutadiene derivatives, para-
aminobenzoates, salicylic derivatives, cinnamates, ß, ß
-diphenyiacrylate derivatives, benzylidene camphor
derivatives, triazine derivatives, imidazoline
derivatives, benzalmalonate derivatives, merocyanin
derivatives, benzophenone derivatives, phenyl
ben20triazols derivatives, bis-resorcinyl triazine
derivatives and benzoxazole derivatives; and
- hydrosoluble screens, for example:
terephthalylidene dicamphor sulfonic acid, bis-
bensoazolyl derivatives, p-aminobenzoic acid (PABA)
derivatives and benzophenone derivatives comprising at
least one sulfonic radical.
81.A composition according 10 any one of claims 70 to 80,
wherein the particles of photonic material, in
particular particles having a polymeric multilayer
interference structure, are plate-like.
82 . A cosmetic composition comprising, in a cosmetically
acceptable medium, at least particles of photonic
material, in particular particles having a polymeric
multilayer interference structure, as defined in any
one of claims 7 0 to 81.
83. A method of preparing a composition according to any
one of claims 70 to 82, comprising:
a) a step of bringing a swelling agent including a
dissolved UV screen into contact with a photonic
material, in particular with a polymeric multilayer
structure;
b) a step cf fragmenting a film of photonic
material, in particular a film having said polymeric
multilayer structure, into particles of photonic
material, in particular into particles having a
polymeric multilayer structure with a largest
dimension of less than 100µm and a smallest dimension
greater than 100 nm; and
c) a step of dispersing the particles of phoronic
material, in particular particles having a polymeric
multilayer interference structure, obtained after
carrying out steps a) and b} in a suitable medium;
step b) being carried out before or after step a).
84.A method of photoprotecting a material against solar
UV radiation, the method comprising treating said
material with a photoprotective composition according
to any one of claims 70 to 82 or integrating at least
said composition into said material.
85.A method of non-therapeutic and in particular cosmetic
photoprotection of human keratinous materials against
solar UV radiation, the method comprising applying a
cosmetic composition according to claim 82 to human
keratinous materials.
86. A method of photoprotecting an ink, a paint, or a
coating, the method comprising incorporating at least
one composition as defined in any one of claims 70 to
82 into said ink or paint or said coating.
87. A method of photoprotecting a material manufactured
from at least one synthetic or natural polymer, the
method comprising treating said polymer with at least
one composition as defined in any one of claims 7G to
82 or integrating at least said composition into said
material.
88.A method of photoprotecting an organic or mineral
glass, the method consisting in treating said glass
with at least one composition as defined in any one of
claims 70 to 82 or integrating at least said
composition into said glass.
89. A method of photoprotecting a material comprising at
least natural fibers and/or artificial fibers and/or
synthetic fibers such as textiles or papers, the
method comprising treating said material with at least
one composition, as defined in any one of claims 7 0 to
82 or integrating at least said composition into said
material.
90.A film that photoprotects against solar UV radiation,
the film including a photonic material, in particular
a multilayer interference structure screening solar UV
radiation, wherein at least two layers comprise an
amphiphilic polymer having a UV screen within it.
ABSTRACT
The present invention provides a photoprotective composition, in particular a cosmetic composition, including particles
of photonic material in particular having a polymeric multilayer interference structure, at least two layers of said structure
comprising an amphiphilic polymer. The invention provides a method of photoprotecting a material against solar UV radiation,
the method consisting in treating said material with a photoprotective composition including particles of photonic material in particular
having a polymeric multilayer interference structure, at least two layers of said structure comprising an amphiphilic polymer
or integrating at least said composition into said material. Said material may in particular be selected from inks, paints, glasses,
textiles, papers and polymers. The invention also provides a film that photoprotects against solar UV radiation, the film including
a photonic material in particular having a multilayer interference structure screening solar UV radiation, wherein at least two
layers comprise an amphiphilic polymer.