Patent Application
20110180510
The present invention relates to containers provided with a coating on their inner surface, which containers are suitable especially for the packaging of cosmetic compositions, especially liquid compositions or compositions in gel form. The invention more specifically relates to containers of that type having e transparent body and wherein the inner coating comprises a colouring agent and/or an agent that absorbs ultraviolet radiations.
The term “container”, as used herein, denotes any device suitable for containing, inter alia, a liquid composition. Typically, a container within the scope of the present description is a vial, a bottle, a jar, a tube, a round bottle or a canister. More generally, it can be any article for packaging cosmetics.
When a container is completely filled with a liquid, only part of its surface is in contact with said liquid. Within the scope of the present description, the “inner surface” of the container denotes the part of the surface of the container that is in contact with the liquid when the container is completely filled. By contrast, the remainder of the surface of the container, which is not in contact with the liquid when the container is filled completely, is referred to as the “external surface”.
Furthermore, the volume of the container that is filled with liquid when the container is full is referred to as the “inner cavity” of the container.
Various types of container that are coated on all or part of their surface, especially for the purpose of aesthetic decoration, labeling or protection, are known at the present time.
Most of the time, such coatings are applied to all or part of the external surface of the containers (typically by the deposition of paints, inks, polymers or varnishes), the deposition of which on the container generally does not present any specific technical problems.
Especially in the field of cosmetics packaging, a different, more specific type of coating is desired, namely a coating provided on all or part of the inner surface of the containers.
Inner coatings of that type are found to be particularly valuable when the body of the container is transparent and reveals the deposited inner coating (for example when the container is made of glass or plastics). In particular, coloured inner coatings deposited on the surface of transparent vials provide an interesting aesthetic effect, with a depth effect of the colouring applied to the inner coating contrasting with the thickness of the vial, that effect generally being more pronounced when the vial has facets and the thicker its walls.
Containers provided with coloured inner coatings of the above-mentioned type have been proposed, especially for packaging perfumes. Nevertheless, within that context, only the disclosures relate to the deposition of inner coatings that do not permit direct contact with a cosmetic composition.
More precisely, it has been proposed to colour the inner surface of perfume vials by lacquering, typically by depositing coloured varnishes or paints. A problem is that the colouring agents present in the coloured coatings deposited by lacquering tend to migrate to the cosmetic compositions with which they are in contact, especially when the compositions are alcoholic compositions such as perfumes. This can lead in the very short term to unacceptable colouring of the cosmetic composition and/or to a loss of the colouring of the inner coating, which is also disadvantageous.
Therefore, with containers provided with coloured inner coatings of the above-mentioned type, the cosmetic composition cannot be contained as such in the container. The packaging of a cosmetic composition in such containers has certainly been described but, in that specific case, not the composition itself is contained in the container but a flexible container, such as plastics pocket, which protects the composition. In that case, the packaging of the cosmetic composition in the intermediate flexible container allows avoiding any contact between the cosmetic composition and the inner coating.
The instant invention aims at providing a novel type of container that is coated on its inner surface by a coating layer which can be coloured and which is further suitable for the direct packaging of a cosmetic composition without having to inhibit contact between the cosmetic composition and the coating layer.
To that end, according to a first aspect, one object of the invention is a container having, on all or part of its inner surface, a mineral-oxide-based coating obtained by a sol-gel process.
The term “sol-gel process” is here to be understood in its broad meaning and denotes a process of known type wherein a medium comprising at least one mineral alkoxide precursor (in most cases an alkoxide of formula M(OR)n wherein M denotes silicon or a metal such as Al or Ti; n denotes the valence of the element M; and the n groups —OR are identical or different organic groups, for example alkoxy groups) is hydrolysed. As it hydrolyses, the precursor of the alkoxide type used in a sol-gel process is converted into hydroxylated species (typically of formula M(OH)n wherein M and n have the meanings given hereinbefore) which condense together to form mineral oxide particles by a process which is comparable to a polymerisation of the mineral precursor. Typically, those hydrolysis and condensation reactions first yield a sol (suspension of oxide particles) which gradually becomes concentrated, the particles that are forming occupying an ever larger volume fraction, whereby a gel is obtained; hence the generic expression “sol-gel” given to processes of this type.
A coating obtained by a sol-gel process, of the type that is applied to the inner surface of a container according to the present invention, is obtained by depositing a gel as obtained by the process described hereinbefore and then drying the gel. The deposition of the gel on the surface on which coating is to be carried out can be obtained either by preparing the gel under the above-mentioned conditions and then applying it to the surface, or by applying to the surface to be treated a composition comprising the mineral precursor in the partially hydrolysed state only (for example in the sol state) and then allowing gelling of the medium to take place only in the deposit so made (this second mode of operation allowing the deposition of a coating of more controlled thickness, especially in the form of thin films). In order to strengthen the deposit obtained after drying of the solvent, it can be of interest to subject the dried deposit obtained after evaporation of the solvent to heat treatment, in a so-called “annealing” step. It is to be noted that coatings (deposits) produced by the sol-gel technique do not require the use of high temperatures (the hydrolysis-condensation reactions that yield the gel can typically be carried out at ambient temperature and the optional annealing step generally does not require temperatures above 200° C. and can typically be carried out at temperatures of from 70 to 200° C., for example from 80 to 180° C.).
For further details regarding sol-gel processes and the production of coatings by that technique, reference may be made especially to the documents described below:
The coatings deposited on the inner surface of a container according to the invention can be prepared by any process of the prior art known per se. It is generally preferred for the deposited coating to be obtained by acid hydrolysis of a mineral oxide of the above-mentioned formula M(OR)n. Alternatively, it is, however, also possible for the coating deposited according to the invention to be obtained by hydrolysis of a mineral alkoxide in a basic medium.
The sol-gel coating present on the inner surface of a container according to the invention generally has a thickness ranging from several nanometres to several hundred micrometres, the thickness preferably being from 100 nm to 500 microns and more preferably from 40 microns to 300 microns.
Advantageously, the coating present on the inner surface of a container according to the invention is obtained by a sol-gel process using as mineral precursor at least one silicon alkoxide, whereby the sol-gel deposit formed comprises a matrix based on a silica network, which is broadly similar to a glass having controlled porosity. According to this embodiment, the silicon alkoxide used advantageously has the following formula (I):
Si(OR)3R′ (I)
wherein:
The coatings of the sol-gel type which can be used according to the present invention, in particular those obtained from precursors of the silicon alkoxide type, have the advantage that they can be applied to a large number of materials, especially to glass or metal, or alternatively to other materials, such as plastics.
Another advantage of the sol-gel coatings of the invention is that their properties can readily be modulated as a function of the intended application of the coating.
To that end, it should first be emphasised that coatings produced by the sol-gel technique are in the form of crosslinked mineral oxide matrices wherein different species (particles, polymers, molecules of large size) can be trapped, which can be used to modify the physicochemical properties of the coating. In order to trap such species within the coating, the species must simply be introduced into the medium for forming the sol, the species thereby ultimately being trapped in the gel and then in the solid matrix obtained after drying of the gel.
In addition, according to the sol-gel technique, it is possible in a very simple manner to obtain coatings that are functionalised by specific functional groups which are bonded, advantageously covalently, to the coating. Such functionalisation of the coating can especially be obtained by making use, as starting materials mineral precursors carrying desired functional groups (for example by using precursors of the above-mentioned formula (I) wherein R is a functional group of the desired type).
These various possibilities, in conjunction with the fact that the deposition of a coating by the sol-gel technique can be carried out at very low temperatures, allow a great modularity for the coated containers according to the invention. The invention accordingly permits access to a wide range of containers suitable for very many applications.
In a container according to the invention, the coating present on the inner surface in most cases comprises macromolecular species (organic or inorganic particles or polymers) which are trapped within its mineral-oxide-based structure and/or is functionalised by functional groups bonded, preferably covalently, to said coating. Within this context, the coating present on the inner surface of a container according to the invention is preferably a hybrid organic/inorganic crosslinked network comprising organic species dispersed in the mineral-oxide-based structure and/or bonded to said structure.
In this scope, according to a first interesting embodiment of the invention, the coated container according to the invention has a transparent body and the coating present on the inner surface of the transparent container is a coating which is coloured or has a visual appearance which is different from that of the body of the container, and which is visible through the body of the container. The expression “body of the container” is here understood as meaning the part that constitutes the container, separate from the coating. According to this embodiment, the body of the container is advantageously made of glass.
The containers according to this first embodiment of the inventive show an interesting aesthetic effect, the inner layer being visible through the body of the container, which confers thereon an appearance which is coloured or decorated in depth, such an appearance being especially prized and sought-after notably in the cosmetics packaging. Within the scope of the invention, contrary to the techniques proposed hitherto for obtaining such a decorative effect, the cosmetic composition can be brought directly into contact with the inner coating of the container.
According to the first embodiment of the invention, the coating present on the inner surface of the container can be a coating of the translucent or transparent type, suitable for revealing a cosmetic composition contained in the container or, on the other hand, it can be an opaque coating which conceals the composition. Within this context, coatings of the opaque type are found to be generally of interest, especially insofar as they confer on the container a deeply coloured or decorated appearance which is particularly pronounced.
The coating present on the inner surface of a container according to the first embodiment of the invention can advantageously comprise:
According to a first variant of the first embodiment of the invention, the coating present on the inner surface of the container comprises a colouring agent which is fixed to the surface of the coating by way of a covalent bond.
Within the scope of the present description, the expression “colouring agent” is understood as meaning a compound that absorbs and/or emits radiation in the visible range. The term includes especially conventional colouring agents, which absorb radiation in the visible range, as well as fluorescent or phosphorescent compounds, which emit a visible light when they are excited.
A method of interest for obtaining according to the invention, a coating comprising covalently bonded colouring agents of the above-mentioned type comprises preparing the coating by the sol-gel technique using one or more mineral precursors including a mineral precursor to which said colouring agent is bonded covalently. Especially, a coating comprising colouring agents bonded covalently to its surface can be obtained by carrying out the following steps:
(A1)) a colouring agent carrying a reactive functional group Rr is reacted with a silicon alkoxide having the following formula (I1):
Si(OR)3Rc (I1)
wherein:
Si(OR)3R′ (I),
wherein R has the meaning given hereinbefore and wherein R′ is a group resulting from the reaction of the functional group Rc with the colouring agent carrying the reactive functional group Rr; then
(B1) the sol-gel deposition is carried out on the inner surface of the container using as mineral precursor the silicon alkoxide (I) obtained in step (A1), preferably in association with a silicon alkoxide of formula Si(OR″)4 wherein each of the groups R″, which may be identical or different, denotes an alkyl group, preferably an alkyl or a methyl.
According to this variant, the functional group Rr carried by the colouring agent can typically be a hydroxyl functional group —OH, the functional group Rc carried by the silicon alkoxide (I1) then preferably being an isocyanate functional group —C═N═O, these two functional groups reacting to form a carbamate covalent bond between the silicon alkoxide and the colouring agent, according to the following reaction scheme:
[alkoxide]—CNO+[colouring agent]—OH→alkoxide—CNH—COO—[colouring agent].
A silicon alkoxide carrying an isocyanate functional group which is very suitable in this context is 3-isocyanatopropyltriethoxysilane, of formula (C2HSO)3Si—(CH)3—NCO, also known by the acronym ICPTEOS. Many colouring agents carry —OH functional groups and can be used conjointly with ICPTEOS or other silicon alkoxides carrying an isocyanate functional group, among which there may be mentioned, for example, the following colouring agents: the colouring agent red 1, especially in the form DR1 (dispersed red 1) or alternatively the colouring agents solvent violet 13, solvent blue 90 or solvent yellow 82, as well as purpurin, anthrapurpurin or alizarin.
More generally, the functional groups Rr and Rc carried, respectively, by the colouring agent and the silicon alkoxide (I1) used in step (A1) can be selected from any pair of functional groups suitable for forming a covalent bond. Within this context, and without implying any limitation, the functional groups Rr and Rc may be selected especially as follows:
Rr=—OH and Rc=—C═N═O; or
Rr=—NH2 and Rc=—COOH.
In step (B1), the coating obtained by the sol-gel technique is preferably produced using, as mineral precursor, a mixture of the silicon alkoxide of formula (I) as obtained following step (A1) with a silicon alkoxide having the above-mentioned formula Si(OR″)4, preferably in a molar ratio alkoxide (I)/Si(OR″)4 of from 10% to 50%, advantageously from 25% to 35%. In step (B1), TEOS (tetraethoxysilane of formula Si(OC2H5)4) is preferably used as the alkoxide of formula Si(OR″)4.
According to a second variant of the first embodiment of the invention, the coating present on the inner surface of the container comprises particles that modify the light absorption, reflection or refraction properties, which particles are trapped within the mineral-oxide-based structure of the coating. Where applicable, those particles, which are isotropic or anisotropic, typically have sizes ranging from 10 to 500 microns, more preferably from 20 to 400 microns.
The particles present in the coating according to this second particular variant can especially comprise:
Coatings comprising particles of the above-mentioned type are typically obtained by preparing the coating by the above-mentioned sol-gel technique and introducing into the medium for forming the gel from the mineral precursor the particles which are ultimately to be incorporated in the inner coating deposited on the inner surface of the container according to the invention.
According to a second embodiment of the invention (which is compatible with the preceding embodiment), the coated container according to the invention has a transparent body, and the coating present on the inner surface of the transparent container comprises a compound that absorbs radiation in the ultraviolet range (that is to say an ultraviolet filter also called anti-ultraviolet filter) which is covalently bonded to said coating. According to this embodiment, the body of the container is advantageously made of glass. The presence of an anti-ultraviolet filter in the coating according to the second embodiment of the invention makes it possible to protect the cosmetic composition contained in the container, the properties of which might otherwise be affected when the container is exposed to radiation in the ultraviolet range, for example when the container is exposed to sunlight. Containers according to this embodiment accordingly enable a protective effect to be provided for the compositions they contain.
The anti-ultraviolet filters used in the second embodiment of the invention can be selected, for example, from the benzophenones or alternatively from the benzotriazoles.
Coatings comprising anti-ultraviolet filters of the above-mentioned type bonded covalently to said coating can be prepared especially by using the sol-gel technique and employing one or more mineral precursors including a mineral precursor to which there is bonded covalently a compound that absorbs in the ultraviolet range.
Especially, a coating comprising anti-ultraviolet filters bonded covalently to its surface can be obtained by carrying out the following steps:
(A2) a compound that absorbs radiation in the ultraviolet range and carrying a reactive functional group R′ is reacted with a silicon alkoxide having the following formula (I2):
Si(OR)3Rc (I2)
wherein:
Si(OR)3R′ (I),
wherein R has the meaning given hereinbefore and wherein R′ is a group resulting from the reaction of the functional group Rc with the compound that absorbs in the ultraviolet range and carrying the reactive functional group Rr; then
(B2) the sol-gel coating is carried out on the inner surface of the container using as mineral precursor the silicon alkoxide (I) obtained in step (A2), preferably in association with a silicon alkoxide of formula Si(OR″)4
wherein each of the groups R″, which may be identical or different, denotes an alkyl group, preferably an alkyl or a methyl.
According to this variant, steps (A2) and (B2) are preferably carried out under the preferred conditions defined for steps (A1) and (B1) employed within the scope of the first variant of the first particular embodiment of the present invention. In particular, the functional group Rr carried by the compound that absorbs in the ultraviolet range can typically be a hydroxyl functional group —OH, the functional group Rc carried by the silicon alkoxide (I1) then preferably being an isocyanate functional group —C═N═O, those two functional groups reacting to form a carbamate covalent bond between the silicon alkoxide and the compound that absorbs in the ultraviolet range.
In that case too, a silicon alkoxide carrying an isocyanate function that is highly suitable within this context is 3-isocyanatopropyltriethoxysilane, having the formula (C2HSO)3Si—(CH)3—NCO) (ICPTEOS mentioned hereinbefore).
In addition, in step (B2), the coating obtained by the sol-gel technique is preferably formed using, as mineral precursor, a mixture of the silicon alkoxide of formula (I) as obtained following step (A2) with a silicon alkoxide having the formula Si(OR″)4, that additional alkoxide preferably being TEOS (tetraethoxysilane of formula Si (OC2H5)4).
Whatever the nature of the inner coating present on the inner surface of a container according to the invention, the coating can be produced by any process known per se for producing a coating of that type. For containers having a wide opening (for example a wide-necked jar), the majority of the known techniques can generally be used, especially spray coating techniques. More generally, it is also possible to use the known spin coating methods or alternatively dip-coating, flow-coating and capillary coating methods.
For containers having a narrow neck or, more generally, for containers having undercut surfaces (that is to say containers which cannot be moulded in one piece, such as bottles or vials), more specific techniques are to be used. For such containers, the inner coating can typically be produced by a spin coating technique. Within this context, the gelled material obtained from the mineral precursor (or a more fluid medium obtained by only partial hydrolysis of the mineral precursor) is preferably deposited in the container and the container is subjected to a circular movement according to one of its axes so that the composition that has been introduced is deposited on the inner surface of the container. Another technique which can be used is spray coating, in which an injection nozzle is introduced into the container, through which the gelled material obtained from the mineral precursor (or a more fluid medium obtained by only partial hydrolysis of the mineral precursor) is projected onto the inner surface of the container. Such spin coating and spray coating techniques are highly suitable for producing an inner coating on any type of container, whatever its shape.
As emphasised hereinbefore in the present description, the containers according to the present invention are particularly suitable for the packaging of cosmetic compositions, where they permit direct contact between the inner coating and the cosmetic composition. According to another aspect, this particular use of the containers of the invention constitutes another particular object of the present invention.
Within this context, the container according to the invention is preferably a vial or a bottle, preferably made of glass. When the term glass is used in the present description, it preferably refers to a dihizocalcic, sodocalcic or borosilicate glass, preferably to a glass of type III, especially of the type conventionally used to constitute perfume vials. Alternatively, monosilate glasses can be used.
The containers of the invention are especially suitable for the packaging of cosmetic compositions in the form of liquids (perfumes, oils, lotions, etc.), but they are also suitable for the packaging of other types of cosmetic formulations, including especially gels, creams, or alternatively compositions in powder form. The containers of the invention are used in particular in the packaging of water- or alcohol-based cosmetic compositions and they are advantageously employed to contain perfumes or alternatively milks, creams, gels, pastes and, more generally, any other cosmetic product.
Various aspects and advantages of the invention are further described in the illustrative examples described hereinbelow, wherein sol/gel coatings have been produced on the inner surface of vials made of sodocalcic and borosilicate glass.
Deposition of a Sol-Gel Film Prepared from TEOS
In a first example, a sol-gel coating was deposited on the inner surface of a vial, the sol-gel coating being obtained by hydrolysis of tetraethoxysilane TEOS.
2 ml of TEOS and then 0.5 ml of ethanol were introduced into a beaker, and the mixture was stirred for one minute. A hydrochloric acid solution obtained by adding one drop of 35% HCl to 0.5 ml of distilled water was added dropwise, with stirring, to the mixture so obtained.
When the addition of acid was complete, the mixture was stirred for a further 24 hours.
A silica gel was thus obtained.
That gel was used to cover the inner surface of a vial which had previously been cleaned in an ethanol bath and then rinsed with water. To that end, the gel was deposited on the inner surface of the vial by spin coating; the resulting film was then dried for 5 minutes and was dried for two hours at 160° C. It is to be noted that deposition can also be carried out by spray coating techniques or alternatively by spin coating, dip coating, flow coating and capillary coating.
Deposition of a Sol-Gel Film Obtained from a Mixture of Precursors TEOS+PhTES+GPTES
In the example, a gel was produced from three different silanes, namely TEOS as used in Example 1, PhTES (phenyltriethoxysilane) and GPTES (3-(glycidylpropyl)-triethoxysilane).
The gel was prepared under the following conditions:
0.2 ml of TEOS, 0.34 ml of GPTES and 0.5 ml of PhTES were introduced into a beaker, then 5.25 ml of ethanol were introduced into the mixture so formed.
An HCl solution obtained by adding one drop of 35% HCl to 0.2 ml of distilled water was then introduced dropwise into that mixture, at ambient temperature (25° C.) and with stirring. When the addition was complete, the mixture was stirred for a further 5 minutes. One drop of a 20% ammonia solution and a Microlith pigment (pigment marketed by CIBA) were then introduced, and stirring was continued for a further 10 minutes.
The resulting gel was used to cover the inner surface of a vial which had previously been cleaned in an ethanol bath and then rinsed with water. To that end, the gel was deposited on the inner surface of the vial by spin coating and then the resulting film was dried for two days and was heat treated at 160° C. for 2 hours.
In this example, a coating comprising a colouring agent (colouring agent red DR1 “dispersed red 1”) was produced on the inner surface of a vial made of glass.
To that end, the following protocol was carried out.
In a 100 ml wide-necked pill-making machine, 1.24 ml of ICPTEOS were reacted for 24 hours at 70° C. with 145 mg of DR1 in 21.1 ml of pyridine, under an inert N2 atmosphere and with stirring.
The resulting mixture was cooled to ambient temperature (25° C.), and then 3.8 ml of TEOS (tetraethoxysilane Si(OC2H5)4) and 25.3 ml of ethanol were added, with stirring.
The mixture so produced was stirred for a further 10 minutes.
An HCl solution obtained by mixing 11 microlitres of a 35% HCl solution (11 M) and 1.5 ml of distilled water was then introduced dropwise into the mixture, at ambient temperature (25° C.) and with continued stirring. When the addition was complete, stirring was continued for 45 minutes, whereby a gel including the colouring agent DR1 bonded covalently to the synthesised silica was obtained.
The resulting gel was used to cover the inner surface of a vial which had previously been cleaned in an ethanol bath and then rinsed with water. To that end, the gel was deposited on the inner surface of the vial by spin coating, and the resulting film was then dried for 2 hours at 80° C.
In this example, a coating comprising an anti-UV filter was produced on the inner surface of a vial made of glass, according to the following protocol.
In a 100 ml wide-necked pill-making machine, 1.24 ml of ICPTEOS (3-isocyanato-propyltriethoxysilane of formula (C2HSO)3Si—(CH)3—NCO) were reacted for 24 hours at 70° C. with 0.4 g of 2-hydroxy-4-methoxybenzophenone in 21.1 ml of pyridine, under an inert N2 atmosphere and with stirring.
The resulting mixture was cooled to ambient temperature (25° C.), and then 3.8 ml of TEOS (tetraethoxysilane Si(OC2H5)4) and 25.3 ml of ethanol were added, with stirring.
The mixture so produced was stirred for a further 10 minutes.
An HCl solution obtained by mixing 11 microlitres of a 35% HCl solution (11 M) and 1.5 ml of distilled water was then introduced dropwise into the mixture, at ambient temperature (25° C.) and with continued stirring. When the addition was complete, stirring was continued for 45 minutes, whereby a gel including benzophenone bonded covalently to the synthesised silica was obtained.
The resulting gel was used to cover the inner surface of a vial which had previously been cleaned in an ethanol bath and then rinsed with water. To that end, the gel was deposited on the inner surface of the vial by spin coating, and the resulting film was then dried for 2 hours at 80° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0856087 | Sep 2008 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2009/061632 | 9/8/2009 | WO | 00 | 3/8/2011 |
| Number | Date | Country | |
|---|---|---|---|
| 61103261 | Oct 2008 | US |
