Peelable film as temporary support

Abstract

The present invention relates to a peelable film as a temporary support, comprising: - a substrate with a first surface which has a predetermined roughness and / or a predetermined brightness, said substrate being selected from the group comprising a plastic or a metal compound; and a thin layer comprising at least one compound which comprises SiCxOy:H and at least one SiCH3 functional group, the first face of the thin layer adhering to the substrate and being arranged to receive, on its second face, a polymerizable reaction composition, characterized in that the thin layer has an adjustable peel strength of greater than 5 N / 25 mm, and in that the thin layer has a surface roughness equivalent to the surface roughness of the substrate.

Description

[0001] PEELABLE FILM ACTING AS A TEMPORARY SUPPORT

[0002] The present invention relates to a peelable film which acts as a support to enable polymerization of a reaction composition.

[0003] Typically, peelable films are used to temporarily support a product and are then removed for use.

[0004] There are several methods for obtaining such films, generally by surface treatment of a substrate. This substrate can be made of polymer. The deposition can be carried out in different ways in order to obtain a thin layer on the substrate.

[0005] This thin layer is generally used to reduce adhesion between the substrate and the product to be protected. Typically, a "release" effect is targeted to allow easy removal of the film.

[0006] However, these films are not suitable for coating a polymerizable composition or a reaction composition on them. One of the major drawbacks is the insufficient adhesion between the peelable film and the polymerizable composition or the dewetting of the surface during coating. It is therefore difficult to use them as support elements.

[0007] Furthermore, other known peelable films are also limited in that they do not ensure good adhesion of the peelable film during the coating of the polymerizable composition (dewetting of the surface) and even afterwards, when the composition is polymerized.

[0008] Known peelable films have such adhesion that they do not provide sufficient support, adhesion and hold which allow easy handling of the reaction composition or the polymerized composition, for example polyurethanes or resins.

[0009] There is therefore a real need to provide a peelable film that can act as a support (base coat) to allow application of a polymerizable reaction composition. In this context, it is desirable to ensure a support effect throughout its use, to maintain sufficient film strength over time and to maintain adequate adhesion to sufficiently support the elements between them and allow removal of the peelable film, if this is necessary depending on the intended application.

[0010] To solve this problem, the present invention provides a peelable film acting as a temporary support, being arranged to allow polymerization of a reaction composition which comprises a compound which contains at least one isocyanate terminal group and a compound which has a group reactive to said at least one isocyanate terminal group, and comprising:

[0011] - a substrate with a first surface which has a predetermined roughness and / or a predetermined gloss, said substrate being selected from the group comprising a plastic material or a metallic compound; and

[0012] - a thin layer comprising at least one compound which comprises SiC x O y:H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, said thin layer having a first face and a second face, said first face of said thin layer adhering to said first surface of said substrate and being arranged to receive, on its second face, said polymerizable reaction composition, characterized in that said thin layer has an adjustable peel force greater than 5 N / 25 mm, preferably greater than 10 N / 25 mm, more preferably greater than 15 N / 25 mm relative to said substrate, and in that said first face of said thin layer has a surface roughness and / or a gloss equivalent to the surface roughness and / or gloss of said first surface of said substrate and, optionally in that said substrate and said thin layer are arranged to allow a transfer of roughness from said substrate to the surface of the polymerized composition.

[0013] Preferably, the polymerized composition is based on polyurethanes or resins.

[0014] Thus, the peelable film according to the invention acts as a support, i.e. a base support for a multi-layer system. This means that the second side of the thin layer is ready to receive a (reactive) composition, preferably polymerizable. Thus, application is easy because it is possible to ensure a homogeneous application on the peelable film. In addition, the layers between them, i.e. the peelable film and the composition, do not separate during or after application, which is particularly advantageous for the user. It is thus possible to handle the assembly easily according to the envisaged method. For example, precisely cutting the multi-layer product.

[0015] Finally, the removal of the peelable film is also easy without damaging the surface of the composition, which offers the film according to the invention a number of varied uses.

[0016] It has also been found that the lifetime of the film according to the invention is advantageous in that the film retains its peel strength and surface energy properties after a period of at least 3 months, in particular when it comprises the polymerized composition. Thus, the control of the adhesion energy imparted by the peel strength makes it possible to provide a peelable film whose adhesion is sufficient to handle and cut the multi-layer product, when used as a support, without the layers separating from each other. The level of adhesion is, however, sufficiently low so that the support film can be removed without damaging the material that has been formed and without leaving a mark on it. The peelable film according to the invention can be peeled off by hand or by thermal transfer onto another substrate.Also, the silicone content in the film according to the invention is limited, which makes it possible to avoid transfer to the composition (material applied to the second face of the thin layer).

[0017] Surprisingly, it was found that when the thin film is formed on the substrate, the thin film conforms to the surface roughness of the substrate. Thus, the thin film substantially matches the surface roughness of the substrate, which is particularly surprising. This is also the case in terms of gloss. Let us imagine that the substrate has a gloss value of 50. After deposition of the thin film, this degree of gloss remains equivalent to the level of the thin film (equivalent, read approximately equal to the gloss value of the substrate). This is advantageous for the user.

[0018] In addition, said substrate and said thin layer are optionally arranged to allow a transfer of roughness from said substrate to the surface of the polymerized composition. In other words, the polymerized composition which may be in the form of a coating will have an equivalent roughness obtained by transfer. This may also be the case in terms of gloss.

[0019] More specifically, this also means that the gloss level of the substrate is not adversely affected by the deposition of the thin layer. Preferably, the support provided by the peelable film is effectively ensured over time during and after application of a composition, preferably polymerizable.

[0020] The composition according to the invention may be an ink (preferably polyurethane or resin) to be coated to then allow a pattern to be transferred onto a t-shirt or any other substrate, a composition to be sprayed, a printable composition, such as that intended for application on a vehicle (commonly called "cast wrapping film" in English) and which would preferably be in the form of a printable coating on the film of the present invention.

[0021] Also, in the case of a polymerizable reaction composition, it is applied (by spraying, flowing, coating, printing for example) on the thin layer. When the reaction composition comprises a compound which comprises a polyol and a compound which comprises an isocyanate terminal group, a polyurethane is formed on the thin layer. The resulting product is treated to obtain a cure (for example by the use of an oven). The peelable film can be removed when the coating is used.

[0022] Preferably, the polymerizable reaction composition according to the invention is a resin, optionally pre-polymerized, chosen from the group comprising epoxy resins, polyimide resins, phenolic resins, bismaleimide resins, cyanoacrylate resins and mixtures thereof. Advantageously, the resin is an epoxy resin for a “pre-preg” type system, as defined below.

[0023] Typically, the side of the coating that was in contact with the thin layer is then applied in various application areas and constitutes the layer of interest, notably as a "cast (wrapping) film" or covering all types of objects. Also, when the composition is an ink to form a polyurethane pattern, this type of application is often used to allow the transfer of a pattern from one substrate to another, such as a t-shirt.

[0024] Preferably, the peelable film according to the invention is arranged to allow polymerization of a reaction composition, advantageously comprising a compound which contains at least one terminal isocyanate group and a compound which has a group reactive to said at least one terminal isocyanate group.

[0025] Advantageously, the peel strength of the second face of the thin layer is less than 30 N / 25 mm, preferably less than 28 N / 25 mm, more preferably less than 25 N / 25 mm, more preferably still less than 15 N / 25 mm, advantageously less than 10 N / 25 mm, more advantageously less than 8 N / 25 mm, more advantageously still less than 5 N / 25 mm, measured according to the FINAT 10 (FTM 10) standard with a Tesa®7475 adhesive.

[0026] The film can also be preferably used as a support to allow application of an ink, preferably based on polyurethane or resins, with the aim of carrying out a transfer onto a separate substrate.

[0027] It has also been found that the adjustable peel force greater than 5 N / 25 mm makes it possible to achieve the effects of the present invention. One of the characteristic points of the invention is the fact that this peel force can be adjusted and reach a value of up to 15 N / 25 mm, preferably up to 29, 30, 31, 32, 33, 34 or 35 N / 25 mm. Preferably, said thin layer has a thickness less than or equal to 6 nm, preferably less than or equal to 5 nm, more preferably less than 3 nm. Even more preferably, it is possible to achieve a thickness of 1 nm. This makes it possible, depending on the desired application, to provide a thin layer which will have a certain quantity of silicone, while retaining the advantages described in the context of the present invention.

[0028] Advantageously, said film of the invention has a surface energy of between 20 and 30 mN / m, preferably between 25 and 30 mN / m.

[0029] Controlling the surface energy allows for easy application of the composition by limiting or even avoiding any dewetting zone, which allows for an application, preferably a coating of the composition that is uniform and defect-free.

[0030] The combination of surface energy and peel force advantageously makes it possible to provide an even more efficient peelable film. This is even more advantageous when the peel force of the second face of the thin layer according to the invention (which comprises the polymerized composition) has a peel force of less than 30 N / 25 mm, preferably less than 28 N / 25 mm, more preferably less than 25 N / 25 mm, more preferably still less than 15 N / 25 mm, advantageously less than 10 N / 25 mm, more advantageously less than 8 N / 25 mm, even more advantageously less than 5 N / 25 mm, measured according to the FINAT 10 (FTM 10) standard with a Tesa®7475 adhesive. This peel force thus advantageously characterizes the second face of the thin layer which is intended to be in contact with the polymerized composition.

[0031] More preferably, said substrate is made of polymer material, preferably of bi-oriented polymer material. Advantageously, the substrate is a film made of polyester, polyimides, polyamides, polyether ketones and their derivatives.

[0032] Even more advantageously, the substrate is made of PET film or polyimides when the polymerizable reaction composition is a resin, optionally pre-polymerized, according to the invention.

[0033] Even more advantageously, the substrate material is co-extruded and / or bi-oriented.

[0034] Preferably, the substrate is a film made of material selected from the group consisting of polyethylene terephthalate (PET), polyimide, polyamide, poly(ethylene naphthalate) (PEN), polyether ether ketone (PEEK) and their derivatives. These materials can thus be bi-oriented, preferably co-extruded and bi-oriented.

[0035] PET will preferably be chosen, in particular when the polymerizable composition comprises at least one polyisocyanate and one polyol to form a polymerized polyurethane as defined according to the invention.

[0036] Advantageously, the polyimide will be chosen in combination with the resin as defined in the invention.

[0037] According to a preferred embodiment, the peelable film acting as a temporary support also comprises a resin, optionally pre-polymerized, the film comprising:

[0038] - a substrate with a first surface which has a predetermined roughness and / or a predetermined gloss, said substrate being selected from the group comprising a plastic material or a metallic compound; and

[0039] - a thin layer comprising at least one compound which comprises SiC x O y:H and at least one SiCHs functional group, where x is or less equal to 2 and y is at least equal to 0.5, said thin layer having a first face and a second face, said first face of said thin layer adhering to said first surface of said substrate and including, on its second face, said resin, optionally pre-polymerized, characterized in that said thin layer has an adjustable peel force greater than 5 N / 25 mm, preferably greater than 10 N / 25 mm, more preferably greater than 15 N / 25 mm relative to said substrate, and in that said first face of said thin layer has a surface roughness and / or a gloss equivalent to the surface roughness and / or gloss of said first surface of said substrate and, optionally in that said substrate and said thin layer are arranged to allow a transfer of roughness from said substrate to the surface of the polymerized composition.

[0040] All the characteristics mentioned above can be combined with this preferred embodiment, in the presence of the resin (pre-polymerized).

[0041] Advantageously, the peelable film according to the invention is obtainable (or directly obtained) by an atmospheric pressure plasma process applied, preferably continuously and which comprises the following steps:

[0042] Preparation of a plasma gas chosen from the group consisting of noble gases and their mixtures;

[0043] Preparation of a volatile precursor selected from the group consisting of cyclic siloxanes, linear siloxanes and mixtures thereof, Rolling said substrate which has a first surface, preferably in a roll-to-roll device (commonly called "roll-to-roll" in English), within a coating cell equipped with a plasma,

[0044] Exposing said first face of said substrate to cold plasma deposition in an atmospheric pressure chamber, in which there is a gaseous atmosphere comprising said plasma gas, preferably with a dielectric barrier controlled discharge (DBD), and in the presence of said precursor to apply plasma polymerization,

[0045] Forming and depositing said thin layer on said first surface of said substrate, said thin layer comprising at least one compound which comprises SiC x O y :H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, with formation of said film.

[0046] Particularly advantageously, said exposure of said first face of said substrate takes place during a period of time between 50 and 2500 milliseconds.

[0047] According to a particular mode, the exposure is carried out by maintaining the plasma enclosure and / or the substrate at a temperature below 100°C within the enclosure at atmospheric pressure.

[0048] According to a preferred embodiment, the cyclic siloxanes are chosen from the group consisting of hexamethylcyclotrisiloxane (D3), octamethylcyclopentasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), vinyl 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane and mixtures thereof.

[0049] Linear siloxanes are preferentially chosen from compounds which have the following structure [SiOjCHs Jn, in which n is equal to at least 2.

[0050] Even more preferably, the linear siloxanes are chosen from the group consisting of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.

[0051] Advantageously, the total quantity of plasma gas is injected at a flow rate of between 45 and 80 m 3 / hour, preferably between 45 and 75 m 3 / hour, for a useful film width of 2 m.

[0052] Advantageously, the running speed of the substrate is between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min. In a particularly advantageous manner, the running speed of the substrate is linked to a certain total quantity of plasma gas injected.

[0053] Even more advantageously, said precursor is injected at a flow rate of between 50 and 200 g / hour, preferably between 50 and 150 g / hour, more preferably between 75 and 115 g / hour for a useful film width of 2 m. Preferably, the substrate travel speed is between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min. These two flow rate and travel speed parameters can be combined with each other.

[0054] According to a preferred configuration, the method further comprises an application of a composition, preferably a polymerizable reaction composition, on said second face of said thin layer, after formation of said film.

[0055] As explained above, the support film used as a base layer makes it possible to receive a composition according to the invention. This composition is preferably polymerizable and can be a resin (originating from a pre-preg) or be obtained by reacting a polyisocyanate with a polyol as described in the present application.

[0056] In the case of a resin (coming from a pre-preg) which is pre-polymerized, the peelable film according to the invention can be placed on the resin in order to protect it.

[0057] According to an example of manufacturing a pre-preg, the resin can be placed on the film according to the invention which is then laminated with a reinforcing material (e.g. a carbon fiber) to transfer the resin onto it. This can be done on both sides of the reinforcing material (carbon fiber). In other words, the film according to the invention which is present on both sides of the pre-preg. One of the two films can then be removed and the other kept in order to be able to wind the film into a reel and allow its storage. The peeling forces can thus be distinct and adjusted according to the necessary needs.

[0058] Other methods of manufacturing pre-preg are possible and known to those skilled in the art. Preferably, said polymerizable reaction composition is obtained by reacting a compound comprising at least one terminal isocyanate group with a compound which has a group reactive to said at least one terminal isocyanate group or by applying a resin, optionally pre-polymerized.

[0059] Examples of polyfunctional isocyanates include, but are not limited to: ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and -1,4-diisocyanate, and mixtures of isomers thereof; isophorone diisocyanate; 2,4- and 2,6-hexahydrotoluene diisocyanate and mixtures of isomers thereof; dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI or HMDI); 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of isomers thereof (TDI); diphenylmethane-2,4'- and / or -4,4'- diisocyanate (MDI); naphthylene-1,5-diisocyanate; triphenylmethane-4,4',4"-triisocyanate; polyphenyl-polymethylene-polyisocyanates of the type obtainable by condensation of aniline with formaldehyde, followed by phosgenation (polymeric MDI); m- and p-isocyanatophenyl sulfonylisocyanates; perchlorinated aryl polyisocyanates;polyfunctional modified isocyanates containing carbodiimide groups, urethane groups, allophonate groups, isocyanurate groups, urea groups, or biruret groups; polyfunctional isocyanates obtained by telomerization reaction, polyfunctional isocyanates containing ester groups; and polyfunctional isocyanates containing fatty acid groups. The person skilled in the art will recognize that it is possible to use mixtures of polyfunctional isocyanates described above, preferably by using a mixture of polymeric MDI, and a mixture of MDI isomers.;

[0060] A compound which has a reactive group with said at least one terminal isocyanate group is advantageously a polyfunctional polyol or a polyfunctional amine.

[0061] The polyfunctional polyols according to the present invention may be, but are not limited to, polyether polyols, polyester polyols, bio-sourced or renewable polyols, polymer polyols, flammable polyols, such as phosphorus-based or halogen-based polyols. These polyols may be used alone or in combination as a mixture.

[0062] The amount of polyfunctional polyol may be between 10 and 90% by weight relative to the total weight of the polymerizable composition, preferably between 30 and 80% by weight.

[0063] The polyether polyols of the present invention include alkylene oxide polyether polyols, e.g., ethylene oxide polyether polyols and propylene oxide polyether polyols and ethylene and propylene oxide copolymers with terminal OH groups that are derived from polyhydric compounds, including diols and trials; e.g., ethylene glycol, propylene glycol, 1,3-butane dial, 1,4-butane dial, 1,6-hexane dial, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane, and similar low molecular weight polyols.

[0064] Polyester polyols of the invention include, but are not limited to, those produced by reacting a carboxylic acid with an excess of dial, for example, adipic acid with ethylene glycol or butanedial, or reacting a lactone with an excess of dial, such as caprolactone with propylene glycol. In addition, polyester polyols of the invention may also include linear (partially) branched aliphatic polyols (primarily adipates) with terminal OH groups; low molecular weight aromatic polyesters; polycaprolactones; polycarbonate polyols. Branched or linear (partially) aliphatic polyols (primarily adipates) that have terminal OH groups produced by reaction between dicarboxylic acids and an excess of diols, trials and mixtures thereof.The renewable polyols according to the present invention include castor oil, sunflower oil, palm kernel oil, palm oil, canola oil, rapeseed oil, soybean oil, corn oil, peanut oil, olive oil, algae oil and mixtures thereof.

[0065] Examples of polyfunctional polyols also include, but are not limited to, graft polyols or polyurea-modified polyols. Graft polyols include a triol in which vinyl monomers are graft copolymerized. Suitable vinyl monomers include, for example, styrene or acrylonitrile. A polyurea-modified polyol is a polyol containing a polyurea dispersion formed by the reaction of a diamine and a diisocyanate in the presence of a polyol. A variation of polyurea-modified polyols are isocyanate polyaddition (IPPA) polyols, which are formed by the in situ reaction of an isocyanate and an alkanolamine in a polyol.

[0066] The polyfunctional amine for use in the present disclosure may include polyether polyamine or polyester polyamine.

[0067] In a preferred embodiment, a compound that has a reactive group at said at least one terminal isocyanate group is a polyether polyol.

[0068] Advantageously, the reaction composition makes it possible to provide a polyurethane. The polyurethane may also be a thermoplastic polyurethane that the person skilled in the art can provide.

[0069] Preferably, said polymerizable reaction composition is a resin, optionally pre-polymerized, chosen from the group comprising epoxy resins, polyimide resins, phenolic resins, bismaleimide resins, cyanoacrylate resins and mixtures thereof. Advantageously, the resin is an epoxy resin, optionally pre-polymerized. According to an advantageous embodiment, the (pre-polymerized) resin is formed on a composite structure which includes a reinforcing material chosen from the group comprising carbon fiber, glass fiber, aramid fiber and combinations thereof.

[0070] Thus, a “pre-preg” type structure may comprise the peelable film according to the present invention. This film can thus be removed at the time when the “pre-preg” type structure is to be completely polymerized.

[0071] Preferably, said composition is polymerized and the surface roughness of the first surface of said substrate is transferred to the surface of the polymerized composition.

[0072] This means that when the polymerized composition is obtained, it in some way matches the surface roughness of the substrate and the thin layer so as to form a substantially equivalent roughness on the polymerized composition.

[0073] Advantageously, after removal of said film from said polymerized reaction composition, the shine of said polymerized composition, preferably in the form of a coating, is retained.

[0074] This allows the composition to be used as a coating, for example, on another substrate. In the case of resin, it can be part of a pre-preg type structure.

[0075] Advantageously, the (reaction) composition is applied by coating, flowing, spraying, pulverizing or printing (in the case of coating application) or by gaseous means.

[0076] According to a more preferred embodiment, said peelable film has a lifetime corresponding to at least 2 uses, preferably at least 5 uses, preferably at least 8 uses as a support film with maintenance of the surface energy and / or the peeling force of said film during repeated uses, and in which each use corresponds to an application of a separate additional (reaction) composition on said second face of said thin layer.

[0077] Other embodiments of the film according to the invention are indicated in the appended claims.

[0078] The present invention also relates to a method for manufacturing a peelable film acting as a temporary support, being arranged to allow polymerization of a reaction composition which comprises a compound which contains at least one isocyanate end group and a compound which has a group reactive to said isocyanate end group, comprising the following steps: a. Preparation of a plasma gas selected from the group consisting of noble gases and mixtures thereof, b. Preparation of a volatile precursor selected from the group consisting of cyclic siloxanes, linear siloxanes and mixtures thereof, c. Running a substrate having a first surface and having a predetermined gloss and / or a predetermined surface roughness, preferably in a roll-to-roll device, within a coating cell equipped with atmospheric plasma, d.Exposure, optionally for a period of time between 200 and 2500 milliseconds, of said first face of said substrate to cold plasma deposition in an atmospheric pressure chamber, in which there is a gaseous atmosphere comprising said plasma gas, preferably with a dielectric barrier discharge (DBD) and in the presence of said precursor, e. Formation and deposition of said thin layer having a first and second surface and which comprises at least one compound which comprises SiC. x O y:H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, f. Collection of said peelable film, characterized in that said thin layer has a peel force greater than 5 N / 25 mm, preferably greater than 10 N / 25 mm, more preferably greater than 15 N / 25 mm relative to said substrate, and in that said first face of said thin layer has a surface roughness and / or a gloss equivalent to the surface roughness and / or gloss of said surface of said substrate and, optionally in that said substrate and said thin layer are arranged to allow a transfer of roughness from the first surface of said substrate to the surface of the polymerized composition.

[0079] All the characteristics listed above for the peelable film also apply to the process as well as all possible combinations of implementation.

[0080] Other embodiments of the method according to the invention are indicated in the appended claims.

[0081] The present invention further relates to a multi-layer system comprising:

[0082] A polymerizable reaction composition which optionally comprises a compound which contains at least one isocyanate terminal group and a compound which has a group reactive with said at least one isocyanate terminal group or a resin, optionally pre-polymerized,

[0083] A peelable film acting as a temporary support for said composition comprising: o a substrate with a first surface which has a predetermined roughness and / or a predetermined gloss, said substrate being selected from the group comprising a plastic material or a metallic compound; and thereon o a thin layer comprising at least one compound which comprises SiC x O y:H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, said thin layer having a first face and a second face, said first face of said thin layer adhering to said first surface of said substrate and said second face of said thin layer being in contact with said polymerizable reaction composition, characterized in that said thin layer has a peel strength greater than 5 N / 25 mm, preferably greater than 10 N / 25 mm, more preferably greater than 15 N / 25 mm relative to said substrate, and in that said first face of said thin layer has a surface roughness and / or a gloss equivalent to the surface roughness and / or gloss of said first surface of said substrate and,optionally in that said substrate and said thin layer are arranged to allow a transfer of roughness from the first surface of said substrate to the surface of the polymerized composition.,

[0084] Again, all the characteristics mentioned above for the process and for the film of the invention apply to the multi-layer system also including all possible combinations of characteristics.

[0085] Other embodiments of the multi-layer system are indicated in the appended claims.

[0086] The present invention also relates to a pre-preg article or multilayer or system which comprises the film according to the present invention. A pre-preg structure can thus exemplify this embodiment.

[0087] The invention also relates to a pre-preg type article which comprises a first face and a second face, characterized in that said first and second faces are each provided with a film according to the invention.

[0088] Advantageously, the peel force of the second face of the thin layer which covers the first face of the pre-preg type article has a lower peel force than the peel force of the other thin layer which covers the second face of said pre-preg type article.

[0089] Other embodiments of the article or multi-layer according to the invention are indicated in the appended claims.

[0090] The present invention also relates to an additional embodiment which relates to a peelable film acting as a temporary support, being arranged to allow deposition thereon of a metallic layer to allow formation of a hologram, and comprising: a substrate having a first surface and being selected from the group comprising a plastic material or a metallic compound; and thereon a thin layer comprising at least one compound which comprises SiC x O y:H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, said thin layer having a first face and a second face, said first face of said thin layer adhering to said first surface of said substrate and being arranged to receive, on its second face, said polymerizable reaction composition, characterized in that said thin layer has an adjustable peel force greater than 20 N / 25 mm, preferably greater than 22 N / 25 mm, more preferably greater than 23 N / 25 mm, advantageously less than 30 N / 25 mm relative to said substrate, particularly advantageously between 22 and 29 N / 25 mm.

[0091] Thus, the peelable film according to the invention acts as a support, read background support of a multi-layer system. This means that the second face of the thin layer is ready to receive the deposition of the metal layer. The layers between them, that is to say the peelable film and the metal layer, do not separate during or after application, which is particularly advantageous for the user. It is thus possible to handle the assembly easily according to the intended handling. For example, precisely cut the multi-layer product. Finally, the removal of the peelable film is also easily ensured without damaging the surface of the composition, which offers the film according to the invention a number of varied uses. The control of the adhesion energy conferred by the peel force makes it possible to provide a peelable film whose adhesion is sufficient to handle, cut the multi-layer product, when it is used as a support, without the layers separating from each other.The adhesion level is, however, low enough that the carrier film can be removed without damaging the material that has been formed and without leaving a mark on it. The peelable film according to the invention can be peeled off by hand, generally when the final product is obtained. This means that other layers can still be added. During the final use of this product, the peelable film according to the invention can be removed. Also, the silicone content in the film according to the invention is limited, which makes it possible to avoid transfer to the composition (material applied to the second side of the thin layer).

[0092] In this case, the composition is not necessarily reactive. It is a composition that can be deposited in the form of a metallic layer by gaseous means, preferably by chemical vapor deposition or by evaporation or even applied by liquid means. The person skilled in the art will know how to apply this composition in order to provide a metallic layer on the peelable film of the invention.

[0093] Advantageously, the peel strength of the second face of the thin layer of the film according to the invention relative to the metal layer is less than 5 N / 25 mm, preferably less than 4 N / 25 mm, more preferably less than 3 N / 25 mm, more preferably still less than 1 N / 25 mm, advantageously less than 0.5 N / 25 mm, more advantageously less than 0.05 N / 25 mm measured according to the FINAT 10 (FTM 10) standard with a Tesa®7475 adhesive.

[0094] Additionally and preferably, the metal layer is deposited on the substrate, for example PET. Then, the metal layer is transferred from the PET to an embossed varnish, which makes it possible to provide the hologram.

[0095] Preferably, the support provided by the peelable film is ensured effectively over time during and after application of a composition, preferably polymerizable.

[0096] Preferably, said thin layer has a thickness less than or equal to 6 nm, preferably less than or equal to 5 nm, more preferably less than 3 nm and said film has a surface energy of between 20 and 30 mN / m, preferably between 25 and 30 mN / m.

[0097] Preferably, the noble gases are chosen from argon, helium and their mixtures.

[0098] More preferably, said substrate is made of polymer material, preferably of bi-oriented polymer material.

[0099] More preferably, said substrate is made of polymer material, preferably of bi-oriented polymer material.

[0100] Advantageously, the substrate is a film made of polyester, polyimides, polyamides, polyether ketones and their derivatives.

[0101] Even more advantageously, the substrate material is co-extruded and / or bi-oriented.

[0102] Preferably, the substrate is a film made of material selected from the group consisting of polyethylene terephthalate (PET), polyimide, polyamide, poly(ethylene naphthalate) (PEN), polyether ether ketone (PEEK) and their derivatives. These materials can thus be bi-oriented, preferably co-extruded and bi-oriented.

[0103] PET will be preferably chosen. Advantageously, the film according to this additional embodiment is obtainable by a continuously applied atmospheric pressure plasma process which comprises the following steps:

[0104] - Preparation of a plasma gas chosen from the group consisting of noble gases and their mixtures;

[0105] - Preparation of a volatile precursor chosen from the group consisting of cyclic siloxanes, linear siloxanes and their mixtures,

[0106] - Scrolling of said substrate which has a first surface, preferably in a roller-to-roller device, within a coating cell equipped with a plasma,

[0107] - Exposure of said first face of said substrate to cold plasma deposition in an atmospheric pressure enclosure, in which there is a gaseous atmosphere comprising said plasma gas, preferably with a dielectric barrier controlled discharge (DBD), and in the presence of said precursor to apply plasma polymerization,

[0108] - Forming and depositing said thin layer on said first surface of said substrate, said thin layer comprising at least one compound which comprises SiC x O y :H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, with formation of said film.

[0109] Advantageously, the total quantity of plasma gas is injected at a flow rate of between 45 and 80 m 3 / hour, preferably between 45 and 75 m 3 / hour, for a useful film width of 2 m. Advantageously, the substrate running speed is between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min. Particularly advantageously, the substrate running speed is linked to a certain total quantity of plasma gas injected.

[0110] Even more advantageously, said precursor is injected at a flow rate of between 50 and 200 g / hour, preferably between 50 and 150 g / hour, more preferably between 75 and 115 g / hour for a useful film width of 2 m. Preferably, the substrate travel speed is between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min. These two flow rate and travel speed parameters can be combined with each other.

[0111] According to an advantageous embodiment, said method further comprises chemical vapor deposition of a metal layer on said thin layer, after formation of said film.

[0112] According to a preferred configuration, the peelable film has a lifetime corresponding to at least 2 uses, preferably at least 5 uses, preferably at least 8 uses as a support film with maintenance of the surface energy and / or the peel force of said film during repeated uses, and in which each use corresponds to an application of a new separate metal layer by chemical vapor deposition on said second face of said thin layer.

[0113] The additional embodiment according to the present invention also relates to a method for manufacturing a peelable film acting as a temporary support, being arranged to allow deposition of a metal layer comprising the following steps: a. Preparation of a plasmagenic gas selected from the group consisting of noble gases and mixtures thereof, b. Preparation of a volatile precursor selected from the group consisting of cyclic siloxanes, linear siloxanes and mixtures thereof, c. Running a substrate, preferably in a roll-to-roll device, within a coating cell equipped with atmospheric plasma, d. Exposure of said first face of said substrate to cold plasma deposition in an atmospheric pressure chamber, in which there is a gaseous atmosphere comprising said plasmagenic gas, preferably with a dielectric barrier discharge (DBD) and in the presence of said precursor, e.Formation and deposition of said thin layer having a first and second surface and which comprises at least one compound which comprises SiC. x O y :H and at least one functional group SiCFh, where x is at least equal to 2 and y is at least equal to 0.5, f. Collection of said peelable film, thin layer has an adjustable peel force greater than 20 N / 25 mm, preferably greater than 22 N / 25 mm, more preferably greater than 23 N / 25 mm, advantageously less than 30 N / 25 mm relative to said substrate, particularly advantageously between 22 and 29 N / 25 mm.

[0114] Particularly advantageously, said exposure of said first face of said substrate takes place during a period of time between 50 and 2500 milliseconds. TJ

[0115] According to a particular mode, the exposure is carried out by maintaining the plasma enclosure and / or the substrate at a temperature below 100°C within the enclosure at atmospheric pressure.

[0116] According to a preferred embodiment, the cyclic siloxanes are chosen from the group consisting of hexamethylcyclotrisiloxane (D3), octamethylcyclopentasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), vinyl 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane and mixtures thereof.

[0117] Linear siloxanes are preferentially chosen from compounds which have the following structure [SiOjCHs Jn, in which n is equal to at least 2.

[0118] Even more preferably, the linear siloxanes are chosen from the group consisting of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.

[0119] Advantageously, the total quantity of plasma gas is injected at a flow rate of between 45 and 80 m 3 / hour, preferably between 45 and 75 m 3 / hour, for a useful film width of 2 m.

[0120] Advantageously, the running speed of the substrate is between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min. In a particularly advantageous manner, the running speed of the substrate is linked to a certain total quantity of plasma gas injected.

[0121] Even more advantageously, said precursor is injected at a flow rate of between 50 and 200 g / hour, preferably between 50 and 150 g / hour, more preferably between 75 and 115 g / hour for a useful film width of 2 m. Preferably, the substrate travel speed is between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min. These two flow rate and travel speed parameters can be combined with each other.

[0122] Other embodiments of the additional embodiment of the film according to the invention are indicated in the appended claims.

[0123] The additional embodiment of the peelable film also includes a multi-layer system comprising:

[0124] A metallic layer,

[0125] A peelable film acting as a temporary support to allow said metal layer to be deposited and comprising: o a substrate with a first surface, said substrate being selected from the group comprising a plastic material or a metal compound; and thereon o a thin layer comprising at least one compound which comprises SiC x O y:H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, said thin layer having a first face and a second face, said first face of said thin layer adhering to said first surface of said substrate and said second face of said thin layer being in contact with said metal layer, thin layer having an adjustable peel force greater than 20 N / 25 mm, preferably greater than 22 N / 25 mm, more preferably greater than 23 N / 25 mm, advantageously less than 30 N / 25 mm relative to said substrate, particularly advantageously between 22 and 29 N / 25 mm.

[0126] Other embodiments of the additional embodiment of the method according to the invention are indicated in the appended claims.

[0127] Furthermore, this additional embodiment also relates to an article or a multi-layer which comprises the peelable film according to this 2 èmeembodiment.

[0128] All the characteristics mentioned for the additional embodiment of the film are combinable with each other, in other words for the film, film obtained by the process, the film manufacturing process, the system, the article or the multi-layer.

[0129] Other embodiments of the article according to the invention are indicated in the appended claims.

[0130] The invention also relates to an article comprising a pre-preg provided with a film according to the invention (as described above), in which said film is used as a release film.

[0131] Other embodiments of the additional embodiment of the method according to the invention are indicated in the appended claims.

[0132] The method according to the invention requires the use of a device that generates a plasma. The device comprises a roll-to-roll system on which the substrate passes continuously. A reactor is also provided and comprises the following elements:

[0133] A processing cylinder (e.g. 400 mm diameter and 800 mm long) with a suitable dielectric coating. This cylinder drives the substrate to be processed under processing electrodes, preferably at least 3 electrodes, at a speed chosen from the range between 7 and 60 m / min;

[0134] A treatment chamber located above the treatment cylinder and comprising electrodes and gas injection devices; injection devices adjacent to the electrodes make it possible to inject the gas(es) directly in front of the electrodes and onto the surface of the substrate to be treated, namely: the inerting gas, the plasma gas, the precursor, the vector gas, the possible doping gas.

[0135] The plasma gas according to the invention is preferably argon or helium.

[0136] The electrodes are connected to a low frequency HV generator (typically one to a few hundred kHz) and of variable power (0.1 to 10 W / cm 2 ) . The power density is between 0.10 W / cm2 and 10 W / cm 2 , preferably between 0.15 W / cm 2 and 8 W / cm 2 , or even between 0.2 W / cm 2 and 5 W / cm 2 , more preferably between 0.25 W / cm 2 and 0.8 W / cm 2, and even more preferably between 0.35 W / cm 2 and 0.7 W / cm 2 , the unit of area referring to the cumulative surface area of ​​the electrodes.

[0137] Thus, the substrate unwinding, exposure and film formation steps can be combined with the above elements.

[0138] An extraction system in the treatment chamber allows the plasma gas and any by-products created in the plasma and not transformed into a deposit to be evacuated. The plasma gas generates the plasma; this is a specific feature of atmospheric pressure discharge. The carrier gas is injected to accompany the precursor (monomer). The dopant can be injected in small quantities compared to the inerting, plasma gas and carrier gases. The inerting gas, the plasma gas and / or the carrier gas can be the same or different, and can be argon and / or helium.

[0139] Advantageously, an inert treatment atmosphere is maintained in the treatment reactor with an oxygen level of less than 50 ppm, preferably less than 20 ppm, and even more preferably less than 10 ppm.

[0140] A reactor such as this is for example described in patent application WO 2016 170 242 and in application WO 2019 154 976.

[0141] The inerting gas, plasma gas and / or carrier gas may be the same or different, and may be argon and / or helium.

[0142] Advantageously, the spacing between the active surface of the electrodes and the film running beneath them on the treatment cylinder can be adjusted to ensure the stability and homogeneity of the plasma. For example, if the distance between the film and the active surface of the electrodes is set to 1 mm, this distance is advantageously stable with a standard deviation of ± 0.2 mm.

[0143] The precursor is advantageously injected directly into the discharge, this allows to maximize its concentration between the electrodes. This is useful to make treatment possible in a single pass. A high concentration of precursor in the discharge generally leads to the formation of powder in the plasma; these powders make the product unusable and cause many maintenance problems for the reactor. With a high gas velocity, the residence time of the precursor molecules in the plasma can be reduced; this avoids the formation of powder. Thus, it is possible to work at a high precursor concentration, which allows the deposition to be carried out in a single pass without forming powder.

[0144] Advantageously, the total quantity of plasma gas is injected at a flow rate of between 45 and 80 m 3 / hour, preferably between 45 and 75 m 3 / hour, for a useful film width of 2 m.

[0145] Advantageously, the running speed of the substrate is between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min. In a particularly advantageous manner, the running speed of the substrate is linked to a certain total quantity of plasma gas injected.

[0146] Even more advantageously, said precursor is injected at a flow rate of between 50 and 200 g / hour, preferably between 50 and 150 g / hour, more preferably between 75 and 115 g / hour for a useful film width of 2 m. The substrate travel speed is between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min. These two flow rate and travel speed parameters can be combined with each other.

[0147] Particularly advantageously, it has been found that for the coating of a polymerizable reaction composition to form a polyurethane, a treatment at 60 m / min on a substrate (satin film - Hostaphan MT 50) is advantageous. Even more advantageously and additionally, the coating of a polymerizable reaction composition to form a polyurethane on a substrate (ultramat film - Hostaphan XMTK) is carried out at 15 m / min. Thus, depending on the needs and properties envisaged, the running speed of the film will be adapted. The power generated in the plasma is preferably between 900 W and 2000 W, more preferably between 900 W and 1500 W. The plasma gas is preferably argon.

[0148] When the term "resin" is used, this designates, within the scope of the invention, a resin, optionally pre-polymerized, chosen from the group comprising epoxy resins, polyimide resins, phenolic resins, bismaleimide resins, cyanoacrylate resins and mixtures thereof. Advantageously, the resin is an epoxy resin for a "pre-preg" type system as defined below.

[0149] The terms "pre-preg", "pre-preg structure" or "pre-preg product" or "pre-impregnated material" or any equivalent refer to a pre-impregnated structure which comprises a composite structure which includes a reinforcing material preferably selected from the group consisting of carbon fiber, glass fiber, aramid fiber and combinations thereof and a resin, optionally pre-polymerized, selected from the group consisting of epoxy resins, polyimide resins, phenolic resins, bismaleimide resins, cyanoacrylate resins and mixtures thereof. Advantageously, the resin is a (pre-polymerized) epoxy resin.

[0150] The term "pre-preg" means "pre-impregnation". In other words, the pre-preg product comprises the resin, which is preferably pre-polymerized (so that it can be preserved / stored), and the reinforcing material. The peelable film according to the invention protects the pre-preg product until the final polymerization.

[0151] In the pre-preg manufacturing process, the reinforcing material is uniformly pre-impregnated with a quantity of resin that is usually partially cured, meaning it is not completely cured but has some degree of polymerization. This state of partial polymerization allows the material to be stored and transported without premature polymerization.

[0152] Pre-preg structures are used in the production of high-performance composite components for industries such as aerospace, automotive and sports equipment.

[0153] Thus, the peel film according to the invention is a temporary protective layer that plays a role in the manufacturing process of pre-preg type structures, ensuring correct handling, preventing premature curing of the resin and facilitating the production of high quality composite structures with pre-impregnated materials.

[0154] In the manufacturing process of composite materials using prepregs, the release film is usually removed before final curing. The release film serves as a temporary protective layer during installation and handling of the prepreg material, but it is designed to be easily removed before (or after) the curing process.

[0155] Typically, the manufacture of the pre-preg with the film according to the invention can be presented as follows:

[0156] - The layers of the pre-preg structure, often provided with the film according to the invention, are stacked to form the desired composite structure,

[0157] - In some cases, a debubbling step (applying pressure and heat) may be included before final curing to remove air and excess resin and ensure good consolidation of the layers, - Before final curing, the peel film is carefully removed from the composite structure. This is usually done to allow the resin in the prepreg material to fully cure without being hindered by the film.

[0158] For the purposes of the present invention, "equivalent" means a value or parameter which is close to or equal to the value or parameter taken as reference. This term also means that the value analyzed is approximately equal to the value or parameter taken as reference.

[0159] The term "roughness" refers to a surface roughness that can be determined by a roughness meter or by profilometry which allows to obtain the coefficient Ra (arithmetic mean of the deviations from the mean line) whose value indicates the average roughness of the surface for the length of the measurement carried out, that is, the average deviation between peaks and valleys. In addition, an Atomic Force Microscopy (AFM) method can also be considered.

[0160] The expression “acting as a temporary support” advantageously means that the film according to the invention is predisposed to being removed and is thus a support which plays the role of temporary protection of the product which it covers / supports.

[0161] The term "gloss" refers to the gloss of a surface or material determined using a device such as the IGT Gloss Meter G60 (ISO 2813, ASTM D2457 and ASTM D523). The device used in the examples is the IGT G75, which corresponds to the TAPPI reference T480 om-2009 and ISO 8254-1. This device uses a converging beam and allows a gloss measurement that involves an angle of 75° to the substrate. A predetermined gloss or a predetermined roughness means that the gloss has a certain starting value.

[0162] The terms "thin films" relate to the plasma-related field and are perfectly understood by those skilled in the art.

[0163] The surface energy used in the present invention is calculated from contact angle measurements of two liquids (water and diiodomethane) according to the Owens, Wendt, Rebel and Kaelble (OWRK) model with a Krüss DSA 25 instrument.

[0164] The peel strength is determined in relation to a test carried out on the adhesive “tesa® 7475”, according to the FTM 10 standard with the AR1000 device, preferably 20 hours at 70°C, unless otherwise stated.

[0165] The FTM 10 standard, known to those skilled in the art, is published by FINAT (International Federation of Manufacturers and Converters of Adhesives and Iron-on Adhesives on Paper and Other Media):

[0166] FTM 10 “Quality of silicone coated substrates for self-adhesive laminates: release force (300 mm per minute)”.

[0167] The thickness can be induced by applying an XPS technique or by using a TEM (Transmission Electron Microscopy) sectional image method known to those skilled in the art.

[0168] Example 1

[0169] Several films according to the invention have been provided using argon and the monomer DMCPS (D5) as a precursor. Table 1 below indicates the type of PET substrate used as well as the running speed applied to form the thin layer on the substrate. The peel force is expressed in the column "Tesa 7475" in N / 25 mm.

[0170] Table 1 Table 2

[0171] Table 2 shows the obtained surface energy values ​​for the different films according to Example 1.

[0172] Example 2

[0173] It is noted that the degree of gloss before deposition of the thin layer and after deposition of the latter is preserved (see table below).

[0174] Example 3

[0175] Example 3 relates to a Nylon (polyamide) substrate which is treated according to the plasma method according to the invention in order to provide the peelable film which comprises the thin layer on one of its faces (see table below).

[0176] Example 4 Example 4 relates to a polyimide (kapton) substrate which is treated according to the plasma method according to the invention in order to provide the peelable film which comprises the thin layer on one of its faces, as illustrated in the table below.

[0177] The peel strength (Fp) of Examples 3 and 4 was expressed either relative to Tesa®7475 adhesive or relative to TESA® 501 10 adhesive. Comparative example

[0178] An untreated PET film with a matte surface roughness has a given degree of gloss. After applying the silicone-based thin layer to the PET, a reduction in the matte effect is observed.

[0179] Also, with this type of film the observed peel force is 0.1 N / 25 mm.

[0180] In the context of the present invention, any singular article such as, for example, "a", "an", "the", "the", "of", "of the" may be replaced by an article which designates a plural such as, for example, "at least 2", "at least 3", "several" etc.

[0181] The word "include", "contains" or any equivalent or derivative term may be replaced by "consisting of" in order to define a list or exclusive selection possibilities so as not to include other elements not mentioned in the expression used.

[0182] Also, the terms “obtainable” or “obtainable” or any similar or derivative expression may be replaced by “directly obtained”.

[0183] It is understood that the present invention is in no way limited to the embodiments described above and that many modifications may be made thereto without departing from the scope of the appended claims.

Claims

CLAIMS 1. A peelable film acting as a temporary support, being arranged to allow polymerization of a reaction composition which comprises a compound which contains at least one terminal isocyanate group and a compound which has a group reactive with said at least one terminal isocyanate group, and comprising: - a substrate with a first surface which has a predetermined roughness and / or a predetermined gloss, said substrate being selected from the group comprising a polymeric material or a metallic compound; and - a thin layer comprising at least one compound which comprises SiC x O y:H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, said thin layer having a first face and a second face, said first face of said thin layer adhering to said first surface of said substrate and being arranged to receive, on its second face, said polymerizable reaction composition, characterized in that said thin layer has an adjustable peel force greater than 5 N / 25 mm, preferably greater than 10 N / 25 mm, more preferably greater than 15 N / 25 mm relative to said substrate, and in that said first face of said thin layer has a surface roughness and / or a gloss equivalent to the surface roughness and / or gloss of said first surface of said substrate and, optionally in that said substrate and said thin layer are arranged to allow a transfer of roughness from said substrate to the surface of the polymerized composition.

2. Film according to claim 1, characterized in that said thin layer has a thickness less than or equal to 6 nm, preferably less than or equal to 5 nm, more preferably less than 3 nm and said film has a surface energy of between 20 and 30 mN / m, preferably between 25 and 30 mN / m.

3. Film according to claim 1 or 2, characterized in that the peel strength of the second face of the thin layer is less than 30 N / 25 mm, preferably less than 28 N / 25 mm, more preferably less than 25 N / 25 mm, more preferably still less than 15 N / 25 mm, advantageously less than 10 N / 25 mm, more advantageously less than 8 N / 25 mm, more advantageously still less than 5 N / 25 mm, measured according to the FINAT 10 (FTM 10) standard with a Tesa®7475 adhesive.

4. Film according to any one of the preceding claims, characterized in that said substrate is made of polymer material, preferably of bi-oriented polymer material, more preferably the substrate is a film made of polyester, polyimides, polyamides, polyether ketones and their derivatives.

5. Film according to any one of the preceding claims, characterized in that it is obtainable by a continuously applied atmospheric pressure plasma process which comprises the following steps: - Preparation of a plasma gas chosen from the group consisting of noble gases and their mixtures; - Preparation of a volatile precursor chosen from the group consisting of cyclic siloxanes, linear siloxanes and their mixtures, - Scrolling of said substrate which has a first surface, preferably in a roller device rollers, within a coating cell equipped with plasma, - Exposure of said first face of said substrate to cold plasma deposition in an atmospheric pressure enclosure, in which there is a gaseous atmosphere comprising said plasma gas, preferably with a dielectric barrier controlled discharge (DBD), and in the presence of said precursor to apply plasma polymerization, - Formation and deposition of said thin layer on said first surface of said substrate, said thin layer comprising at least one compound which comprises SiCxOy:H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, with formation of said film.

6. Film according to claim 5, characterized in that the total quantity of plasma gas is injected at a flow rate of between 45 and 80 m 3 / hour, preferably between 45 and 75 m 3 / hour for a useful film width of 2m, possibly for a substrate running speed of between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min.

7. Film according to claim 5 or 6, characterized in that said precursor is injected at a flow rate of between 50 and 200 g / hour, preferably between 50 and 150 g / hour, more preferably between 75 and 115 g / hour, optionally for a substrate running speed of between 9 and 70 m / min, preferably between 9 and 65 m / min, more preferably between 40 and 65 m / min, and for a useful film width of 2 m.

8. A film according to any one of claims 5 to 7, wherein said method further comprises applying a polymerizable reaction composition on said second face of said thin layer, after formation of said film.

9. Film according to any one of claims 5 to 8, characterized in that said polymerizable reaction composition is obtained by reacting a compound comprising at least one terminal isocyanate group with a compound which has a group reactive to said at least one terminal isocyanate group or by applying a resin, optionally pre-polymerized.

10. Film according to any one of claims 5 to 9, characterized in that said composition is polymerized and in that the surface roughness of the first surface of said substrate is transferred to the surface of the polymerized composition. 1 1. Film according to claim 10, characterized in that, after removal of said film, the shine of said polymerized composition, preferably in the form of a coating, is preserved.

12. Film according to any one of claims 5 to 11, characterized in that said reaction composition is applied by printing, coating, flowing, spraying, pulverizing or by gaseous means.

13. Film according to any one of claims 5 to 12, characterized in that said peelable film has a lifetime corresponding to at least 2 uses, preferably at least 5 uses, preferably at least 8 uses as a support film with maintenance of the surface energy and / or the peel force of said film during repeated uses, and in which each use corresponds to an application of a separate additional reaction composition on said second face of said thin layer.

14. A method for manufacturing a peelable film acting as a temporary support, being arranged to allow polymerization of a reaction composition which comprises a compound which contains at least one isocyanate end group and a compound which has a group reactive with said isocyanate end group, comprising the following steps: a. Preparation of a plasma gas selected from the group consisting of noble gases and mixtures thereof, b. Preparation of a volatile precursor selected from the group consisting of cyclic siloxanes, linear siloxanes and mixtures thereof, c. Running a substrate having a first surface and having a predetermined gloss and / or a predetermined surface roughness, preferably in a roll-to-roll device, within a coating cell equipped with atmospheric plasma, d. Exposure of said first face of said substrate to cold plasma deposition in an atmospheric pressure chamber, in which there is a gaseous atmosphere comprising said plasma gas, preferably with a dielectric barrier discharge (DBD) and in the presence of said precursor, e.Formation and deposition of said thin layer having a first and second surface and which comprises at least one compound which comprises SiC. x O y :H and at least one SiCFh functional group, where x is at least equal to 2 and y is at least equal to 0.5, f. Collection of said peelable film, characterized in that said thin layer has a peel force greater than 5 N / 25 mm, preferably greater than 10 N / 25 mm, more preferably greater than 15 N / 25 mm relative to said substrate, and in that said first face of said thin layer has a surface roughness and / or a gloss equivalent to the surface roughness and / or gloss of said surface of said substrate and, optionally in that said substrate and said thin layer are arranged to allow a transfer of roughness from the first surface of said substrate to the surface of the polymerized composition.

15. A multi-layer system comprising: A polymerizable reaction composition which optionally comprises a compound which contains at least one isocyanate terminal group and a compound which has a group reactive with said at least one isocyanate terminal group or a resin, optionally pre-polymerized, A peelable film acting as a temporary support for said composition comprising: o a substrate with a first surface which has a predetermined roughness and / or a predetermined gloss, said substrate being selected from the group comprising a plastic material or a metallic compound; and thereon o a thin layer comprising at least one compound which comprises SiC x O y:H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, said thin layer having a first face and a second face, said first face of said thin layer adhering to said first surface of said substrate and said second face of said thin layer being in contact with said polymerizable reaction composition, characterized in that said thin layer has a peel force greater than 5 N / 25 mm, preferably greater than 10 N / 25 mm, more preferably greater than 15 N / 25 mm relative to said substrate, and in that said first face of said thin layer has a surface roughness and / or a gloss equivalent to the surface roughness and / or gloss of said first surface of said substrate and, optionally in that said substrate and said thin layer are arranged to allow a transfer of roughness from the first surface of said substrate to the surface of the polymerized composition.

16. An article or multilayer or pre-preg type system comprising the film according to any one of claims 1 to 13.

17. Pre-preg type article according to claim 16, characterized in that said article comprises a first face and a second face which are each provided with said.

18. A peelable film acting as a temporary support, being arranged to allow deposition thereon of a metallic layer to allow formation of a hologram, and comprising: - a substrate having a first surface and being selected from the group comprising a plastic material or a metallic compound; and thereon - a thin layer comprising at least one compound which comprises SiC x O y :H and at least one SiCHs functional group, where x is at least equal to 2 and y is at least equal to 0.5, said thin layer having a first face and a second face, said first face of said thin layer adhering to said first surface of said substrate and being arranged to receive, on its second face, said polymerizable reaction composition, thin layer has an adjustable peel force greater than 20 N / 25 mm, preferably greater than 22 N / 25 mm, more preferably greater than 23 N / 25 mm, advantageously less than 30 N / 25 mm relative to said substrate, particularly advantageously between 22 and 29 N / 25 mm.

19. An article comprising a pre-preg provided with a film according to any one of claims 1 to 13, wherein said film is used as a release film.

Images