• 专利附录
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    • 专利摘要:
    A composition comprising: a) at least 50% by weight of a polyolefin; b) a polysiloxane functionalized with epoxy functions; c) a compatibilizing agent of the polyolefin with the polysiloxane, said compatibilizing agent being obtained by forming imide functional groups between the polyolefin grafted with maleic anhydride functional groups and a polysiloxane mono- or difunctionalized with primary amine functions; the polyolefin of the matrix and of the compatibilizing agent being either a polyethylene or a polypropylene. This composition can be extruded and stretched to form a film which, after having been subjected to UV radiation, can serve as a support in a self-adhesive label, which support has non-adherent surface properties.
    公开号:FR3032199A1
    申请号:FR1550771
    申请日:2015-02-02
    公开日:2016-08-05
    发明作者:Etienne Fleury；Philippe Chaumont；Nathalie Sintes；Thomas Theodorou；Cecile Daniel；Eric Magni；Clementine Arnaut
    申请人:Soc Des Polymeres Techniques；
    IPC主号:
    专利说明:

    [0001] Field of the Invention The invention relates to the technical field of plastic films having properties of non-stick surfaces and processes for their manufacture. PRIOR ART It is known to use self-adhesive labels for the purpose of presenting information, such as a price, a denomination or a barcode, or for decorative purposes. The structure of a self-adhesive label is shown schematically in FIG. 1. Such a label (1) comprises a support layer (3), transparent or not, on which can be printed an information or a decorative pattern, and a layer protective (2) (referred to in English as the "release liner"). The printable support layer comprises a generally plastic or paper film (4) coated on its side facing the protective layer by an adhesive layer (5). The printable support layer is easily peeled off from the protective layer just before it is applied to the surface of an object, such as a packaging or a container for example of glass or plastic.
    [0002] The adhesive layer is made of a substance which imparts to the printable support layer immediate tackiness at room temperature (often referred to as "tack"), which allows instantaneous adhesion of the printable backing layer to a product. under the effect of a slight pressure. The protective layer may consist of a film (7) of paper or polymer, for example a polyester or a polyolefin. The face of the protective layer in contact with the adhesive layer generally has anti-adhesive properties which facilitate a fast and uniform release of the printable support layer. These anti-adhesive properties are conferred by the presence of a layer of a release coating (6). This is the case for example of the protective layer used in the manufacture of a self-adhesive stamp book. Each stamp is a printable support layer which adheres to a protective layer whose surface has anti-adherent properties. It is known to impart non-stick surface properties by applying to the surface of the protective layer a polysiloxane film, also called silicone, a few microns thick. A polysiloxane is a polymer consisting of an inorganic main chain consisting of a repetition of siloxane bonds (... -Si-O-Si -...). Organic groups are bonded to silicon atoms. The most common silicone is linear poly (dimethylsiloxane) or PDMS, in which two methyl groups are bonded to a silicon atom in the main chain as illustrated hereinafter. The protective layer coated with a non-stick silicone film may be manufactured by a process comprising the following two steps: production of a film either by a paper-making process or by a process of extrusion of Film in the case of a plastic film; - Coating of one of the faces of the film with a silicone material, the thickness of the silicone material layer being generally of the order of one micron thick. The silicone after crosslinking ("drying") gives the film anti-adhesive properties. The silicones of the "TEGO® RC-silicone" range marketed by Evonik can be used as silicone material in this two-stage process. One of the limitations of this process stems from the lack of flexibility regarding the choice of support film. It is difficult to manage a stock with a large number of movie references; these films can indeed vary according to their color, their thickness, their touch, their mechanical properties, their appearance properties. Another limitation is the impossibility of producing small series because of the high inertia of the coating systems. Indeed, the devices used for coating the film are complex to adjust because of the small thickness of the layer of silicone material (0.5 to 2 μm after possible evaporation of the solvent). These devices often require thermal equipment to deposit the silicone material, evaporate any solvent and crosslink the silicone material. An alternative method developed by Coating Plasma Industrie consists in chemically grafting silicone onto the surface of a film using the plasma technique. The film is passed through an enclosure where there is a "cold plasma" environment containing a gas consisting of silicone molecules. Under the effect of plasma excitation, the film surface and the gas are chemically activated and their recombination leads to surface silicone grafting. This method is unsuited to the low volumes of film to be produced and for films whose width is variable. This process is described on the site http://www.cpiplasma.com/pdf/cpi en.pdf. . Another alternative method is to incorporate a silicone-based additive concentrate, also called masterbatch or masterbatch, in a polymer film during its extrusion. The masterbatch is used in dilution in the polymer. However, a propensity has been observed for the silicone to migrate from the protective layer to the adhesive layer, which has the effect of degrading the adhesive properties of the printable layer. The patent application FR 1301557 describes a masterbatch composition intended to be mixed with a polyolefin. The masterbatch is extruded to form a film. The film is then irradiated with UV radiation. This last step gives it anti-adherent properties. The described manufacturing method makes it possible to dispense with the step of coating the silicone material on the film. This masterbatch composition contains a polymerization initiator photo. It has been observed that the photoinitiator polymerization undergoes a degradation of its properties due to the heat released at the time of extrusion of the masterbatch. We are therefore looking for a way to be able to overcome the step of adding the polymerization initiator photo at the time of manufacture of the masterbatch. It also seeks a polymerization initiator photo which is not degraded by heat. It is also desired to obtain a release composition which, when extruded as a film, has anti-adherent surface properties which are superior to those obtained for a film obtained from the masterbatch described in Application FR 0 01557.
    [0003] Finally, a nonstick composition is sought in which the silicone is permanently attached to the surface of the film. SUMMARY OF THE INVENTION The subject of the invention is a composition comprising: a) at least 50% by weight of a polyolefin matrix; b) a polysiloxane functionalized with epoxy functions; c) a compatibilizing agent of the polyolefin with the polysiloxane, said compatibilizing agent being obtained by forming imide functional groups between a polyolefin grafted with maleic anhydride functional groups and a polysiloxane mono- or difunctionalized with primary amine functions; the polyolefin of the matrix and of the compatibilizing agent being either a polyethylene or a polypropylene.
    [0004] According to one embodiment, the composition comprises less than 1%, preferably 0.1% or less by weight of a cationic polymerization initiator, activatable by UV radiation. According to one embodiment, the composition does not comprise a cationic polymerization initiator, activatable by UV radiation.
    [0005] According to one embodiment, the polysiloxane mono- or difunctionalized by primary amine functional groups has, before functionalization, a molar mass of between 200 and 20000 g / mol, preferably between 3000 and 12000 g / mol, more preferably between 6000 and 10000 g. / mol. According to one embodiment, the composition comprises: a) from 80 to 97.9% by weight of polyolefin; b) from 2 to 10% by weight of polysiloxane functionalized with epoxy functional groups; c) from 0.1 to 10% by weight of compatibilizer. According to one embodiment, the polyolefin is a polyethylene with a density of between 0.910 and 0.930 g-cm-3 according to the IS01183 standard.
    [0006] The invention also relates to a process for producing the composition according to the invention, said process comprising the steps of: i) preparing a compatibilizing agent by forming imide functional groups between a polyolefin grafted with maleic anhydride functional groups and a polysiloxane mono- or difunctionalized with primary amine functions; ii) mixing the compatibilizing agent with a polyolefin and a polysiloxane functionalized with epoxy functions, the polyolefins used in steps i) and ii) being either a polyethylene or a polypropylene; iii) optionally, adding a polymerization initiator to the mixture of step ii). The subject of the invention is also a method for manufacturing a film comprising the steps of: a) supplying the composition according to the invention or preparing said composition according to the process for manufacturing the composition as described above; b) extruding the composition to form a film; c) stretching the film; d) exposure of the film to UV radiation. According to one embodiment, the composition obtained in step a) is coextruded in step b) with a film of polyethylene or polypropylene. According to one embodiment, a cationic polymerization initiator, activatable by UV radiation, preferably at a proportion of less than 1% by weight of the composition in step b), is added. According to one embodiment, the proportion of the cationic polymerization initiator, activatable by UV radiation is less than or equal to 0.1% by weight of the composition.
    [0007] The subject of the invention is also a film that can be obtained by the process according to the method described above. Finally, the invention relates to a self-adhesive label comprising a support layer and a protective layer comprising the film described above.
    [0008] DESCRIPTION OF THE FIGURES FIG. 1 represents a self-adhesive label (1) of the prior art. Figure 2a shows a polyolefin matrix (8) comprising inclusions of polysiloxane (9) in the form of droplets. The spherical surface of the polysiloxane inclusions is covered by a compatibilizing agent (10).
    [0009] Figure 2b schematizes the structure of the film obtained after extrusion of the composition of the invention, which film comprises a polyethylene matrix in which the polysiloxane has migrated to the surface. There may remain inclusions of polysiloxane in the matrix. The compatibilizer is found at the interface between the polysiloxane and the matrix. Figure 3 shows the structure of a film obtained by coextrusion of two layers (2 ') and (11). 4 shows the structure of a film obtained by coextrusion of three layers (2 '), (11) and (2 ") DETAILED DESCRIPTION 1) Synthesis of a compatibilizing agent: A polysiloxane and a polyolefin are polymers The role of the compatibilizer is to stabilize the polysiloxane dispersion in a polyolefin matrix As shown in Figure 2a, the compatibilizer (10) is positioned at the interface between the polysiloxane (9) and the polyolefin (8) of the matrix by reducing the interfacial tension between these two materials The polysiloxane is then in the form of inclusions dispersed in the polysiloxane matrix According to the invention, the compatibilizing agent is a copolymer obtained by reaction between a polyolefin functionalized with maleic anhydride functional groups and a polysiloxane functionalized with primary amine functions, preferably the polysiloxane is polydimethylsiloxane. Maleic anhydride functions and primary amine functions lead to the formation of an imide function. The reaction of formation of the imide function is the following one: The presence of imide functions can be demonstrated by the technique of infra-red spectroscopy (IR) which makes appear a peak with 1706 cm-1 , characteristic of the imide function.
    [0010] The primary amine function can be at each end of the polysiloxane chain. We are talking about difunctionalized polysiloxane. It can also be located on one end only of the polysiloxane chain. We speak of monofunctionalized polysiloxane. Preferably, the polysiloxane chain is monofunctionalized. The monofunctionalization makes it possible to obtain a copolymer having a comb structure which promotes the entanglement of the polysiloxane chains of the copolymer with the polysiloxane chains functionalized by epoxy functional groups as described below. The compatibility of the polyolefin with the polysiloxane carrying epoxy functions is improved. The difunctionalized polysiloxane gives less good results than the monofunctionalized polysiloxane because of its tendency to crosslink.
    [0011] According to one embodiment, the compatibilizing agent comprises: from 90 to 99% by weight of polyolefin grafted with maleic anhydride functional groups and from 1 to 10% by weight of polysiloxane functionalized with primary amine functions.
    [0012] Preferably, the compatibilizing agent comprises: from 90 to 95% by weight of polyolefin grafted with maleic anhydride functional groups and from 5 to 10% by weight of polysiloxane functionalized with primary amine functions.
    [0013] According to another embodiment, the compatibilizing agent comprises: from 92 to 97% by weight of polyolefin grafted with maleic anhydride functions and from 3 to 8% by weight of polysiloxane functionalized with primary amine functions.
    [0014] The number-average molar mass of the polysiloxane used in the preparation of the compatibilizing agent may be between 200 and 20000 g / mol. Preferably, it is between 3000 and 12000 g / mol, more preferably between 6000 and 10000 g / mol. A particularly preferred range is 5500 to 6500 g / mol. These ranges of molar mass are those which make it possible to obtain the best thermal stability of the compatibilizing agent.
    [0015] The polyolefin which is grafted by the maleic anhydride functional groups is either a polyethylene or a polypropylene. Polyethylene is understood to mean homopolymers of polyethylene or copolymers containing at least 70 mol% of ethylene units. Polypropylene is understood to mean homopolymers of polypropylene or copolymers containing at least 70 mol% of propylene units. Preferably, the polyethylene and polypropylene copolymers contain at least 95 mol% of ethylene or propylene units respectively. A polyolefin grafted with maleic anhydride functions is available from Arkema under the trade name Orevace 18302N. This is 0.912 g / cm 2 density polyethylene containing 5000 ppm maleic anhydride. The concentration of reactive functions is 5.10 10-5 mol / g. The mixture of the polysiloxane functionalized with amine functional groups and the polyolefin grafted with maleic anhydride functions can be carried out by any type of extrusion apparatus, preferably a twin-screw extruder, Leistritze (60D) or Maris® (31D). . The temperature of the reaction mixture is chosen so as to reduce the viscosity of the polyolefin so as to make it malleable while avoiding its decomposition. The mixture of the grafted polyolefin and the functionalized polysiloxane may, for example, be carried out at a temperature of between 100 and 280 ° C. In the case of a Leistritze-type extruder (60D), the screws can be rotated at a speed of about 1200 rpm for a low flow rate of 3 kg / h. In the case of a Maris®-type extruder (31D), the screws can be rotated at a speed of about 900 rpm for a flow rate of 20 kg / h. A twin-screw extruder develops sufficient shear forces to obtain an intimate mixture of the two polymers, which promotes the formation of covalent bonds between the functionalized polysiloxane and the grafted polyolefin. The compatibilizing agent thus obtained is preferably converted into granules at the exit of the extruder. The amount of unreacted polysiloxane with the grafted polyolefin can be measured after extraction into cyclohexane or tetrahydrofuran and drying. 2) Manufacture of the masterbatch or compound The term "masterbatch" denotes in the following a composition characterized by a high mass proportion of polysiloxane functionalized by epoxy functions, for example at least 40% by weight relative to the mass of the composition. The masterbatch is intended to be diluted in a polyolefin.
    [0016] The following description also applies to a compound, a term which designates a composition characterized by a lower proportion of functionalized polysiloxane than for the masterbatch, for example less than or equal to 20% by weight relative to the mass of the composition. The compound is intended to be used as is. In this step, the compatibilizing agent obtained is mixed with: a polysiloxane functionalized with epoxy functional groups which will make it possible, after the extrusion of the masterbatch in the form of a film, to crosslink the polysiloxane under the effect of UV radiation; a polyolefin which may be different from that used in the manufacture of the compatibilizing agent; optionally a cationic polymerization initiator, activatable by UV radiation. a) Polysiloxane Functionalized by Epoxy Functions: The polysiloxane comprises reactive epoxy functions which induce its crosslinking under the action of the UV decomposition of a polymerization initiator. This polysiloxane incorporated in the polyolefin used for the matrix decreases the surface tension of the polyolefin. A small percentage of polysiloxane, i.e. less than or equal to 10%, is sufficient to modify the surface tension since it has been observed that the polysiloxane migrates to the surface of the polyolefin. The mechanical characteristics of the polyolefin film are not however modified by the presence of the polysiloxane. A polysiloxane functionalized with epoxy functional groups is commercially available from the company Evonik under the trademark TEGO® RC 1403. It has the formula: ## STR2 ## Polyolefin used for the matrix: The polyolefin used as a matrix is either a polyethylene or a polypropylene. Polyethylene is understood to mean homopolymers of polyethylene or copolymers containing at least 70 mol% of ethylene units. Polypropylene is understood to mean homopolymers of polypropylene or copolymers containing at least 70 mol% of propylene units. Preferably, the polyethylene and polypropylene copolymers contain at least 95 mol% of ethylene or propylene units respectively. The term matrix means that the polyolefin serves as a support for the polysiloxane inclusions functionalized by the epoxy functional groups, these being dispersed in the polyolefin. The polyolefin used for the matrix may be a low density polyethylene, that is to say between 0.910 and 0.930 g-cm-3 according to ISO 1183. Such a polyethylene is commercially available for example from the company Basell under the trade names Lupolene 2420F and Lupolene 3020K. Lupolene 2420F and Lupolene 3020K have experimentally estimated molar masses of approximately 16500 and 9000 g / mol respectively. c) Polymerization Primer: A cationic polymerization initiator may be added to the mixture comprising the matrix polyolefin, the epoxy functionalized polysiloxane and the compatibilizer. This initiator may be iodonium hexafluoroantimonate. It is commercially available from the company Evonik under the trade name TEGOe PC 1467. H3C-ECH2 CH2 CH3 SbF-6 Other cationic polymerization initiators such as UV CATA 211 (iodonium borate) or UV CATA 232 of the Bluestar Silicones company are also suitable. The polymerization initiator may be incorporated into the blend comprising the matrix polyolefin and the compatibilizer either at the time of extrusion of the masterbatch or at the subsequent film extrusion step.
    [0017] It is generally introduced into the masterbatch at a proportion of less than or equal to 1% by weight of the masterbatch, preferably at a proportion of less than or equal to 0.5% by weight, more preferably at a proportion less than or equal to 0.1% by weight. d) Masterbatch and Compound Compositions: The polyolefin used for the matrix is generally at least 50%, preferably at least 70%, more preferably at least 90% of the weight of the masterbatch, e.g. 95%. The compatibilizing agent is present in a proportion generally less than or equal to 10% of the mass of the masterbatch, for example from 3 to 7%.
    [0018] The polysiloxane functionalized with epoxy functions is present in a proportion generally less than or equal to 15% of the mass of the masterbatch, for example 5, 10 or 13%. If present, the polymerization initiator is used in a proportion of less than or equal to 1% by weight of the masterbatch, preferably less than or equal to 0.5%, more preferably less than or equal to 0.1%.
    [0019] In a preferred embodiment, the following masterbatch composition may be manufactured: 90% by weight of a polyethylene matrix; - 5% by weight of polysiloxane functionalized by epoxy functions; - 5% by weight of compatibilizer obtained by reaction of a mixture comprising: - 95% by weight of polyethylene grafted with maleic anhydride and - 5% by weight of a polysiloxane. 0.1% by weight of cationic polymerization initiator is added to this composition.
    [0020] Preferably, the mono-functional polysiloxane functionalized with primary amine functions has a molar mass of about 6000 g / mol before functionalization. The various constituents are mixed at a temperature between 160 and 240 ° C, preferably between 180 and 220 ° C, preferably about 200 ° C. To achieve mixing, two extrusion technologies can be used: a) Busse-type technology that allows elongation rather than shear stress, which reduces friction and reduces material degradation and reduces risk crosslinking of silicone-epoxy during extrusion. b) The so-called "twin-screw" technology of the Maris® type which makes it possible to obtain, via shearing, a fine dispersion of a material in the other material. Compared with Buss technology, this tool has the ability to generate greater pressure which will promote mixing. 3) Extrusion of the masterbatch to form a film: The masterbatch is extruded after it has been optionally mixed with a polyolefin to form a film. The polyolefin which may be used may be different from those used in the step of manufacturing the compatibilizing agent and the step of manufacturing the masterbatch. The mixture is brought to a temperature sufficient to allow its melting. A single-screw extruder is generally used. The melt transition of the masterbatch allows migration of the functionalized polysiloxane by epoxy functions to the surface of the polyolefin matrix as shown in Figure 2b, at the screw outlet. Partial demixing of the polysiloxane facilitates the formation of a low energy layer on the surface of the film.
    [0021] The masterbatch may also be coextruded with a plastic film, such as polypropylene or polyethylene, to provide a protective layer of a self-adhesive label. The masterbatch or the compound may also be coextruded with other materials (polyolefin or other), in order to obtain a multilayer film having the surface properties of the film according to the invention and the core properties specific to the application. referred. An example would be the self-adhesive label, product of the coextrusion of the masterbatch or surface compound and a polyethylene or polypropylene core to provide the necessary stiffness properties to the label.
    [0022] The extrusion temperature must be sufficiently high to obtain a masterbatch which is sufficiently fluid to form a film, but it must not be so high as to prevent the functionalized polysiloxane from being crosslinked by epoxy functions, which could lead to a blockage of the screw of the extruder. When the photoinitiator has not been introduced at the time of manufacture of the masterbatch, it may be introduced at the time of extrusion of the masterbatch, in the following forms: a) in liquid form, b) in the form of premix with a polyolefin powder, for example polyethylene, of the same grade as that used for the masterbatch.
    [0023] In these two cases, the initiator photo may either be premixed with the granules of the masterbatch to be introduced simultaneously into the hopper of the extruder, or be injected separately by a suitable metering device (or a pump) at the beginning of the screw. extrusion or in the middle of the extruder, for example via a special compartment in the barrel of the extruder.
    [0024] Once extruded, the film is stretched. The extrusion-stretching step of the film can be performed by the known extrusion-inflation method. In this process, the mixture of granules is poured into a hopper to feed the screw of the extruder. In the extruder, it is heated and softened by a worm which is in a heated tube to make the mixture malleable. The screw causes mixing to an annular die.
    [0025] At the exit of the annular die, air is blown so as to inflate and rise vertically a long film bubble. The stretching of the film is obtained by injecting air into the film still in the liquid state. In this method, the stretching of the film is in the running direction of the film and also in the direction perpendicular to the running direction of the film.
    [0026] The extrusion-stretching step of the film can still be carried out by the known "extrusion-cast" process, also called "flat extrusion", in which the mixture of granules is poured into a hopper to feed the screw of the extruder. In the extruder, it is heated and softened, thanks to a worm which is in a heated tube to make the mixture malleable. The screw causes mixing to a flat die. At the output of the flat die, the mixture passes over at least two rolls. By increasing the rotational speed of a first roll relative to that of a second roll placed upstream of the first roll, a unidirectional stretching of the film is caused in the running direction of the film. The stretch is obtained by adjusting the speed difference between two successive rolls. The film obtained generally has a thickness of between 20 and 100 microns, preferably between 25 and 60 microns. 3) Irradiation of the film: The film is then exposed to UV radiation. This radiation induces the decomposition of the polymerization initiator which allows the initiation of the ring-opening polymerization reaction of the epoxy functional groups present on the polysiloxane chains. The polysiloxane chains will therefore crosslink and allow the formation of a polymer layer having a strong adhesion to the polyolefin film. The cohesion of the PDMS-polyolefin system is enhanced by the compatibilizing agent developed in the first step and present in the formulation. The film can receive UV radiation at a dose of 50 and 500 W / cm, preferably 100-200 W / cm, at a film speed of about 50 m / min. The energy dispersive analysis (EDX) technique makes it possible to confirm the presence of silicon atoms at the surface, which confirms the migration of the polysiloxane chains after extrusion-stretching of the film towards the surface of the film. The dynamic tensiometry technique also makes it possible to confirm the presence of silicone at the extreme surface of the film, by calculating the surface tensions via the measurement of contact angles formed by reference solvents (water, diiodomethane) on this film.
    [0027] Measurements in hysteresis make it possible to qualify the visco-elastic character (freedom of movement) of this surface. The release properties of the film can be evaluated by measuring the peel strength needed to remove an adhesive applied to the film. The peel strength can be measured by following the test developed by the International Federation of Manufacturers and Processors of Adhesives and Iron-on Paper and Other Media (FINAT), FTM 10, entitled "Quality of silicone coated substrates for self-adhesive laminates: release force (300 mm per minute) ". The following adhesives may be used: - tesae 7475: modified acrylic adhesive mass; - tesae 7476: rubber adhesive mass. Preferably, the face exposed to UV after exposure has a peel force less than or equal to 10 cN / cm, preferably less than or equal to 5 cN / cm. The film obtained preferably has a surface energy of between 20 and 35 mN / m, preferably ranging from 21 to 28 mN / m, and still more preferably ranging from 21 to 25. The process according to the invention has the following advantages: - It makes it possible to obtain a film having a lower surface energy than that described in Application FR 01557. - Fixing of the silicone in the polyolefin matrix, after crosslinking by UV, is increased. This makes it possible to reduce the migration of the silicone towards the adhesive composition, thus reducing the pollution of the adhesive composition by the silicone. - It allows to use less silicone for a given mass of polyethylene. it prevents the appearance of a whitish coloration of the film caused by a poor dispersion of the silicone in the film. This poor dispersion causes the formation of white dots in the film. it makes it possible to obtain a film having a better thermal stability than the film described in FR-01557. It makes it possible to improve the mechanical properties of the film described in FR-01557. Indeed, the film described in FR-01557 can present reticulated areas that have a negative impact on the mechanical properties. FIG. 3 represents an embodiment of the invention in which a film is obtained by coextrusion of a composition according to the invention (2 ') with a polymeric composition (11), for example based on polyethylene or polypropylene, intended to serve as a protective layer. During coextrusion, the inclusions (9) of polysiloxane coated with compatibilizing agent (10) and dispersed in the matrix (8) migrate spontaneously to the surface of the layer which is not in contact with the polymeric composition. It is found that after extrusion, the face of the layer (2 ') in contact with the layer (11) resulting from the polymeric composition is substantially free of polysiloxane, while the upper face of the layer (2') in contact with the the ambient air contains almost all the polysiloxane (9). After extrusion, the irradiation with UV radiation of the upper surface of the film makes it possible to crosslink the epoxidized functionalized polysiloxane so as to freeze it on the surface of the film so that it no longer migrates, both in the film and in the film. on another medium.
    [0028] FIG. 4 schematically represents a second embodiment of the invention in which a film comprising three layers (2 ', 11 and 2 ") is obtained by coextrusion of two compositions according to the invention (layers 2', 2") and a polymeric composition (11). The polymeric layer (11) is sandwiched between the two layers (2, 2 ") During the extrusion, the polysiloxane present in the compositions leading to the layers (2) and (2") migrates spontaneously to the surface of the layer in contact with the ambient air, that is to say the lower and upper faces of the film. After extrusion, these are irradiated with UV radiation, which makes it possible to crosslink the polysiloxane functionalized with epoxy functions. The invention makes it possible to dispense with the deposition of a layer of a material conferring anti-adhesive properties, such as the layer (6) of FIG. 1. The film according to the invention is generally used in label applications. , adhesive tapes, films for graphic arts (advertising media, information). The advantage of the process according to the invention is that it allows, by the only extrusion and stretching steps, to obtain a film having non-adherent surface properties, while the method for manufacturing a non-adherent film of the prior art requires after the extrusion and stretching steps, a subsequent step of coating the resulting film.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. A composition comprising: a) at least 50% by weight of a polyolefin matrix (8); b) a polysiloxane (9) functionalized by epoxy functions; c) a compatibilizing agent (10) of the polyolefin with the polysiloxane, said compatibilizing agent being obtained by forming imide functional groups between a polyolefin grafted with maleic anhydride functional groups and a polysiloxane mono- or difunctionalized with primary amine functions; the polyolefin of the matrix and of the compatibilizing agent being either a polyethylene or a polypropylene.
    [0002]
    2. Composition according to claim 1, comprising less than 1%, preferably 0.1% or less by weight of a cationic polymerization initiator, activatable by UV radiation.
    [0003]
    3. Composition according to claim 2, comprising no cationic polymerization initiator, activatable by UV radiation.
    [0004]
    4. Composition according to one of the preceding claims, wherein the polysiloxane mono- or difunctionalized by primary amine functions has before functionalisation a molar mass of between 200 and 20000 g / mol, preferably between 3000 and 12000 g / mol, of more preferably between 6000 and 10000 g / mol.
    [0005]
    5. Composition according to one of claims 1 or 4, comprising: a) from 80 to 97.9% by weight of polyolefin; b) from 2 to 10% by weight of polysiloxane functionalized with epoxy functional groups; c) from 0.1 to 10% by weight of compatibilizer.
    [0006]
    6. Composition according to one of claims 1 to 5, wherein the polyolefin is a polyethylene density of between 0.910 and 0.930 g.cm-3 according to the IS01183 standard.
    [0007]
    7. A method of manufacturing the composition according to one of the preceding claims comprising the steps of: i) preparation of a compatibilizing agent (10) by forming imide functional groups between a polyolefin grafted with maleic anhydride functions and a mono polysiloxane or difunctionalized by primary amine functions; ii) mixing the compatibilizing agent with a polyolefin (8) and a polysiloxane (9) functionalized by epoxy functions, the polyolefins used in steps i) and ii) being either a polyethylene or a polypropylene; iii) optionally, adding a polymerization initiator to the mixture of step ii).
    [0008]
    8. A process for producing a film (2 ') comprising the steps of: a) supplying the composition according to one of claims 1 to 6 or preparing said composition according to the method as described in claim 7; b) extruding the composition to form a film; c) stretching the film; d) exposure of the film to UV radiation. 15
    [0009]
    9. The method of claim 8, wherein the composition obtained in step a) is coextruded in step b) with a film (11) of polyethylene or polypropylene.
    [0010]
    10. The manufacturing method according to claim 8, wherein a cationic polymerization initiator, activatable by UV radiation, preferably in a proportion of less than 1% by weight of the composition in step b) is added.
    [0011]
    11. The manufacturing method according to one of claims 8 to 10, wherein the proportion of the cationic polymerization initiator, activatable by UV radiation is less than or equal to 0.1% by weight of the composition.
    [0012]
    12. Film obtainable by the method according to one of claims 8 to 11.
    [0013]
    A self-adhesive label comprising a support layer (11) and a protective layer (2 ', 2 ") comprising the film of claim 12.
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    同族专利:
    公开号 | 公开日
    FR3032199B1|2017-02-24|
    EP3050911A1|2016-08-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1533339A1|2003-11-21|2005-05-25|Tosoh Corporation|Resin composition for use in release film and release film produced therefrom|
    FR3007765A1|2013-07-01|2015-01-02|Polymeres Tech Soc D|POLYOLEFIN FILM HAVING ANTI-ADHERENT SURFACE PROPERTIES|
    FR1301557A|1960-09-22|1962-08-17|Philips Nv|Electronic calculator with directly accessible memory and indirectly accessible memory|US9796837B2|2012-07-16|2017-10-24|Polyone Corporation|Polyethylene compounds having non-migratory slip properties|
    US9796839B2|2012-07-16|2017-10-24|Polyone Corporation|Polypropylene compounds having non-migratory slip properties|
    CN110724271B|2019-10-21|2021-11-09|北京化工大学常州先进材料研究院|Preparation and application of foam homogenizing agent special for polyolefin foaming product|
    法律状态:
    2016-01-08| PLFP| Fee payment|Year of fee payment: 2 |
    2016-08-05| PLSC| Search report ready|Effective date: 20160805 |
    2016-08-05| EXTE| Extension to a french territory|Extension state: PF |
    2016-11-29| PLFP| Fee payment|Year of fee payment: 3 |
    2018-11-30| ST| Notification of lapse|Effective date: 20181031 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1550771A|FR3032199B1|2015-02-02|2015-02-02|POLYOLEFIN FILM HAVING ANTI-ADHERENT SURFACE PROPERTIES|FR1550771A| FR3032199B1|2015-02-02|2015-02-02|POLYOLEFIN FILM HAVING ANTI-ADHERENT SURFACE PROPERTIES|
    EP16152691.8A| EP3050911A1|2015-02-02|2016-01-26|Polyolefin film having anti-adhesive surface properties|
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