MXPA00004416A - Multilayered halopolymer poly(alkylene naphthalate) films with uv blocking characteristics - Google Patents

Abstract

The present invention provides coextruded or laminated multilayer films having at least one layer of a halopolymer such as poly(chlorotrifluoro ethylene) (PCTFE), at least one layer of a naphthalene containing polymer such as poly(ethylene naphthalate) (PEN), and an intermediate adhesive layer. The invention further provides methods of producing oriented, multilayer films which comprise either coextruding or laminating at least one layer of a halopolymer to a surface of at least one layer of a naphathalene containing polymer by an intermediate adhesive layer. The multilayer film may be uniaxially or biaxially stretched, and an optional thermoplastic polymer layer may be attached to another surface of either the halopolymer layer, the naphthalene containing polymer layer, or both, by another intermediate adhesive layer.

Description

MULTI-LAYER FILMS OF HALOPOLI ERO POLI (ALKYLENE NAFTAYATE) WITH UV BLOCKING CHARACTERISTICS REFERENCE TO RELATED APPLICATION This application claims the benefit of provisional application 60 / 064,474 filed on November 6, 1997.

BACKGROUND OF THE INVENTION CAMPÓ DE LA INVENCIÓN The present invention relates to multilayer films. More specifically, the invention pertains to coextruded or laminated films having at least one layer of a halopolymer such as poly (chlorotrifluoroethylene) (PCTFE), at least one layer of naphthalene containing the polymer such as poly (ethylene naphthalate) (PEN). ), poly (butylene naphthalate) (PBN) and the like including the copolymers and mixtures thereof, and an intermediate adhesive layer.

DESCRIPTION OF THE RELATED ART The production of multilayer polymeric films is well known in the art. for example, see U.S. Patent Nos. 4,677,017 and 5,139,878, which are incorporated herein by reference. These show a multilayer film having a thermoplastic fluoropolymer layer and a thermoplastic polymer layer bonded to the thermoplastic fluoropolymer layer, preferably by an intermediate adhesive layer. These films can be prepared by well known lamination and / or co-extrusion techniques. Lamination methods are also known from US Patent No. 3,355,347 which is incorporated herein by reference. These multilayer films may be symmetrical or asymmetric, oriented or non-oriented. Orientation or stretching of the films is also known in the art as shown by U.S. Patent Nos. 4,677,017 and 5,139,878. It has been a problem in the art to produce transparent or translucent films with sufficient clarity to protect light sensitive materials, especially in outdoor applications, since many of these materials have a tendency to degrade. The films that are used to protect food, medicines, paints, adhesives, biomaterials, chemicals, etc. they require properties such as good thermal and environmental stability, excellent moisture barrier, UV blocking characteristics and transparency at the wavelengths of visible light. Fluoropolymers have been commonly used in outdoor applications due to their extraordinary stability to UV light. These include poly (tetrafluoroethylene-co-ethylene) (ETFE), and tetrafluoroethylene-Hexafluoropropylene (FEP) copolymers, etc. Since these are transparent in most wavelength regions of UV light (ie 200 nm-400 nm), they can not adequately protect the contents below them even though they are extremely stable. It is known in the art to use UV absorbers, for example, benzotriazole derivatives, hindered amines, hydroxybenzophenone derivatives, etc. to impart UV blocking characteristics. However, these UV absorbers are materials of low molecular weight (ie, molecular weight less than 1000) that are sanctioned for direct contact with food and pharmaceutical applications or restricted for use at low concentrations due to the tendency of these Absorbers to migrate to the surface of the film. These are also not very stable to heat. As a result, its UV blocking characteristics are ineffective and limited, especially in a thin film. Except for fluoropolymers, most polymers that are moisture barrier are not UV stable. For example, polyvinylidene chloride (PVdC) turns yellow and becomes brittle under UV light. Other moisture barrier polymers, such as polyolefins, also need UV stabilization to prolong their life in storage under harsh UV environments. It has been known that poly (ethylene naphthalate) (PEN) has excellent UV blocking characteristics. However, due to its extremely slow crystallization speed, the PEN is very fragile and its cast film can not be used alone as a free film. Therefore, only oriented PEN films are available commercially. However due to its already highly oriented structure, it can not be termed in packets for blister or ampoule for pharmaceutical applications, the PEN polymer also lacks moisture barrier, compared to PVdC or PCTFE; and as a result it is rarely used as a packing material against moisture. The PEN polymer is known to lack chemical resistance and is rarely used in an external application as such. Poly (chlorotrifluoroethylene) polymer (PCTFE) has excellent barrier property against moisture and is not sticky despite its lack of characteristics for blocking UV light.

SUMMARY OF THE INVENTION The invention provides a multilayer film containing at least one layer of halopolymer, attached to at least one layer of naphthalene-containing polymer by an intermediate adhesive layer. The invention also provides a method for producing a multilayer film consisting of coextruding at least one layer of a halopolymer, and at least one layer of naphthalene-containing polymer bound to the halopolymer layer by means of an intermediate adhesive layer. The invention further provides a method for producing a multilayer film consisting of laminating at least one layer of a halopolymer to a layer of a naphthalene-containing polymer by an intermediate adhesive layer.

The invention achieves a multilayer film with better UV blocking properties, a non-stick surface as well as protection against moisture. The combination of a film containing naphthalane and a halopolymer film provides a multilayer film that blocks light at the UV wavelength (ie, 200-400 nm), is transparent in the range of visible light (i.e. 400-800 nm), it is stable in outdoor environment, and has excellent barrier properties against moisture and chemical resistance. It would be desirable to produce a multilayer film that is a combination of a PEN polymer layer and a PCTFE layer that not only blocks light at the UV wavelength while maintaining transparency in the region of visible light, but also also be environmentally stable due to the excellent protection against moisture and chemical resistance offered by the PCTFE. It would also be desirable to produce a multilayer film by combining the PEN and PCTFE films through an intermediate adhesive polymer to reduce the brittle nature of the emptied PEN film and allow the film to have practical use.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the UV-Vis effect of a film Single layer PCTFE produced according to Comparative Example 1. Figure 2 shows the UV-Vis spectrum of a three layer film produced according to the invention in Example 2. Figure 3 shows the UV-Vis spectrum of a laminated structure produced according to the invention in Example 3.

DETAILED DESCRIPTION OF THE PREFERRED MODALITY In the practice of the present invention, a multilayer film is prepared composed of a halopolymer layer bonded to a layer of naphthalene-containing polymer. The halopolymer layer is bonded to the naphthalene-containing polymer layer by an intermediate adhesive layer.

The homopolymer layer may be composed of homopolymer and fluoropolymer copolymers, chloropolymers or fluorochloropolymers having from about 2 to about 20 carbon atoms, wherein at least one carbon atom is substituted with at least one halogen atom, and mixtures thereof. Specific examples of suitable homopolymers include poly (chlorotrifluoroethylene) homopolymers and copolymers (PCTFE) and ethylene chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene-propylene copolymers (FEP) perfluoroalkoxy polymer (PFA), poly (fluoride) vinylidene), poly (vinyl fluoride), poly (vinylidene chloride), poly (vinyl chloride), homopolymers and copolymers of tetrafluoroethylene, homopolymers and copolymers of hexafluoropropylene, homopolymers and copolymers of vinylidene fluoride and mixtures thereof. These halopolymers are commercially available or can be easily produced by means well known in the art. The second component of the inventive structure is a layer of a naphthalene-containing polymer that binds to the halopolymer layer. The naphthalene-containing polymers useful in this invention are characterized by the presence of recurring carbonyl ester or carbonamide functional groups as an integrated part of the polymer chain. These naphthalene-containing polymers are also commercially available or can be easily produced by means well known in the art. Illustrative examples of the polyesters are those having recurring monomer units represented by the general formula: - (C =) CRC - (= 0) 0 -R? -0- or 0-R-OC (= 0) -Rr-C (= 0) - where R is the naphthalene unit, and Rx is an alkylene group having at least 2 carbon atoms, preferably alkylene having from about 2 to about 12 carbon atoms, or an arylene group, preferably substituted or unsubstituted phenylene, alkylenephenylene or dialkylenephenylene and wherein the aliphatic portions have from 1 to about of 7 carbon atoms, wherein the permissible substituents are alkyl, alkoxy or halo. Illustrative examples of the polyamides are those having recurring monomer units represented by the general formula: -C (= 0) -RC (= 0) -NH-Rx-NH or -NH-R-NHC- (= 0) -R? ~ C (0) - where R is the naphthalene unit, and Ri is a alkylene group of at least 2 carbon atoms, preferably alkylene having from about 2 to about 12 carbon atoms, or an arylene group, preferably substituted or unsubstituted phenylene, alkylenephenylene or dialkylenephenylene and wherein the aliphatic portions have from 1 to about 7 carbon atoms, wherein the permissible substituents are alkyl, alkoxy or halo. The naphthalene unit of R can be based on di-ol, diamine, di-carboxylic acid or di-carboxylate, i.e., 1,5-naphthalenediol, 1,5-naphthalenediamine, 1,5-naphthalenedicarboxylic acid, 2,6-acid. -naphthalenedicarboxylic acid, dicarboxylic acid di-methyl-2, ß-naphthalene, 2,6-naphthalenediol, 2,6-naphthalenediamine, 2,7-naphthalenedicarboxylic acid, and the like. Suitable naphthalene-containing polymers not exclusively include poly (ethylene naphthalate) (PEN), poly (butylene naphthalate) (PBN), and copolymers and mixtures thereof. Mixtures and copolymers formed from the above recurring units of the aforementioned polyesters and polyamides can also be used. By way of illustration and not limitation, these polyester copolymers include poly (ethylene terephthalate-ethylene naphthalate) (PET-co-PEN), poly (butylene terephthalate-ethylene naphthalate) (PBT-co -PEN), PET-co-PBN, PBT-co-PBN; and similar.

The preferred attachment means between each halopolymer layer and naphthalene-containing polymer layer is an adhesive layer; also known in the art as a "binder" layer. In accordance with the present invention, the adhesive polymers not exclusively include modified polyolefin compositions having at least one functional portion selected from the group consisting of unsaturated polycarboxylic acids and anhydrides of the Other adhesives can be ethylene copolymers, modified or unmodified with unsaturated carboxylic acids and anhydrides These can be homopolymers or copolymers of acrylic acid, alkylacrylic acid, acrylates, alkyl acrylates and mixtures thereof which can be modified with acids and anhydrides. unsaturated carboxylic acids The unsaturated carboxylic acids and anhydrides include maleic acid and anhydride, fumaric acid and anhydride, crotonic acid and anhydride, citraconic acid and anhydride, itaconic acid and anhydride and the like, of which maleic anhydride is most preferred. dyes not exclusively include copolymers of alkyl ester of olefins and alkyl esters of α, β-ethylenically unsaturated carboxylic acids such as those described in U.S. Patent 5,139,878. The preferred modified polyolefin composition contains from about 0.001 and [sic] about 10% by weight of the functional portion, based on the total weight of the modified polyolefin. Most preferably, the functional portion contains from about 0.005 and about 5% by weight [sic], and more preferably from about 0.01 and [sic] about 2% by weight. The modified polyolefin composition can also contain up to about 40% by weight of thermoplastic elastomers and alkyl esters as described in U.S. Patent No. 5,139,878. The multilayer films of the present invention can have a variety of structures. A common film structure includes a three-layer structure, which contains a layer of naphthalene-containing polymer, an adhesive layer and a layer of the halopolymer. Another common film structure is a five-layer structure, which contains a naphthalene-containing polymer layer, an adhesive layer, a halopolymer layer, another adhesive layer and another layer of naphthalene-containing polymer. Another variation is a 5-layer structure containing a halopolymer layer, an adhesive layer, a naphthalene-containing polymer layer, another adhesive layer and another halopolymer layer. These are only three of many possible combinations of multilayer film structures, and it is possible to make any order and thickness variation of the halopolymer layers and the naphthalene-containing polymer layer.

The multilayer films of this invention can be produced by conventional methods useful in the production of multilayer films including coextrusion, extrusion lamination and adhesive lamination techniques. Suitable coextrusion techniques are described in U.S. Patent Nos. 5,139,878 and 4,677,017. Coextrusion techniques include methods that use a feed block with a standard nozzle, a multiple nozzle such as that used in the formation of multilayer films to form flat cast films and cast sheets. An advantage of co-extruded films is the formation of a multilayer film in a process step by combining the melted layers of each of the halopolymer film layers, the composition of the bonding layer and the naphthalene-containing polymer, as well as optionally more layers of film, in a unit film structure. In order to produce a multilayer film by a coextrusion process, it is necessary that the constituents used to form each of the individual films be compatible with the extrusion process of the film. The term "compatible" in this sense means that the film-forming compositions used to form the films have fusion properties that are sufficiently similar to allow co-extrusion. The melting properties of interest include, for example, melting points, melt flow rates, apparent viscosity, as well as melt stability. It is important that this compatibility is present to guarantee the production of a multilayer film having good adhesion and relatively uniform thickness throughout the width of the film that is produced. As is known in the art, film-forming compositions that are not sufficiently compatible to be useful in a coextrusion process often produce films having poor interfacial lamination, poor physical properties as well as poor appearance. One of ordinary skill in the art can readily weigh the aforementioned compatibility to select the polymers having the desirable physical properties and determine the optimal combination of the relative properties in the adjacent layers without undue experimentation. If a coextrusion process is used it is important that the constituents used to form the multilayer film be compatible within a relatively narrow temperature range to allow extrusion through a common nozzle. Otherwise, the multilayer films of the present invention can be produced by lamination whereby a multilayer film structure is formed from prefabricated film sheets. The fundamental methods used in film lamination techniques are fusion, wet combination, and thermal reactivation. Fusing, which is a method of laminating two or more sheets of film using heat and pressure without the use of other adhesives, can only be used where the films being laminated are composed of polymers that easily form interfacial adhesion. The wet combination and the technical reactivation are used in lamination of incompatible films using adhesive materials. Usually, the lamination is performed by placing the individual layers of the inventive film one on top of the other under conditions of sufficient heat and pressure to cause the layers to combine into a unitary film. Commonly the films of the halopolymer, adhesive and naphthalene-containing polymer are placed one on top of the other, and the combination passes through the space between a pair of heated laminating rolls by well-known techniques such as those described in US Patent No. 3,355,347 which is incorporated herein by reference. These can be laminated in a single step where the adhesive layer, which can be a polymer melt, water or solvent-based adhesives, or adhesives without solvents, combines the naphthalene-containing polymer with the halopolymer, which is preferably corona treated on the surface and then printed with a layer that promotes adhesion (ie, primer) . These can be laminated in multiple passes (or stations) where the halopolymer and the adhesive layer are first combined in a first step (station), followed by lamination of the naphthalene-containing polymer in a second step (station). The thermolamination can be carried out at temperatures in the range from about 120 ° C to about 175 ° C, preferably from about 150 ° C to about 175 ° C at pressures in the range from about 5 psig (0.034 MPa) to about 100 psig (0.68 MPa) for from about 5 seconds to about 5 minutes, preferably from about 30 seconds to about one minute. The multilayer film, whether containing a structure of three or more layers, can be elongated or oriented in any desired direction using methods well known to those skilled in the art. Examples of these methods include those set forth in U.S. Patent 4,510,301. In this orientation operation, the film can be oriented uniaxially in the direction coincident with the direction of movement of the film being stretched from the casting roller, also known in the art as the "longitudinal" direction, or in the direction which is perpendicular to the longitudinal direction, also known in the art as a "transverse" direction, or biaxially in the longitudinal direction and the transverse direction. The multilayer film of the invention are particularly useful for making multicomponent articles by the processes known in the art. For example, the invention can be used to prepare coextruded articles such as films and tubes, laminates such as films and sheets, and injection molded and blow molded articles. The invention may also be useful in the formation of thermoformed three-dimensional shaped articles such as blister or blister packs for pharmaceutical products. This can be done by forming the film around a suitable mold and heating it up in a method well known in the art. The films of the present invention have sufficient dimensional stability to be stretched at least 1.5 and preferably more than three times and more preferably from more than three times to about 10 times in the longitudinal direction or the transverse direction, or both. Although each layer of the multilayer film structure may have different thickness, the thickness of each of the layers of halopolymer and naphthalene-containing polymer of the films in the multilayer film structure, subsequently stretched preferably is from about 0.05 mils ( 1.3 μ) to about 100 mils (2540 μ), more preferably from about 0.05 mils (1.3 μ) to about 50 mils (1270 μ) and more preferably from about 0.50 mils (12.7 μ) to about 10 mils (254 μ). The thickness of the post-stretched adhesive layer can vary, but is generally in the range of from about 0.02 mils (.5 μ) to about 12 mils (305 μ), preferably from about 0.05 mils (1.3 μ) to about 1.0 mils (25 μ) and more preferably from about 0.1 mils (25 μ) to about 0.8 mils (20 μ). Although these thicknesses are preferred to provide an easily flexible film, it will be understood that it is possible to produce other film thicknesses to meet a specific need and still fall within the scope of the present invention.; These thicknesses that are contemplated include plates, thick films and sheets that are not easily flexible at room temperature (approximately 20 ° C). A preferred embodiment of the invention provides a multilayer film structure containing a halopolymer layer bonded to a naphthalene-containing polymer layer, wherein an intermediate adhesive layer is the preferred means of bonding. In another embodiment, an optional layer of a thermoplastic polymer is bonded to another surface of the polymer layer containing naphthalene or the halopolymer layer or both, by another intermediate adhesive layer. These layers of thermoplastic polymer may be materials such as polyesters, polyesters, polyolefins, polyacrylonitrile, polystyrene, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate, PETG, polyacrylates, polyurethanes, etc. and mixtures and copolymers thereof. Polyamides include crystalline and amorphous nylon such as Nylon 4, Nylon 6, Nylon 6, 6, Nylon 7, Nylon 8, Nylon 9, Nylon 11, Nylon 12, Nylon 4,2, Nylon 4,6, Nylon 4,1 Nylon 6.9, nylon 6.10, nylon 6.1, nylon MXD6, nylon 6.12, nylon 6,6,6, nylon 6,6 / 61. nylon 6, 6, 6T, trimethyl nylon, 6.2 / 6.2, nylon 6,6 / 6,9,2, nylon 6,6 / 9/6. The polyesters include polyethylene terephthalate and polybutylene terephthalate, the polyolefins include polyethylene, polypropylene and polybutylene. Each of the layers of the multilayer film structure may contain other additives recognized in the art as UV stabilizers and absorbers, colorants such as colors and pigments, fillers, slip additives, plasticizers, lubricants, antiblocking agents, antioxidants and heat stabilizers in amounts well known in the art. These may be present in an amount of about 10% or less, based on the weight of the layer. The commonly used UV absorbers and stabilizers can be added to any of the layers of the present invention to extend the UV blocking length from about 375 nm to about 400 nm. These UV absorbers and stabilizers include substituted or unsubstituted benzotriazole derivatives, benzotriazine derivatives, hindered amines, hydroxybenzophenone derivatives, etc. Examples are 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3 ', h '-di-tert-butyl-2' -hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-dihydroxy-4, A '-dimethoxybenzophenone, 2- (4,6-diphenyl-1,3,5-triazin-2) -yl) 5- (hexyl) olyl-phenol, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl-5-octyloxy) phenol, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, and the like. Commonly used pigments or dyes that can be added to any of the layers of the present invention to extend UV / isible wavelength blocking at a longer wavelength, i.e., 480-500 nm include metal oxides, by example, titanium oxide, carbon black and oxidized colored pigments, and so on. Organic pigments include azo compounds (monoazo, diazo, salts of azo-colored acids, etc.) pigmentos.no azo (polycyclic structure such as phthalocyanine, quinacridones, perylene, naphthalene tetracarboxylic acid derivatives, etc.), fluorescent pigments (naphthazine, etc.), organic dyes (anthraquinone, quinophthalone, pyrazolone, xanthene, azine, etc.); and similar. The following non-limiting examples serve to illustrate the invention.

EXAMPLE 1 (COMPARATIVE) Poly (chlorotrifluoroethylene) homopolymer (PCTFE) (density 2.11 g / cc, melting point 211 ° C, manufactured by Allied Signal Inc. - HP Ation) was extruded through a Killion propeller with a diameter of 3.2 cm (1.25") (L / D = 24/1) equipped with three heating zones and two adapter zones. The barrel temperature 'extruder was set at 27 ° C, 316 ° C, 316 ° C for zone 1-3 and the adapters were maintained at 307 ° C. The temperature of the melt was measured at 312 ° C. The extrudate, after passing through a nozzle for extrusion film maintained at 288 ° C, was then cast on a roller at 49 ° C, followed by a cooling roller set at 32 ° C. The resulting monolayer film has a thickness of 15 μ. The film was then tested in a UV-VIS-NIR photometer spectrum (Cary 5E, manufactured by Varial Analytical Instruments). Figure 1 is the UV-VIS spectrum of this single layer PCTFE film. As can be seen, the spectrum is very clear, that is, greater than 80% transmittance, from about 215 nm to 400 nm in the UV wavelength range as well as in the visible wavelength region from 400 nm to 800 nm.

EXAMPLE 2 A three layer film was co-extruded using the PCTFE homopolymer (same as in Example 1), a poly (ethylene naphthalate) homopolymer (PEN) (melting point 280 ° C, intrinsic viscosity 1.64, made by Du pont). ), and a polyolefin binding resin modified with maleic anhydride (density: 0.88 g / cc, melt index 0.4 g / 10 min at 190 ° C, developed by Mitsui Chemicals America, Inc.) to prepare the following structure: PCTFE / union / PEN. The poly (ethylene naphthalene), after drying at 121 ° C for 8 hours, was extruded through a Killion single-screw extruder of 3.8 cm (1.5") diameter (L / D = 24/1) equipped with Three heating zones and two adapter zones The temperature of the extruder barrel was set at 293 ° C, 307 ° C, 310 ° C and the adapters were maintained at 307 ° C. The temperature of the melt was 302 ° C. modified union with maleic anhydride was extruded through a 3.2 cm Killion single screw extruder (1.25") in diameter equipped with four heating zones and two adapter zones.The temperature of the extruder barrel were set at 193 ° C, 227 ° C, 279 ° C, 285 ° C and the adapters were maintained at 285 ° C. The melt temperature was 285 ° C. The PCTFE homopolymer was extruded following the same procedure described in Example 1. The three-layer extrudate, after passing through a film nozzle by co-extrusion maintained at 288 ° C, was then cast on a roll which was maintained at 49 ° C. ° C, followed by a cooling roller set at 32 ° C. The resulting three-layer film had a total thickness of 36 μ, where the PCTFE layer alone is about 9 μ, the PEN layer is about 16 μ and the binding resin is about 11 μ. The three-layer film was tested in a UV-VIS-NIR spectrophotometer. Figure 2 is the UV-Vis spectrum of this three-layer film. As can be seen, the UV wavelength from 200 nm to about 375 nm was completely blocked while the spectrum is extremely clear (greater than 80% transmittance) at the wavelength from about 380 nm to 800 nm . What this spectrum means is that the incorporation of PEN almost blocks the whole region of the UV wavelength while transmitting all the visible light. The moisture barrier, measured by the water vapor transmission rate (VTR), based on ASTM F1249, was close to 0.682 g / m2 / day at, 37.8 ° C and 100% RH for the three layer film (PCTFE / union / PEN) against 18.6 g / m2 / day at 37.8 ° C and 100% RH of the monolayer film control of PEN colada, 16 μ. This shows a nearly 27-fold improvement in moisture barrier. The multilayer film was also tested for mechanical properties (ASTM D882) and puncture resistance (ASTM F1306) using cast monolayer PEN, 16 μ as a control. The fragility of the control film was determined with a low yield elongation, that is, close to 150% and the puncture resistance low, that is, 80 g. On the other hand, the incorporation of PCTFE and the adhesive layer significantly increase the elongation produced at 230% and the puncture resistance at 250 g.

EXAMPLE 3 The three-ply film described in Example 2 was subsequently laminated to a polyethylene substrate of 200 μm thickness containing a yellow pigment (master batch of color composed of Reed Spetrum). The laminate was then tested in a UV-VIS-NIR photometer spectrum, in which the UV-Vis spectrum is shown in Figure 3. In this example, greater blockade of the wavelength from 200 nm to near 480 nm. As can be seen from the previous examples, films with good moisture barrier and UV barrier can be prepared according to the present invention. Although the invention has been demonstrated and described with reference to a preferred embodiment, it should not be considered as limited by them, but only considered in accordance with the following claims.

Claims (31)

1. A multilayer film containing at least one layer of halopolymer and at least one layer of naphthalene-containing polymer bound to the halopolymer layer by an intermediate adhesive layer.

The multilayer film of claim 1, wherein the intermediate adhesive layer consists of a polymer containing olefin selected from the group consisting of at least one functionalized polyolefin; at least one copolymer of ethylene and at least one monomer selected from the group consisting of acrylic acid, alkylacrylic acid, acrylates and alkyl acrylates; and mixtures thereof.

3. The multilayer film of claim 1 further comprises another halopolymer layer bonded to the naphthalene-containing polymer layer by another intermediate adhesive layer.

4. The multilayer film of claim 1 further comprises another layer of naphthalene-containing polymer bound to the halopolymer layer by another intermediate adhesive layer.

5. The multilayer film of claim 1 further comprises a layer of a thermoplastic polymer bonded to the naphthalene-containing polymer layer by another intermediate adhesive layer.

6. The multilayer film of claim 1 further comprises a layer of a thermoplastic polymer bonded to the halopolymer polymer layer [sic] by another intermediate adhesive layer.

7. The multilayer film of claim 1 further comprises a layer of a thermoplastic polymer bonded to the naphthalene-containing polymer layer by an intermediate adhesive layer and another layer of thermoplastic polymer bonded to the halopolymer layer by another intermediate adhesive layer, Thermoplastic polymer layers independently contain one or more materials selected from the group consisting of polyamides, polyesters, polyolefins, polyacrylonitrile, polystyrene, polyacrylates, polyurethanes, polyvinyl chloride and copolymers and mixtures thereof.

8. The multilayer film of claim 1, wherein the film is uniaxially or biaxially oriented.

9. The multilayer film of claim 1, wherein the halopolymer layer consists of fluoropolymers, chloropolymers or fluorochloropolymers having from about 2 to about 20 carbon atoms, wherein at least one carbon atom is substituted with at least one carbon atom. halogen atom.

The multilayer film of claim 1, wherein the halopolymer layer consists of a material selected from the group consisting of poly (chlorotrifluoroethylene) homopolymers and copolymers and ethylene copolymer Chlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene-propylene copolymers, perfluoroalkoxy polymer, poly (vinylidene fluoride), poly (vinyl fluoride) poly (vinylidene chloride), poly (vinyl chloride) homopolymers and tetrafluoroethylene copolymers, homopolymers and copolymers of hexafluoropropylene, homopolymers and copolymers of vinylidene fluoride and mixtures thereof.

The multilayer film of claim 1, wherein the naphthalene-containing polymer film is selected from the group consisting of poly (ethylene naphthalate), poly (butylene naphthalate), and copolymers and mixtures thereof.

The multilayer film of claim 1, wherein the halopolymer layer contains homopolymers and copolymers of poly (chlorotrifluoroethylene) and the naphthalene-containing polymer layer consists of homopolymers and copolymers of poly (ethylene naphthalate).

The multi-layer film of claim 1, wherein at least one of the layers [sic] contains one or more additives selected from the group of UV stabilizers, UV absorbers, colorants, fillers, slip additives, plasticizers, lubricants, antiblocking agents, antioxidants and thermostabilizers.

14. A method for producing a multilayer film oriented, the which consists in coextruding and joining a layer of a halopolymer to a layer of naphthalene-containing polymer by means of a co-extruded intermediate adhesive layer.

15. The method of claim 14 further comprises coextruding and bonding another layer of naphthalene-containing polymer to the halopolymer layer by another intermediate adhesive layer.

16. The method of claim 14 further comprises coextruding and bonding another layer of a halopolymer to the naphthalene-containing polymer layer by another intermediate adhesive layer.

17. The method of claim 14 further comprises joining another layer of a thermoplastic polymer to the layer of the naphthalene containing polymer by an intermediate adhesive layer and bonding another layer of thermoplastic polymer to the halopolymer layer by another intermediate adhesive layer.

18. The method of claim 14 further comprises orienting the uniaxial film biaxially or biaxially.

The method of claim 14 wherein the halopolymer layer consists of fluoropolymers, chloropolymers or fluorochloropolymers having from about 2 to about 20 carbon atoms, wherein at least one carbon atom is substituted with at least one halogen atom.

The method of claim 14, wherein the halopolymer layer consists of a material selected from the group consisting of poly (chlorotrifluoroethylene) homopolymers and copolymers and ethylene chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-propylene copolymers fluorinated, perfluoroalkoxy polymer, poly (vinylidene fluoride), poly (vinyl fluoride] poly (vinylidene chloride), poly (vinyl chloride) homopolymers and Copolymers of tetrafluoroethylene, homopolymers and Copolymers of hexafluoropropylene, homopolymers and copolymers of vinylidene fluoride and mixtures thereof.

The method of claim 14, wherein the film of the naphthalene-containing polymer comprises a material selected from the group consisting of poly (ethylene naphthalate), poly (butylene-naphthalate), and copolymers and mixtures thereof.

The method of claim 14, wherein the halopolymer layer contains homopolymers and copolymers of poly (chlorotrifluoroethylene) and the naphthalene-containing polymer layer consists of homopolymers and copolymers of poly (ethylene naphthalate).

23. A method for producing a multilayer film, which is to laminate a layer of a halopolymer to a layer of the naphthalene-containing polymer by an intermediate adhesive layer.

24. The method of claim 23 further comprises laminating another layer of a naphthalene-containing polymer layer to the halopolymer layer by another intermediate adhesive layer.

25. The method of claim 23 further comprises laminating another layer of a halopolymer to the naphthalene-containing polymer layer by another intermediate adhesive layer.

26. The method of claim 23 further comprises joining one layer of a thermoplastic polymer to another surface of the polymer layer containing naphthalene and to another surface of the halopolymer layer by another intermediate adhesive layer.

27. The method of claim 23 further comprises orienting the film uniaxially or biaxially.

The method of claim 23, wherein the halopolymer layer consists of at least one fluoropolymer, chloropolymer or fluorochloropolymer having from about 2 to about 20 carbon atoms, wherein at least one carbon atom is substituted with when minus one halogen atom.

The method of claim 23, wherein the halopolymer layer consists of a material selected from the group consisting of poly (chlorotrifluoroethylene) homopolymers and copolymers and ethylene chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-propylene copolymers fluorinated, perfluoroalkoxy polymer, poly (vinylidene fluoride), poly (vinyl fluoride), poly (vinylidene chloride), poly (vinyl chloride), homopolymers and copolymers of tetrafluoroethylene, homopolymers and copolymers of hexafluoropropylene, homopolymers and fluoride copolymers of vinylidene and mixtures thereof.

The method of claim 23, wherein the film of the naphthalene-containing polymer comprises a material selected from the group consisting of poly (ethylene naphthalate), poly (butylene naphthalate), and copolymers and mixtures thereof.

31. The method of claim 23, wherein the halopolymer layer contains a material selected from the group consisting of poly (chlorotrifluoroethylene) homopolymers and copolymers and the naphthalene-containing polymer layer consists of a material selected from the group consisting of in poly (ethylene naphthalate) homopolymers and copolymers.