Heat shrinkable laminated film.

0001The present invention relates to a heat-shrinkable laminated film comprising a mixed aliphatic polyamide resin layer (A) comprising aliphatic polyamide resins mixed with each other in a specific ratio and a mixed resin layer (B) comprising a saponified ethylene-vinyl acetate copolymer (hereinunder referred to as "EVOH resin") as the main constituent.

0002Most of fatty food such as raw meat and processed meat have irregular shapes and are not uniform in size. For packaging such foods having various shapes a shrink packaging method using heat-shrinkable films is industrially adopted. General procedures of this method consist of the steps of inserting an object into a bag of a film, removing the air from the bag under vacuum, sealing the opening part of the bag, and heating the bag so as to heat shrink the film and bring the film into close contact with the content, thereby obtaining a package with a fine appearance. In this method, the heat treatment also serves to sterilize the content and is ordinarily carried out at a temperature of 70 to 120°C.

0003A film used for such shrink packaging must be excellent in gas barrier property and adhesiveness, and be sufficiently shrunk when heated with hot water or hot air of 70 to 120°C.

0004As such a shrink packaging film, an EVOH resin film having a high gas barrier property is considered to be suitable. However, an EVOH resin film having an excellent gas barrier property is inferior in a stretchability.

0005To eliminate this defect, various methods have been proposed.

0006For example, a composite film obtained by bringing an EVOH resin film into close contact with a polyamide resin film and stretching the thus-laminated film (Japanese Patent Application Laid-Open (KOKAI) No. 52-115880 (1977) and, a laminated film consisting of a polyolefin layer, a polyamide resin layer and an EVOH resin layer (Japanese Patent Application Laid-Open (KOKAI) No. 56-136365 (1981)) have been proposed.

0007However, the mere lamination of an EVOH resin layer and a polyamide resin layer does not always produce a film which has satisfactory stretchability and uniform heat-­shrinkability.

0008In addition, although the lamination of a polyamide resin layer is necessary for obtaining the heat resistance, since the dimensional stability is deteriorated thereby, heatset by, for example, heat treatment is required, which may lower the workability and production yield.

0009Accordingly, a laminated film of a polyamide resin layer and an EVOH resin layer not only having high gas barrier property and heat resistance but also being excellent in stretchability, heat-shrinkability and dimensional stability is now in demand.

0010The present inventors proposed a laminated film comprising of a mixed resin layer of a polyamide resin and an EVOH resin and a resin layer containing an EVOH resin as the main constituent in U.S.P. Application No. 148,569.

0011As a result of further study undergone by the present inventors in order to improve the stretchability, heat-­shrinkability and dimensional stability of a film while maintaining the high gas barrier property of an EVOH resin and heat resistance of a polyamide resin, it has been found that when a mixed resin containing an EVOH resin as the main constituent is used in order to improve the stretchability of the EVOH resin itself, the gas barrier property and the stretchability are compatible to a certain extent and that a laminated film having both uniform heat-shrinkability and excellent dimensional stability as well as stable processability and very improved stretchability is obtained by laminating a mixed resin layer containing an EVOH resin as the main constituent and a polyamide resin layer obtained by mixing polyamide resins having specific crystalline melting points in a specific ratio. The present invention has been achieved on the basis of this finding.

0012An object of the present invention is to provide a laminated film having excellent stretchability, uniform heat-­shrinkability, excellent gas barrier property and excellent dimentional stability.

0013According to the present invention there is provided a heat-shrinkable laminated film comprising at least two layers: a mixed aliphatic polyamide resin layer (A) comprising 55 to 90 wt% of an aliphatic polyamide resin having a crystalline melting point of 175 to 240°C and 45 to 10 wt% of an aliphatic polyamide resin having a crystalline melting point of from not less than 120°C to less than 175°C , and a mixed resin layer (B) comprising an EVOH resin as the main constituent.

0014A mixed aliphatic polyamide resin layer (A) constituting the present invention is a mixed resin layer comprising 55 to 90 wt% of an aliphatic polyamide resin having a crystalline melting point of 175 to 240°C (hereinunder referred to as "PA resin-1") and 45 to 10 wt% of an aliphatic polyamide resin having a crystalline melting point of from not less than 120°C to less than 175°C (hereinunder referred to as "PA resin-2").

0015Suitable examples of the polyamide resin PA resin-1 include nylon 6, nylon 9, nylon 69, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-66, nylon 6-69, nylon 6-12, etc. are usable. Among these, polyamide resins having a crystalline melting point of 195 to 240°C, namely, nylon 6, nylon 69, nylon 610, nylon 612, nylon 6-66, nylon 6-­69 and nylon 6-12 are preferable from the point of view of heat resistance.

0016A PA resin-1 having a crystalline melting point above 240°C has a high crystallinity which is apt to deteriorate the stretchability. As the PA resin-1, a mixture of PA resin-1 may be used so long as the crystalline melting point is in the specified range. The same is applicable to the PA resin-2.

0017Suitable examples of the polyamide resin PA resin-2 include nylon 6-69, nylon 6-12, nylon 6-66-610 and nylon 6-66-610-12. Among these, polyamide resins having a crystalline melting point of 120 to 160°C are preferable from the point of view of stretchability, heat-shrinkability and dimensional stability.

0018A PA resin-2 having a crystalline melting point of less than 120°C is inferior in stretchability and heat resistance.

0019The EVOH resin used for the mixed resin layer (B) is a partially saponified ethylene-vinyl acetate copolymer. The ethylene content in the EVOH resin is 25 to 49 mol%, preferably 35 to 49 mol%, and the saponification degree is not less than 95 mol%. If the ethylene content exceeds 49 mol%, the gas barrier property is deteriorated, while if the ethylene content is less than 25 mol%, the stretchability becomes inferior. In order to obtain uniform stretchability, the ethylene content is preferably not less than 35 mol%.

0020The layer (A) comprises a mixed resin of 55 to 90 wt% of a PA resin-1 and 45 to 10 wt% of a PA resin-2, preferably of 55 to 75 wt% of a PA resin-1 and 45 to 25 wt% of a PA resin-­2. If the content of the PA resin-1 exceeds 90 wt%, it is impossible to obtain uniform heat-shrinkability and dimensional stability. On the other hand, if the content of the PA resin-1 is less than 55 wt%, it is impossible to obtain heat resistance and uniform heat-shrinkability.

0021The layer (B) comprises a mixed resin containing an EVOH resin as the main constituent. In consideration of the gas barrier property and stretchability, the layer (B) is preferably, for example, a mixed resin layer comprising 70 to 99 wt%, preferably, 85 to 97 wt% of an EVOH resin and 1 to 30 wt%, preferably 3 to 15 wt% of a resin selected from the group consisting of elastomers such as a polyester elastomer (e.g., a block copolymer type thermoplastic polyester elastomer) and a polyamide elastomer (e.g., a polyester amide elastomer and a polyether amide elastomer), an ethylene-vinyl carboxylate copolymer such as ethylene-vinyl acetate copolymer (hereinunder referred to as "EVA"), an ethylene-­acrylate copolymer, an ethylene-acrylic acid copolymer and an acid-modified graft polymer thereof. As the resin mixed with an EVOH resin, polyester elastomer, an ethylene-vinyl carboxylate copolymer containing 75 to 95 mol% of ethylene and an ethylen-acrylate copolymer containing 75 to 95 mol% of ethylene are preferable. When an acid-modified graft polymer of these copolymers or an ethylene-acrylic acid copolymer is used, attention must be paid to the extruding processability. The above-described resins are comparatively easy to mix with an EVOH resin. If the content of an EVOH resin is less than 70 wt%, the gas barrier property is insufficient, while use of an EVOH resin only is apt to make the stretchability insufficient for obtaining uniform heat-shrinkability. The use of 85 to 97 wt% of an EVOH resin is suitable for obtaining a gas barrier property and uniform stretchability.

0022A heat-shrinkable laminated film of the present invention comprises at least the layer (A) and the layer (B), and the numbers of the layers (A) and (B) each may be two or more. When the numbers of the layers (A) and (B) constituting the laminated film are respectively two or more, the resin composition of each layer may be either the same or different. However, in terms of workability and uniform layer thickness, it is preferable that the laminated film consists of only one layer (A) and one layer (B).

0023The thickness of a laminated film of the present invention consisting of the layers (A) and (B) is preferably 6 to 30 µm in terms of flexibility.

0024The thickness of a laminated film comprising the layers (A) and (B) and a thermoplastic resin layer is preferably 15 to 120 µm.

0025It is preferable that the thickness of the layer (A) is larger than that of the layer (B), and if the numbers of the layers (A) and (B) constituting the laminated film are respectively two or more, it is preferable that the total thickness of the layers (A) is larger than the total thick­ness of the layers (B).

0026If the thickness of the layer (A) is smaller than that of the layer (B), the stretchability of the film is sometimes deteriorated. The thickness of the layer (A) is preferably 1.1 to 3 times as large as that of the layer (B).

0027The laminated film of the present invention requires at least two layers of the layer (A) and the layer (B), and it is possible to laminate another thermoplastic resin layer thereon in order to provide the film with various properties. As the thermoplastic resin, an olefin resin is preferable in terms of the extrusion property, stretchability and sealing property.

0028As the olefin resin are preferable a copolymer of ethylene and a vinyl ester monomer such as an EVA; a copolymer of a monomer selected from among an aliphatic unsaturated carboxylic acid and an aliphatic unsaturated carboxylate with ethylene, e.g., a copolymer of a monomer selected from among acrylic acid, acrylate, methacrylic acid, methacrylate with ethylene; an ionomer resin; a linear low-­density polyethylene (hereinunder referred to as "LLDPE"), a mixed resin of an LLDPE and an EVA; a very low-density polyethylene (hereinunder referred to as "VLDPE") having a density of not more than 0.91 and a Vicat softening point (measured with ASTM D-1525) of not higher than 90°C, preferably not higher than 80°C; a mixed resin of such a VLDPE and a small amount of LLDPE; a crystalline propylene-­ethylene random copolymer, a mixed resin of a crystalline propylene-ethylene random copolymer and a polypropylene elastomer (hereinunder referred to as "PP + α"); and a mixed resin of a crystalline propylene-ethylene random copolymer and a VLDPE preferably having a Vicat softening point of not higher than 80°C. As the EVA, those containing 3 to 19 wt% of vinyl acetate are preferable. In a mixed resin of an LLDPE and an EVA, the content of the EVA is preferably at least 55 wt% from the point of view of the stretchability. As the LLDPE, a copolymer of ethylene with a small amount of an α-olefin having 4 to 18 carbon atoms such as butene-1, pentene-1, 4-­methyl-pentene-1, hexene-1 and octene-1 which has a crystalline melting point of 118 to 125°C is preferable. As the ionomer resin, an ion cross linked ionomer is used which is obtained by neutralizing a part of the anions of a copolymer of an α-olefin such as ethylene and propylene and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid and maleic acid or a partially saponified copolymer of said olefin and an unsaturated carboxylate with metal ions such as Na⁺, K⁺, Mg²⁺, Ca²⁺ and Zn²⁺. As the metal ions, Na⁺ and Zn²⁺ are generally used. An ionomer resin partially neutralized with bivalent metal ions containing a polyamide oligomer is also usable. A mixture of those olefin resins is also usable so long as it does not impair the sealing property.

0029In a laminated film of the present invention, at least one olefin layer can be laminated. If it has two olefin resin layers or more, the olefin resins may be the same or different. The olefin resin layer may be disposed either between the layer (A) and the layer (B), or preferably on one side or both sides of the laminated film of the layers (A) and (B). By laminating the olefin resin layer, it is possible to improve the extrusion property, dimensional stability, etc. and to provide the laminated film with an excellent sealing property.

0030The laminate of an olefin resin is exemplified by a layer of EVA/adhesive/(B)/(A)/adhesive/EVA, layer of EVA/adhesive/(B)/(A)/adhesive/ionomer resin/, layer of EVA/adhesive/(B)/(A)/adhesive/mixture of LLDPE and EVA, layer of EVA/adhesive/(B)/(A)/adhesive/mixture of VLDPE and LLDPE, layer of VLDPE/adhesive/(B)/(A)/adhesive/VLDPE and layer of (PP + α)/adhesive/(B)/(A)/adhesive/mixture of VLDPE and LLDPE, layer of crystalline propylene-ethylene random copolymer/adhesive/­(B)/(A)/adhesive/VLDPE, a layer of crystalline propylene-ethylene random copolymer/adhesive/(B)/(A)/adhesive/(PP + α). Naturally, the positions of the layers (B) and (A) may be exchanged.

0031It is possible to add an inorganic additive and/or an organic additive such as a thermoplastic resin, an inorganic filler and a pigment to the layer (A), the layer (B) and the olefin resin layer in such a quantity as not to impair the stretchability and the gas barrier property.

0032Since the adhesiveness between the layer (A) and the layer (B) is good, no particular adhesive layer is required, but an adhesive layer may be provided, if necessary. In this case, the adhesive layer is preferably provided between the olefin resin layer and the layer (A) or between the olefin layer and the layer (B) so as to improve the adhesiveness.

0033As the adhesive, an polyolefin or an olefin copolymer which are modified with a carboxylic acid such as fumaric acid and maleic acid is preferable. As examples of the polyolefin or the olefin copolymer to be modified will be cited a homopolymer of ethylene, a bicopolymer or tricopolymer such as an ethylene-propyrene copolymer, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer and an ethylene-methacrylate copolymer, ethylene-vinyl acetate-acrylic acid copolymer, and a compound thereof which does not impair the transparency. A thermoplastic polyurethane resin may also be used.

0034A sealing layer or the whole layers of such a laminated film may be cross-linked by irradiation such as electron beam irradiation, if necessary. Such cross-linking can provide a good sealing property when the sealing temperature is high, but cross-linking is sometimes disadvantageous when sealing at a low temperature is intended.

0035A process for producing a laminated film according to the present invention will be described hereinunder.

0036A laminate of the layer (A) and the layer (B) is first extruded into a tubular shape so that the thickness of the layer(s) (A) is larger than that of the layer(s) (B) by using an annular die equipped with the same number of extruders as the number of the laminated layers. After the layer (A) and the layer (B) were separately extruded into films, laminating the layers (A) and (B),that is, laminating them out of die is not preferable because the unsatisfactory adhesion of the films sometimes lowers the stretchability. The tubular laminate is immediately rapidly cooled, and the thus-obtained substantially amorphous tubular film is heated. The film is biaxially stretched to 1.3 to 4.0 times, preferably 1.5 to 3 times in the machine and transverse directions, respectively, by an inflation method, thereby producing a laminated film. The heating temperature is not lower than 60°C and lower than 100°C, preferably 80 to 95°C. If the heating temperature is lower than 60°C, the stretchability is deteriorated and a change in dimension is increased. On the other hand, if the heating temperature is 100°C or higher, it is impossible to obtain the desired percentage of heat shrinkage. It is necessary that a heat-­shrinkable film of the present invention has a percentage of heat shrinkage of not less than 10%, preferably not less than 20% in both machine and transverse directions when the film is immersed in a hot water of 90°C for 1 minute. If the percentage of heat shrinkage is less than 10%, a wrinkle may be produced on the surface of a packaging film or the close contact between the content and the packaging film is impaired, thereby the external appearance of the goods is deteriorated.

0037A laminated film of the present invention, which is a biaxially stretched film produced by laminating a mixed resin layer containing an EVOH resin as the main constituent which has well-balanced gas barrier property and stretchability and a mixed aliphatic polyamide resin layer obtained by mixing aliphatic polyamide resins having specific melting points in a specific ratio, can be used as a food packaging film having uniform heat-shrinkability, excellent stretchability and dimensional property.

0038Since the stretchability of the laminated film of the present invention is excellent, it is possible to obtain uniform heat-shrinkability without the need for excessive stretching and orientation and to obtain practical dimensional stability without heat treatment. In addition, the film does not produce any ply separation during a high-­temperature treatment in a sterilization and heat shrinkage process. A laminated film of the present invention also has a good adhesiveness with the content.

0039The present invention will be explained concretely with reference to the following non-limitative examples.

Examples 1 to 7, Comparative Examples 1 to 5

0040Resins shown in Table 1 were separately charged into an annular die by a plurality of extruders, and the laminates having the structures shown in Table 2 were coextruded. Each of the tubular laminates extruded from the die was cooled in a cooling bath of 5 to 20°C, to obtain a tubular laminate having 175 mm in flattened width and 80 to 265 µm in thickness. The tubular laminate was heated for about 6 seconds in a heating bath with the temperature adjusted to the value shown in Table 2 and the heated tubular laminate was stretched to 2.3 times in the machine direction (L) and 2.3 times in the diametrical direction of the tubular laminate. The thus obtained biaxially oriented film was about 403 mm in flattened width and 15 to 50 µm in thickness.

Example 8

0041Resins shown in Table 1 were separately charged into an annular die by a plurality of extruders, and the laminate having the structures shown in Table 2 was coextruded. The tubular laminate extruded from the die was cooled in a cooling bath of 5 to 20°C, to obtain a tubular laminate 262 mm in flat width and 95 µm in thickness. The tubular laminate was heated for about 6 seconds in a heating bath with the temperature adjusted to the value shown in Table 2 and the heated tubular laminate was stretched to 1.5 times in the machine direction (L) and 1.5 times in the diametrical direction of the tubular laminate. The thus-obtained biaxially oriented film was about 393 mm in flattened width and 42 µm in thickness.

Examples 9 to 10

0042Resins shown in Table 1 were separately charged into a ring die by a plurality of extruders, and the laminate having the structures shown in Table 2 was coextruded. The tubular laminate extruded from the die was cooled in a cooling bath of 5 to 20°C, to obtain a tubular laminate 133 mm in flattened width and 378 µm in thickness. In the case of electron beam irradiation (Example 10), the tubular laminate was irradiated with 500 keV so as to give an exposed dose of about 6 megarads. The tubular laminate was heated for about 6 seconds in a heating bath with the temperature adjusted to the value shown in Table 2. The heated tubular laminate had been stretched to 3 times in the machine direction (L) and 3 times in the diametrical direction of the tubular laminate. The thus-obtained biaxially oriented film was about 399 mm in flattened width and 42 µm in thickness.

0043The kinds and physical properties of the resins used in Examples are shown in Table 1, the structures of the layers of the laminated film obtained and the results of the tests on the properties of the film are shown in Table 2, and the methods for the tests on the properties are shown in Table 3. <tables id="tabl0001" num="0001"><img file="EP0331509A2_D0001.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0331509A2_D0002.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0331509A2_D0003.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0331509A2_D0004.tif" /></tables>

0044As shown in Examples 1 to 10, it is clear that a heat-­shrinkable laminated film according to the present invention is a laminated film which is excellent in stretchability and has uniform heat-shrinkability and dimensional stability.

0045On the other hand, in Comparative Example 1, since the laminated film consists of a single polyamide resin layer and a single EVOH resin layer, the stretchability is insufficient for producing a film having practicable dimensional stability. In Comparative Example 2, although the mixed polyamide resin layer is the same as in the present invention, since the second layer is a single EVOH resin layer, the dimensional stability is impracticable in spite of having the improved stretchability. In Comparative Examples 3 to 5, although the EVOH resin layer is the same as in the present invention, since the polyamide resin layer of the fourth layer is not in the range of the present invention, it is impossible to obtain uniform stretchability and practicable dimensional stability.