Abstract:
The present invention is directed to a polymer blend formulation and to heat shrinkable film, bags, pouches and the like made therefrom. The invention is further directed to a method of producing a heat shrinkable film with the proper gas permeability properties so that it is ideal for packaging and preservation of gassing cheese.

Description:
RELATED APPLICATIONS 
       [0001]    This application claims the benefit of European Application No. 08150005.0, filed Jan. 2, 2008, the entire disclosure of which is herein incorporated by reference. 
       TECHNICAL FIELD 
       [0002]    The present invention is directed to a polymer blend formulation and to heat shrinkable film, bags, pouches and the like made therefrom. The invention is further directed to a method of producing a heat shrinkable film with the proper gas permeability properties so that it is ideal for packaging and preservation of gassing cheese. 
       BACKGROUND 
       [0003]    Gassing cheese products are generally characterized by the emission of carbon dioxide during their curing process. Packaging films used for packaging of such cheese must be able to allow carbon dioxide escape, so that a possible “ballooning” effect is avoided. At the same time, oxygen permeability should be as low as possible, so that the oxidation-deterioration of the cheese is minimized. 
         [0004]    Heat shrinkable films are often used for gassing cheese packaging due to the good aesthetic appearance that heat shrinkability induces. High transparency of the pack is also important, so that possible consumers are attracted by the pack. The majority of heat shrinkable films used in this area comprise PVDC as barrier layer. PVDC is difficult to extrude and quite easy to burn and deteriorate during the extrusion process. 
         [0005]    PVDC formulations like for example described in prior art patents are commonly used. 
         [0006]    Generally these PVDC formulations incorporate high percentage of plasticizers or stabilizers in order to increase the permeability to CO2. Common plasticizers/stabilizers are epoxidized compounds like epoxidized soybean oil, epoxidized linseed oil, etc. One negative effect is that these compounds tend to migrate from the PVDC layer to other layers, thus creating delaminations and, most dangerously, change of barrier properties as time passes. This is an undesirable phenomenon. 
         [0007]    So, several features that should characterize a heat shrinkable film intended for use in packaging of gassing cheese are 
         [0000]    1. High shrinkage
 
2. Excellent optics
 
3. Efficient heat sealability so that bags can be made
 
4. Avoidance of plasticizer use
 
5. Good processability of PVDC, no oxidation during extrusion
 
6. High CO2 permeability, not changing over time
 
7. High O2 barrier, not changing over time.
 
         [0008]    These features are matched with the PVDC combination of the present invention and with the heat shrinkable films we further advice. 
       SUMMARY OF THE INVENTION 
       [0009]    It is therefore the object of this invention to make a polymer blend providing the above characteristics. 
         [0010]    This is solved by a polymer blend comprising
       A. PVDC polymer   B. Ethylene vinyl acetate with more than 40% vinyl acetate (per weight)   C. PVC   D. Epoxidized oil compound and optionally other additives.       
 
         [0015]    For example, the invention comprises a PVDC combination with the following recipe: 
       Blend of 
       [0000]    
       
         
           
             a copolymer PVDC as base resin 
             epoxidized materials less than 2% per weight 
             ethylene vinyl acetate copolymer with percentage of 40 to 50% vinyl acetate per weight 
             PVC content more than 0% and less than 2% 
             silica and talc 
             possibly other materials like silicon polymers, high density polyethylene, tetrasodium pyrophospthate 
           
         
       
     
         [0022]    It is further the object of this invention to extrude the above described PVDC formulation without deterioration even in high shear rates. 
         [0023]    It is further the object of this invention to produce a multilayer film incorporating a PVDC layer comprising the above described recipe. The other layers may preferably comprise ethylene alpha olefin copolymers, propylene alpha olefin copolymers, propylene ethylene copolymers, styrene polymers or ionomers. 
       THE DEFINITIONS USED IN THE FOLLOWING ARE AS FOLLOWS 
       [0024]    The term “film” refers to a flat or tubular flexible structure of thermoplastic material. 
         [0025]    The term “heat shrinkable” refers to a film that shrinks at least 10% in at least one of the longitudinal and transverse directions when heated at 90° C. for 4 seconds. The shrinkability is measured according to ASTM 2732 with water as a heating medium. This test method covers the determination of the degree of unrestrained linear thermal shrinkage at given specimen temperatures of a plastic film and sheeting of 0.76 mm thickness or less. 
         [0026]    All measurement methods mentioned herein are readily available for the skilled person. For example, they can be obtained from the American National Standards Institute at: www.webstore.ansi.org 
         [0027]    The phrase “longitudinal direction” or “machine direction” herein abbreviated “MD” refers to a direction along the length of the film. 
         [0028]    The phrase “outside layer” refers to the film layer which comes in immediate contact with the outside environment (atmosphere). 
         [0029]    The phrase “middle layer” refers to the layer which is exactly in the middle between outer and sealing layer, such as outer layer/next layer/middle layer/next layer/sealing layer. 
         [0030]    The phrase “inner layer” refers to the film layer that comes in direct contact with the product packed. This is also called “sealing layer” as this layer must be hermetically sealed in order to protect the product from ingress of air. 
         [0031]    As used herein, the term “homopolymer” refers to a polymer resulting from polymerization of a single monomer. 
         [0032]    As used herein, the term “copolymer” refers to a polymer resulting from polymerization of at least two different polymers. 
         [0033]    As used herein, the term “polymer” includes both above types. 
         [0034]    As used herein the term “polyethylene” identifies polymers consisting essentially of the ethylene repeating unit. The ones that have a density more than 0.940 are called high density polyethylene (HDPE), the ones that are have less than 0.940 are low density polyethylene (LDPE). 
         [0035]    As used herein the phrase “ethylene alpha olefin copolymer” refers to polymers like linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), metallocene catalysed polymers and polyethylene plastomers and elastomers. 
         [0036]    As used herein the phrase “styrene polymers” refers to styrene homopolymer such as polystyrene and to styrene copolymers such as styrene-butadiene copolymers, styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, styrene-ethylene-butadiene-styrene copolymers, ethylene-styrene copolymers and the like. 
         [0037]    As used herein the phrase “ethylene methacrylate copolymers” refers to copolymers of ethylene and methacrylate monomer. The monomer content is preferably less than 40%. 
         [0038]    As used herein the phrase “ethylene vinyl acetate copolymer” refer to copolymers of ethylene and vinyl acetate. 
         [0039]    As used herein, the term EVOH refers to saponified products of ethylene vinyl ester copolymers. The ethylene content is typically in the range of 25 to 50%. 
         [0040]    As used herein the term PVDC refers to a vinylidene chloride copolymer wherein a major amount of the copolymer comprises vinylidene chloride and a minor amount of the copolymer comprises one or more monomers such as vinyl chloride and/or alkyl acrylates and methacrylates. 
         [0041]    As used herein the term polyamide refers to homopolymers and copolymers. Typical examples are polyamide 6, polyamide 66, polyamide 6/66, polyamide 6/12 and MXD nylon. 
         [0042]    As used herein the term “polypropylene” refers to any homopolymer, copolymer, terpolymer, tetrapolymer etc. that includes mer units of propylene. The term as used in the present application includes homopolymers, random copolymers, propylene alpha olefin copolymers, propylene ethylene copolymers propylene-ethylene-alpha olefin copolymers and other propylene polymers. 
         [0043]    As used herein, the term “polybutylene” refers to homopolymer of butene-1 or to copolymers with ethylene or propylene. 
     
    
     DETAILED DESCRIPTION 
       [0044]    The PVDC used in this invention is preferably a copolymer of vinylidene chloride and vinyl chloride or a copolymer of vinylide chloride and methyl acrylate or a blend of both. 
         [0045]    The percentage of EVA used preferably is less than 20% per weight of the total blend. 
         [0046]    The percentage of PVC used preferably is less than 2% per weight of the total polymer blend. 
         [0047]    The percentage of the epoxidized oil compound preferably is less than 5% per weight of the total polymer blend. 
         [0048]    The plasticizer-stabilizer used is preferably one of epoxidized soybean oil, epoxidized linseed oil. 
         [0049]    The blend of EVA copolymer, PVC and additives can be a ready made compound in pallet or powder form. A preferred compound is BAYMOD L2450 purchased by the company Lanxess. 
         [0050]    The epoxidized soybean oil or epoxidized linseed oil may be preblended to the PVDC copolymer or blended at the same time with the rest of components. Well known mixing techniques may be used to secure that the final blend is homogeneous. 
         [0051]    Powder is preferable when the PVDC used is also powder. 
         [0052]    In a second aspect, a plastic film is disclosed comprising a layer comprising the composition as mentioned above. 
         [0053]    Preferably, the film is comprising five layers, where the middle layer comprises the composition as defined above and the film is heat shrinkable. 
         [0054]    In the outside layer the following materials may be used:
       1. A polypropylene homopolymer or copolymer having a vicat softening point of less than 105° C. measured under ASTM D 1525. Preferably the polymer is homogeneous, having low molecular weight distribution and comonomer distribution.   2. PP polymer such as random copolymer or homopolymer (among others)   3. Polyethylene polymer such as an alpha olefin copolymer with density 0.860 to about 0.960 or such as an ethylene ester copolymer   4. a cyclic olefin copolymer   5. a styrene polymer   6. an ionomer or a methacrylic acid copolymer   7. a polyamide (care is needed in the barrier property evaluation).       
 
         [0062]    A preferred version comprises a:
       1. styrene butadiene copolymer   2. a blend of styrene butadiene copolymer and an ethylene alpha olefin copolymer       
 
         [0065]    Between the inner heat sealing layer and the oxygen barrier layer may exist further layers that could comprise any of the polymers mentioned in the possibilities for inner heat sealing layer. Preferred materials are ethylene vinyl acetate, ethylene alpha olefin copolymers, EMA polymers, polypropylene copolymers, polybutylene, styrene homopolymers or copolymers. 
         [0066]    Between the outer layer and the PVDC layer, one or more layers may be present. 
         [0067]    Preferred materials are ethylene vinyl acetate, ethylene alpha olefin copolymers, EMA polymers, polypropylene copolymers, polybutylene, styrene homopolymers or copolymers. 
         [0068]    Typical materials used in the sealing layer are ethylene alpha olefin copolymers and polypropylene copolymers. 
         [0069]    Any of the layers described above may also include additives well known in the art such as slip agents, antiblock, polymer processing aids, antistatic, antifog, acid scavengers, odor scavengers and the like. A person skilled in the art may select the right additives according to any particular needs. 
         [0070]    In a preferred version of the application, the film is irradiated with e beam radiation of levels from 1 to 10 MRAD. 
         [0071]    The material of this invention is preferably biaxially oriented and heat shrinkable. 
         [0072]    In a further aspect, the invention comprises a bag or pouch made by the film of the invention and a cheese packed in such a film. 
       EXAMPLES 
     Example 1 
       [0073]    A 5 layer film is produced in a double bubble commercial line with the following structure: 
         [0000]    Inner (sealing) layer, 100% PL1, thickness 25 microns
 
Adjacent layer 93% E1+7% ADDITIVES, thickness 5 microns
 
Barrier layer PVDC 1, thickness 4.5 microns
 
Adjacent layer 30% M1+65% E3+5% ADDITIVES, thickness 11 microns
 
Outer layer 100% SB1, thickness 7.5 microns
 
See table 1, 2
 
       Example 2 
       [0074]    Inner (sealing) layer, 100% PL1
 
Adjacent layer 93% E1+7% ADDITIVES
 
Barrier layer PVDC 2
 
Adjacent layer 30% M1+65% E2+5% ADDITIVES
 
Outer layer 100% SB1
 
Thicknesses the same as example 1.
 
       Comparative Example 3 
       [0075]    A 5 layer film is produced in a double bubble (the double bubble method is described in U.S. Pat. No. 3,456,044) commercial line with the following recipe 
         [0000]    Inner (sealing layer), 100% PL1
 
Adjacent layer 93% E1+7% ADDITIVES
 
Barrier layer PVDC commercial grade
 
Adjacent layer 30% M1+65% E2+5% ADDITIVES
 
Outer layer 95% S1+5% ADDITIVES
 
         [0076]    The difference between the examples 1 and 2 which represent the invention and ex. 3 is that the PVDC formulation used in ex. 3 is believed to have a much bigger percentage of migratory materials like epoxidized oils (more than 5% in the blend). These materials are used in order to adjust the permeability to CO 2  and O 2 . 
         [0077]    The present invention proposes another way to adjust the permeability, without sacrificing the processability of the blend. As seen in table 3, the formulations of the invention are much more stable even after 3 months. 
         [0078]    With the inventive formulations, problems like delaminations of PVDC are also much improved. 
         [0079]    All the samples were e-beam radiated with a dose of 4 MRAD prior to bag making. 
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                   
                   
                   
                 Melt 
                   
                   
               
               
                   
                   
                   
                 Index 
                 Density 
                 Melting point 
               
               
                 Type 
                 Description 
                 Manufacturer 
                 g/10 min 
                 g/cm 3   
                 ° C. 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 E1 
                 EVA 
                 Dupont 3135 X 
                 0.35 
                 0.93 
                 95 
               
               
                 E2 
                 EVA 
                 Dupont 3165 
                 0.7 
                 0.94 
                 89 
               
               
                 S1 
                 SB 
                 DK13 
                 10 
                 1.01 
               
               
                   
                 COPOLYMER 
               
               
                 M1 
                 EMA copolymer 
                 ARKEMA LOTRYL 
                 2-3.5 
                 0.95 
                 61 
               
               
                   
                   
                 29MAO3 
               
               
                 P1 
                 Ethylene 
                 DOW AFFINITY PL 
                 1 
                 0.902 
                 100 
               
               
                   
                 octene 
                 1880 
               
               
                   
                 copolymer 
               
               
                   
               
             
          
         
       
     
       Manufacture of the Three PVDC 
       [0080]    PVDC 1. Blend of PVDC copolymer (which already incorporates about 2% per weight epoxidized soybean oil) with 11% BAYMOD L2450. 
         [0081]    PVDC 2. Blend of PVDC copolymer (which already incorporates about 2% per weight epoxidized soybean oil) with 16% BAYMOD L2450. This blend is used for packaging of special “high gassing” types of cheeses. 
         [0082]    PVDC 3. Commercial PVDC with more than 5% epoxidized soybean oil. 
         [0083]    Measurements were done three days after the irradiation step. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 O 2   
                 CO 2   
                 CO 2  transmission 
               
               
                   
                 transmission 
                 transmission 
                 After 3 months 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Example 1 
                 155 
                 810 
                 750 
               
               
                   
                 Example 2 
                 410 
                 2100 
                 1950 
               
               
                   
                 Example 3 
                 140 
                 780 
                 450 
               
               
                   
                   
               
             
          
         
       
     
         [0084]    O 2  transmission is measured in 23 C, 75% RH according to ASTM D3985. Units are CC/M 2 *atm*day. 
         [0085]    CO 2  transmission is measured according to internal method using a MOCON type instrument. Units are CC/M 2 *atm*day. Conditions 23° C. at 0% RH. 
         [0086]    We see that the combinations 1 and 2 are much more stable overtime. This is beneficial as it reduces the risks of pack “ballooning” after a certain period of time.