Abstract:
The present invention refers to a polymeric film comprising an odor barrier material and being able to pack malodorous waste.

Description:
[0001]    The present U.S. patent application claims priority to European Patent Application No. 12 154 500.8, filed Feb. 8, 2012, the disclosure of which is incorporated herein by reference in its entirety. 
         [0002]    The present invention refers to a polymeric film comprising an odor barrier material and being able to pack malodorous waste. 
         [0003]    A lot of waste products produce smells that are annoying to the environment. Examples are decayed food, kid nappies and cat litter. 
         [0004]    In the prior art there are many films that could be used for protection from malodors. As well known in the art, the use of materials like EVOH, PVDC, polyacrylonitrile is recommended in order to not allow malodors escape from the container (e.g. bag or other configuration) and create an unpleasant atmosphere. 
         [0005]    There are also a lot of known configurations of packing a certain length of film (e.g. 20 meters) in a compressed form (e.g. in a cassette). Examples of the representative cassettes are shown in U.S. Pat. No. 4,934,529 or U.S. Pat. No. 3,356,192. 
         [0006]    Generally the cassette comprises a tubular core, casing wall and cassette bottom. The film is pulled through the area between the lid of the cassette and the casing wall. The flexible tubing is dispensed from the cassette. After the malodorous item (e.g. diaper) is thrown into the bag the core is rotated and the flexible tube is twisted so that it closes as hermetically as possible the waste/environment area. 
         [0007]    To dispose the next diaper the user pushes the next portion of film. The previous hermetically closed diaper is pushed downwards and the new diaper is packed in a new configuration. All these different packs are stored in a bin which is periodically emptied. 
         [0008]    Separation of one pack to the other can be done by various means. A rotary knife is preferred. 
         [0009]    Recently other methods of packing waste have been emerged such as the use of adhesive films. In prior art patent application US2008/0115463 use of adhesive film is suggested as an alternative way to pack malodorous items. However, there is no detail about how the film could be formulated or any hint about its structure. 
         [0010]    The challenge the present application tackles is to achieve the following film characteristics:
       1. Low thickness material for economical production and competitiveness.   2. Odor barrier.   3. Possibility to bond to itself by a slight hand pressure   4. Easy unwinding of the reel.   5. Good mechanical properties to handle consumer abuse during using.       
 
       Film Characteristics 
       [0016]    We have surprisingly found that all these features can be achieved with a very lightweight multilayer film with a grammage of less than 25 g/m 2 . This is extremely beneficial for the environment as multilayer films are extremely difficult to be produced with so small weight per surface. Prior art films are characterized by a weight per surface ratio of more than 25 g/m 2  and often of more than 30 g/m 2 . 
       SUMMARY OF THE INVENTION 
       [0017]    The invention is directed to a multilayer film with a weight per surface ratio of less than 25 g/m 2  used in malodorous item packaging, where the film comprises at least one oxygen barrier material and a layer comprising a self-adhesive material. 
         [0018]    The films according to the invention show superior results regarding tensile strength and elongation characteristics. Furthermore, the films according to the invention were comparable in odor testing compared to commercially available films. 
       DEFINITIONS 
       [0019]    In this application the following definitions are used: 
         [0020]    The term “film” refers to a flat or tubular flexible structure of thermoplastic material. 
         [0021]    The term “heat shrinkable” refers to a film that shrinks at least 10% in at least one of the longitudinal (MD) and transverse (TD) directions when heated at 90° C. for 4 seconds. The shrinkability is measured in water according to ASTM 2732. For temperatures like 100° C. or more, glycerine is used as a reference liquid. 
         [0022]    The term “total heat shrinkability” refers to the sum of heat shrinkability at the MD (machine) direction and heat shrinkability at the TD (transverse) direction. In all cases, ASTM 2732 is used for measurement of shrinkabilities. 
         [0023]    The term “multilayer” refers to a film comprising 2 or more layers. 
         [0024]    The phrase “longitudinal direction” or “machine direction” herein abbreviated “MD” refers to a direction along the length of the film. 
         [0025]    The phrase “outer layer” refers to the film layer which comes in immediate contact with the outside environment (atmosphere). 
         [0026]    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. 
         [0027]    As used herein, the term “homopolymer” refers to a polymer resulting from polymerization of a single monomer. 
         [0028]    As used herein, the term “copolymer” refers to a polymer resulting from polymerization of at least two different polymers. 
         [0029]    As used herein, the term “polymer” includes both above types. 
         [0030]    As used herein, the term “polyolefin” refers to any polymerized olefin, which can be linear, branched, cyclic, aliphatic, substituted or unsubstituted. More specifically, included in the term polyolefin are homopolymers of olefin, copolymers of olefin, copolymers of an olefin and a non olefinic comonomer (such as ester) etc. 
         [0031]    Specific examples include polyethylene homopolymer, polypropylene homopolymer, polybutene homopolymer, ethylene alpha olefin copolymer, propylene alpha olefin copolymer, butene alpha olefin copolymer, ionomer, ethylene ester copolymer etc. 
         [0032]    As used herein the term “polyethylene” identifies polymers consisting essentially of the ethylene repeating unit, i.e. more than 50% of it are formed by ethylene repeating units. 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). 
         [0033]    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 catalyzed polymers and polyethylene plastomers and elastomers. 
         [0034]    As used herein the term “homogenous ethylene alpha olefin copolymers” refer to ethylene alpha olefin copolymers having a molecular weight distribution less than 2.7 as measured by GPC (gas permeation chromatography). Typical examples of these polymers are AFFINITY® from Dow or EXACT® from Exxon. 
         [0035]    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. 
         [0036]    As used herein the phrase “ethylene methacrylate copolymers” or EMA refers to copolymers of ethylene and methacrylate monomer. The monomer content is less than 40% per mol. 
         [0037]    As used herein the phrase “ethylene vinyl acetate copolymer” or EVA refer to copolymers of ethylene and vinyl acetate. 
         [0038]    As used herein the phrase “ethylene ester copolymer” includes any polymer made from ethylene and ester monomers. It is obvious that this term includes EVAs, EMAs and other polymers. 
         [0039]    As used herein the term “oxygen barrier polymer” refers to polymers which have the property to limit the passage of oxygen through a film or a layer comprising the polymer. Common materials are EVOH, PVDC or polyamide. 
         [0040]    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% per mol. All the later references to EVOH ethylene content will be in % per mol. 
         [0041]    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. A major amount is defined as one of more than 50%. 
         [0042]    As used herein the term “polyamide” refers to homopolymers and copolymers. Polyamide 6, polyamide 66, polyamide 12, polyamide 6/66, polyamide 6/12, polyamide elastomers, MXD polyamides and other copolymers are specifically useful for the invention. 
         [0043]    As used herein the term “polyester” refers to polymers comprising terephthalate units. Examples of polyesters are PET (polyethylene terephthalate), PBT (polybutylene terephthalate), polyester elastomer (block copolymer comprising ester or ether units), PTT (polytrimethylene terephthalate) and other similar polymers. 
         [0044]    As used herein, the term “ionomer” comprises the copolymers of ethylene and methacrylic or acrylic acid being metal neutralized. An example of such material is Surlyn from Dupont. 
         [0045]    As used herein, the term “polypropylene” refers to polymers incorporating propylene structural units. Examples of these, are homo polypropylenes, random copolymers of propylene and ethylene, block copolymers of propylene and ethylene, copolymers or blends of propylene and rubber (such as blends of polypropylene and ethylene propylene rubber), propylene ethylene alpha olefin terpolymers and others. 
         [0046]    The above polymers may be isotactic, syndiotactic or atactic. Isotactic configuration is preferred. 
         [0047]    As used herein the term “self-adhesive material” refers to materials that when produced into film form can be bonded to themselves by pressure only without the need to be heated. The bonding level which separates self-adhesive from non self-adhesive materials is 5 g/15 mm when the bonding has been done on a 100×1500 mm film piece with a pressure of 3 bar under ambient conditions and with a contact time of 5 seconds. Values of equal to or more than 5 g/15 mm according to this test show that the material is self-adhesive whereas values of lower than 5 g/15 mm show the film being non self-adhesive. 
         [0048]    As used herein the term “substantially non resilient material” refers to materials or material compounds comprising at least 40% per weight inorganics like calcium carbonate, titanium dioxide, wollastonite, mica, glass fibers, dolomite and the like. The rest percentage per weight can be polyethylene, polypropylene, styrene polymer or other thermoplastic material. 
         [0049]    As used herein the term “tackifier” refers to low molecular weight materials used to increase the stickiness of the surface of an adhesive. Typical examples are rosins and their derivatives, terpenes and modified terpenes, hydrogenated hydrocarbon resins, C5 aliphatic resins, C9 aromatic resins, C5/C9 resins, terpene/phenol resins and the like. 
         [0050]    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. 
         [0051]    All percentages are based on weight per weight ratio, except when otherwise stated. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0052]    According to a first aspect the present invention is directed to a multilayer film with weight per surface ratio of less than 25 g/m 2  used in malodorous item packaging, where the film comprises a layer comprising a self-adhesive material and a layer comprising an oxygen barrier material. 
         [0053]    According to a further aspect the present invention is directed to a multilayer film with weight per surface ratio of less than 20 g/m 2  used in malodorous item packaging, where the film comprises a layer comprising self-adhesive material and a layer comprising an oxygen barrier material. 
         [0054]    According to a further aspect the present invention is directed to a multilayer film with weight per surface ratio of less than 15 g/m 2  used in malodorous item packaging, where the film comprises a layer comprising self-adhesive material and a layer comprising an oxygen barrier material. 
         [0055]    In a further preferred embodiment, the film comprises the construction: 
       OUTER LAYER/ABUSE LAYER/INTERMEDIATE LAYER/BARRIER LAYER/INTERMEDIATE LAYER/ABUSE LAYER/INNER LAYER 
       [0056]    In another preferred embodiment, the film comprises the construction: 
       OUTER LAYER/INTERMEDIATE LAYER/BARRIER LAYER/INTERMEDIATE LAYER/INNER LAYER 
       [0057]    Detailed description of layers: 
       Barrier Layer 
       [0058]    In a preferred embodiment of the invention, the oxygen barrier material is EVOH. The EVOH used preferably has an ethylene content less than 48%, more preferably less than 44%, more preferably less than 38%, more preferably from 27 to 32% ethylene per mol. 
         [0059]    In another preferred embodiment, the oxygen barrier material comprises polyamide. 
         [0060]    The oxygen barrier material preferably has a weight of less than 3 g/m 2 , more preferably less than 2 g/m 2  and even more preferably less than 1.5 g/m 2 . 
       Outer Layer 
       [0061]    In a preferred embodiment, the outer layer comprises self-adhesive material. 
         [0062]    In a further preferred embodiment, the weight per surface ratio of the outer layer is less than 6 g/m 2 , more preferably less than 5 g/m 2 . 
         [0063]    In a preferred version, the self-adhesive material comprises ethylene vinyl acetate copolymer where the vinyl acetate weight ratio is at least 20%, more preferably at least 25% even more preferably at least 25%, even more preferably at least 40%. 
         [0064]    In another preferred version the self-adhesive material is a propylene ethylene copolymer where the ethylene content is at least 10% per weight. 
         [0065]    In another preferred version the self-adhesive material comprises an ethylene alpha olefin copolymer with density less than 0.9 g/cm 3 , even more preferably less than 0.880 g/m 3 . Preferred alpha olefins are butene, hexene or octene. 
         [0066]    In another preferred version, the self-adhesive material comprises a maleic anhydrite grafted polyolefin. Examples are maleic anhydrite grafted ethylene vinyl acetate copolymer of linear low density polyethylene. 
         [0067]    In another preferred version, the self-adhesive material comprises styrene copolymers with a styrene content of less than 50% per weight. Typical examples are styrene butadiene styrene copolymers, styrene isoprene styrene copolymers, styrene ethylene butadiene copolymers and the like. 
         [0068]    In another preferred version, the self-adhesive material comprises ethylene methyl acrylate copolymer with a methyl acrylate content of at least 20% per weight. 
         [0069]    In another preferred version, the self-adhesive material comprises ethylene butyl acrylate material with a butyl acrylate content of at least 15% per weight. 
         [0070]    In another preferred version, the self-adhesive material comprises poly-isobutylene polymer (PIB) or polybutene copolymer. 
         [0071]    In a further preferred version, the self-adhesive material comprises silicone elastomer. 
         [0072]    The outer layer may also comprise non self-adhesive materials such as polyolefins (preferably polyethylene homopolymers of copolymers) but not to the extent that the self-adhesive properties are falling below 5 grams/15 mm measured by the method described below. 
         [0073]    In another version, the outer layer may comprise tackifiers such as hydrocarbon resins, terpene resins, rosins and the like. Typical examples are Escorez materials from Exxon. 
         [0074]    In a further preferred version the outer layer may comprise materials such as “substantially non resilient materials” (SNR). See the above definition of this term. 
         [0075]    In a preferred version of the invention, the self-adhesive material in the outer layer is an extrudable material, meaning that it is melt processed by extrusion process. 
       Inner Layer 
       [0076]    As defined above, 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. 
         [0077]    Preferred materials for the inner layer include polyolefins, such as low density polyethylene, high density polyethylene, ethylene ester copolymer, ethylene alpha olefin copolymer and polypropylene. Ionomers and styrene copolymers are also possible. Ethylene alpha olefin copolymer is particularly preferred. 
         [0078]    According to a further embodiment, the present invention is of the same configuration where inner layer comprises a “substantially non resilient material” (SNR). 
         [0079]    In a preferred version of the invention, the SNR material is at least 10 percent, preferably at least 20, preferably at least 30 percent per weight of the inner layer. 
         [0080]    In a preferred version the inner layer comprises at least one release agent that is a polymer or chemical substance that allows the surface tension of the inner side to decrease. The reason for this is to allow the easy unwinding of the reel when the inner and the outer side come in contact one to the other. 
       Intermediate Layers 
       [0081]    In the intermediate layers, also called adjacent layers, typical adhesive resins like maleic anhydrite modified polyolefins may be used. Typical examples are BYNEL® from Dupont and OREVAC® from Arkema. 
         [0082]    In another preferred version of the invention, polyamide could be used as intermediate layer. 
       General 
       [0083]    The preferred production method for the film is the hot blown film method, which is well known in the art. Other methods like extrusion through flat cast die are also possible. 
         [0084]    Additives well known in the art may be used in one or more layers of the present invention. Slip additives, antiblock additives, antifog, polymer processing aids may be used if pertinent. Antimicrobial additives may also be used in one or more of the layers to inhibit the microbe formation. Preferably the antimicrobial is put on the side where the waste is in direct vicinity. 
         [0085]    In order to increase the mechanical properties the film may be crosslinked with one of the following methods. 
         [0086]    E-beam radiation, gamma radiation, moisture crosslinking using silane grafting compounds, peroxide crosslinking. 
         [0087]    The film may be in tubular form or sealed at the edges or single sheet configuration. Centerfold configuration is also possible. 
         [0088]    In a preferred version the film tears easily along the transverse direction. Even if the tear is initiated by an operator along the MD, then a further propagation leads the tear along the transverse direction. 
       EXAMPLES 
     Example 1 
       [0089]    A 5 layer film is produced in a commercial hot blown film line with the following recipe: 
         [0000]    
       
         
               
               
             
           
               
                   
               
             
             
               
                 Inner layer, 
                 80% EAO1 + 15% SNR1 + 5% ADDITIVES 
               
               
                 Adjacent layer 
                 100% ADH 1 
               
               
                 Barrier layer 
                 EVOH 1 
               
               
                 Adjacent layer 
                 100% ADH1 
               
               
                 Outer layer 
                 Ethylene vinyl acetate copolymer comprising 80% vinyl 
               
               
                   
                 acetate per weight (= a blend of EVA with 90% 
               
               
                   
                 vinyl acetate + 10% low density polyethylene) 
               
               
                   
               
             
          
         
       
     
         [0090]    See table 1 
         [0091]    The thickness of the structure is 5/1.5/1.5/1.5/4 starting from the inner and going to the outer layer. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                   
                 Density 
               
               
                   
                 Type 
                 Description 
                 g/cm 3   
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 EAO1 
                 Ethylene octene copolymer 
                 0.92 
               
               
                   
                 SNR1 
                 Calcium carbonate compound 
                 1.6 
               
               
                   
                 ADH1 
                 LLDPE mod. 
                 0.92 
               
               
                   
                   
                 Adhesive tie 
               
               
                   
                 EVOH 1 
                 EVOH with 32% ethylene 
                 1.19 
               
               
                   
                   
               
             
          
         
       
     
         [0092]    The weight per surface ratio of the film is 15.2 g/m 2 . 
       Example 2 
       [0093]    A 5 layer film is produced in a hot blown film commercial line with the following recipe 
         [0000]    
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Inner layer, 
                 80% EAO1 + 15% SNR1 + 5% ADDITIVES 
               
               
                   
                 Adjacent layer 
                 100% ADH 1 
               
               
                   
                 Barrier layer 
                 EVOH 1 
               
               
                   
                 Adjacent layer 
                 100% ADH1 
               
               
                   
                 Outer layer 
                 Propylene ethylene copolymer 
               
               
                   
                   
               
             
          
         
       
     
         [0094]    The thickness of the structure is 5/1.5/1.5/1.5/3 starting from the inner and going to the outer layer. 
         [0095]    The weight per surface ratio of the material is 13.2 g/m 2 . 
       Example 3 
       [0096]    A 5 layer film is produced in a commercial hot blown film line with the following recipe 
         [0000]    
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Inner layer 
                 80% EAO1 + 15% SNR1 + 5% ADDITIVES 
               
               
                   
                 Adjacent layer 
                 100% ADH 1 
               
               
                   
                 Barrier layer 
                 EVOH 1 
               
               
                   
                 Adjacent layer 
                 100% ADH1 
               
               
                   
                 Outer layer 
                 A blend of 90% ethylene vinyl acetate copolymer 
               
               
                   
                   
                 comprising 80% vinyl acetate per weight + 10% 
               
               
                   
                   
                 calcium carbonate polyethylene compound 
               
               
                   
                   
               
             
          
         
       
     
         [0097]    See table 1 
         [0098]    The thickness of the structure is 5/1.5/1.5/1.5/4 starting from the inner and going to the outer layer. 
       Example 4 
       [0099]    A 5 layer film is produced in a hot blown film commercial line with the following recipe 
         [0000]    
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Inner layer 
                 80% EAO1 + 15% SNR1 + 5% ADDITIVES 
               
               
                   
                 Adjacent layer 
                 100% ADH 1 
               
               
                   
                 Barrier layer 
                 EVOH 1 
               
               
                   
                 Adjacent layer 
                 100% ADH1 
               
               
                   
                 Outer layer 
                 Styrene butadiene styrene copolymer 
               
               
                   
                   
               
             
          
         
       
     
         [0100]    The thickness of the structure is 5/1.5/1.5/1.5/3 starting from the inner and going to the outer layer. 
         [0101]    The weight per surface ratio of the material is 13.2 g/m 2 . 
       Tests 
       [0000]    
       
         
           
             1. Tensile strength and elongation test is done according to ASTM D 882. 
             2. Odor test is done in the following way. 
           
         
       
     
       Test 1. 
       [0104]    Tensile strength and elongation is measured as per ASTM D882. 
         [0105]    MD stands for machine direction, whereas TD stands for transverse direction. 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
               
               
                   
                 TENSILE 
                 ELONG- 
                 TENSILE 
                 ELONG- 
               
               
                   
                 STRENGTH 
                 ATION 
                 STRENGTH 
                 ATION 
               
               
                 EXAMPLE 
                 (MD) 
                 (MD) 
                 (TD) 
                 (TD) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 25.5 
                 110 
                 23.5 
                 430 
               
               
                 2 
                 27.2 
                 104 
                 24.3 
                 430 
               
               
                 3 
                 26 
                 160 
                 16 
                 400 
               
               
                 4 
                 22 
                 180 
                 18 
                 505 
               
               
                   
               
             
          
         
       
     
       Odor Testing 
       [0106]    10 soiled diapers are put in a film of the present invention and also in a commercially sold film. The commercially sold film is believed to be monolayer. 
         [0107]    The packs are put in PVDC comprising bags, so the odor cannot escape during the time of the evaluation. 
         [0108]    The bags are opened 3 days after the soiling of the diapers and smell was evaluated by a 5 member panel. 
         [0109]    The packs made from examples 1-4 were found substantially less smelly than the commercially sold ones. 
       Adhesive Property Testing 
       [0110]    Films of examples 1, 2, 3, 4 were tested as per adhesive property as follows: 
         [0111]    Two pieces of dimensions 100×1500 mm film are cut by the operator. Then the operator places them under the jaw of a TOSS sealing machine under temperature 20° C. The pressure of the jaws is 3 bar. Contact (sealing time) of the two pieces of the film is 5 seconds. The self-adhesive side of the first piece is bonded to the self-adhesive side of the second piece. 
         [0112]    Then 15 mm stripes are cut either along the MD (machine direction) or along the TD (transverse direction). The adhesive force is measured in an Instron® machine as per the methodology of ASTM D882, 
         [0113]    According to this test the self-adhesive force is 
         [0000]    Example 1, 15 grams
 
Example 2, 11 grams
 
Example 3, 115 grams
 
Example 4, 80 grams
 
         [0114]    The above numbers are averages of the measurements along the MD and TD direction. 
         [0115]    A commercially used film tested as per adhesive property gave practically a self-adhesive force of 0 grams therefore it could not be potentially used in the application. 
       Tear Test 
       [0116]    It was noticed that when a human operator tears the film along the machine direction then a further propagation of the tear follows the transverse direction. This unexpected controlled tear property can be useful in various applications.