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  • 专利说明
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    • 专利摘要:
    Active polystyrene film. The present invention belongs to the field of active polymeric materials. In particular, it refers to an active polystyrene film that has antimicrobial or antioxidant activity and to the production method of said film. It also refers to wraps, containers and separators of slices (interleavers) comprising said film. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2711023A1
    申请号:ES201731261
    申请日:2017-10-27
    公开日:2019-04-29
    发明作者:Castro Raul Gallego；Cerrada Llucià Cordero
    申请人:Viscofan SA；
    IPC主号:
    专利说明:

    [0001]
    [0002] Active polystyrene film
    [0003]
    [0004] 5 Field of the invention
    [0005]
    [0006] The present invention belongs to the field of polymeric materials releasing active substances for protection and / or extension of the useful life of foods. In particular, it refers to an active polystyrene film having antimicrobial or antioxidant activity and to the method of preparation of said film. It also refers to wraps, containers and separator films of slices (interleavers) that comprise said film.
    [0007]
    [0008] Background of the invention
    [0009]
    [0010] 15 In order to improve the oxidative and microbial stability of food products and thus prolong their shelf life, antioxidants and antimicrobial agents are used, respectively, as additives that are added directly to the products.
    [0011]
    [0012] Thus, it is a common practice that during the processing or before the packaging of food products, antioxidants or antimicrobial agents are added directly, in relatively high quantities, so that they can be protected for a long time. During storage and marketing, that initial amount gradually decreases when exerting its antioxidant or antimicrobial effect and eventually ends. At that moment, the oxidation reactions start and the product begins to deteriorate, or when the microorganisms present in the product begin to grow.
    [0013] Oxidation reactions in packaged food products start at the surface, particularly in the portion that first receives the oxygen or light that diffuses through the container wall, so systems have been developed where the container It is used as a vehicle for the application of antioxidant agents.
    [0014]
    [0015] Likewise, the part most vulnerable to microbial contamination of a packaged food is the surface thereof and various systems have been described where the package is used as a vehicle for the application of antimicrobial agents.
    [0016] The producers of films and packaging for food products have been decades trying to develop films and packaging with antioxidant or antimicrobial properties. Several products have been described in the literature.
    [0017]
    [0018] 5 US 8,343,522 B2 discloses coated sheets for antimicrobial treatment based on biopowers, particularly cellulosics and proteomics (for example collagen). The sheet has an antimicrobial character because it is impregnated or coated with at least one a-amino acid ester, where said a-amino acid is covalently bound to the film. Due to said covalent bond, the antimicrobial agent is not capable of being released into the medium.
    [0019]
    [0020] WO 2017/049364 A1 describes a food packaging material comprising a polymeric material and an antioxidant agent. In particular, in the tests shown the polymeric material is polyethylene resin and the antioxidant is a rosemary extract.
    [0021] fifteen
    [0022] US 2012/0276357 A1 discloses a packaging material with antioxidant activity comprising at least 89% of a polymeric substance, between 2-10% of tocopherol and between 0.1-1% of a surface modifying agent. In particular, in the tests shown the polymeric substance is low density polyethylene.
    [0023] twenty
    [0024] US 8,734,879 discloses a method for preserving a food product through a packaging material with preservative properties. Said packaging material comprises a salt of Na-lauroyl-L-arginine ethyl ester and an acyl monoglyceride comprising glycerol monolaurate incorporated in a polymeric material. Said document shows a synergistic effect in the preservative action only between the Na-lauroyl-L-arginine ethyl ester salt and the glycerol monolaurate, there are no tests with other compounds.
    [0025]
    [0026] To date, inventors are not aware of the presence of these products in the market. In particular, they have not found any separator of polystyrene slices with antioxidant or antimicrobial properties.
    [0027]
    [0028] Surprisingly, the authors of the present invention have developed a film in which the active substances migrate to the surface of the film and maintain their functionality despite the process of making the film. With this film you can prepare separators of 35 slices, wraps and containers for food products with antioxidant or antimicrobial properties. Thus, these separators, wraps and containers provide the products food with which they are in contact with antioxidant or antimicrobial properties. This supposes important advantages, between which it is possible to emphasize the prolongation of the useful life of said products.
    [0029]
    [0030] 5 Object of the invention
    [0031] The present invention relates in a first aspect to a polystyrene film for applications in contact with food products characterized in that it comprises at least one layer comprising:
    [0032] - 60% -75% (w / w) of crystal polystyrene (hereinafter referred to as PS);
    [0033] 10 - 10% -35% (w / w) of ethylene copolymer with polar monomers (hereinafter referred to as EMP) with a comonomer content of 15-40% by weight with respect to the total weight of the EMP (p / pt) pEMp);
    [0034] - an active substance selected from the group consisting of antioxidant agent and antimicrobial agent;
    [0035] 15 - 0.5% -2% (p / pt) of migration agent (hereinafter referred to as AdM);
    [0036] - 0% -15% (w / w) of emulsifying agent (hereinafter referred to as AE) with an HLB greater than 8, being 3-15% (w / w) when the active substance is an antimicrobial agent; and where the ratio PS / (EMP + AE) is between 1.2 and 7.5.
    [0037]
    [0038] A second aspect of the present invention relates to a slicing film separator
    [0039] (interleaver) comprising a film according to the first aspect of the invention.
    [0040]
    [0041] A third aspect of the present invention relates to a food package or wrapper that is made from or comprises a film according to the first aspect of the invention.
    [0042] 25
    [0043] A fourth aspect of the present invention relates to the use of a film according to the first aspect of the invention for food packaging or as a food separating film.
    [0044] A fifth aspect of the present invention relates to the method for producing a film according to the first aspect of the invention.
    [0045]
    [0046] Other objects, features, advantages and aspects of the present application will be apparent to the person skilled in the art from the description and the appended claims.
    [0047]
    [0048] 35 Brief description of the figures
    [0049] Figure 1: Graphic representation of bacterial growth (in log CFU / ml) depending on the time (in days), where the red square is the control, the blue triangle is the film without EMP, and the green diamond is the film with EMP. In panel A the initial concentration of Listeria it was 101 and in panel B of 105
    [0050]
    [0051] Figure 2: Graphic representation of bacterial growth (in log CFU / ml) as a function of time (in days), where the red square is the control, the blue triangle is the film without PS and the green diamond is the film with PS. In panel A the initial concentration of Listeria it was 101 102 and panel B 105-106.
    [0052]
    [0053] Figure 3: Graphic representation of bacterial growth (in log CFU / ml) as a function of time (in days), where the red square is the control, the blue triangle is the film without AE and the green diamond is the film with AE. In panel A the initial concentration of Listeria it was 102 and in panel B of 106.
    [0054]
    [0055] Figure 4: Graphic representation of bacterial growth (in log CFU / ml) as a function of time (in days), where the red square is the control, the green diamond is the film with AE and the blue triangle is the film without AE. The initial concentration of lactic acid bacteria was 105.
    [0056]
    [0057] Figure 5: Graphic representation of bacterial growth (in log CFU / ml) as a function of time (in days), where the red square is the control, the blue triangle is the film without AdM and the green diamond is the film with AdM. The initial concentration of Listeria It was 105.
    [0058]
    [0059] Figure 6: Photographs of petri dishes with agar inoculated with the mold object of analysis and with a control film (panel A) or with a film according to the invention (panels B and C).
    [0060]
    [0061] Detailed description of the invention
    [0062] As used in the present application, the singular forms "a / an", "an" and "the" include plurals thereof unless the context clearly indicates otherwise. Unless otherwise defined, all technical terms used herein have the meaning that a person skilled in the art to which this invention belongs usually understands.
    [0063]
    [0064] In order to facilitate the understanding and to clarify the meaning of certain terms in the context of the present invention, the following definitions and particular and preferred embodiment thereof are provided, applicable to all the realization is of the different aspects of the present invention:
    [0065]
    [0066] "Crystal polystyrene" (PS) (also known as amorphous polystyrene or general purpose polystyrene (GPPS, acronym for General Purpose Polystyrene)), is a polymer whose average molecular weight is between 100,000 g / mol and 400,000 g / mol. It is transparent, hard, fragile and smooth below 100 ° C. Above this temperature is easily processable and can be given multiple forms. It is completely atactic, that is to say, the phenyl groups are distributed to one or the other side of the central chain, without any particular order and therefore it is a completely amorphous poflmero.
    [0067] 10
    [0068] "Modified resistant polystyrene" (HIPS, acronym of High Impact Polystyrene), also referred to as high impact polystyrene or medium impact polystyrene, is a graft copolymer as it contains a styrene backbone and grafted polybutadiene chains. This copoflomer is resistant to wear and has a high resistance to impact.
    [0069]
    [0070] "Emulsifying agent" (AE) refers to any emulsifier that has an HLB greater than 8, is processable at a temperature of up to 200 ° C and its use is allowed in contact with food and / or edible. The EA facilitates the solubility of the active substance and its liberation in the medium. In a particular embodiment, the EA is selected from the group consisting of polyethylene glycol 400 dioleate (PEG400DO), polyoxyethylene (20) sorbitan monolaurate (Tween® 20), polyoxyethylene (20) sorbitan monopalmitate (Tween® 40), polyoxyethylene monostearate ( 20) sorbitan, (Tween® 60), polyoxyethylene (20) sorbitan tristearate (Tween® 65), polyoxyethylene (20) sorbitan monooleate (Tween® 80), ethylene polyoxide stearate 25 (PEO40-S), monolaurate of sorbitan (Span® 20) and mixtures thereof. In a
    [0071] preferred embodiment the AE is selected from the group consisting of PEG400DO, Tween® 80, PEO40-S and mixtures thereof, and more preferably the AE is Tween® 80.
    [0072]
    [0073] "Migration agent" (referred to hereafter as "AdM") refers to a molecule 30 that contains a hydrophobic and a hydrophilic portion, which makes it incompatible with the polymer matrix and causes its diffusion through it, accumulating in the surface with its hydrolytic part towards the outside and its hydrophobic part towards the poflmero. Due to the tendency of this molecule to orient itself, diffuse and accumulate on the surface, it causes the entrainment of the active substance, which is attracted by the hydrophobic chain. In a particular embodiment, the AdM is selected from the group consisting of fatty acid amides (e.g.
    [0074] erucamide and oleamide), esters of fatty acids (e.g glycerol monostearate (MG)), metal stearates (e.g. zinc stearate), waxes and mixtures thereof. In a
    [0075] particular embodiment, glycerol monolaurate is not included among the fatty acid esters. Preferably, the AdM is selected from the group consisting of erucamide, oleamide, MG, zinc stearate, waxes and mixtures thereof, and more preferably the AdM is 5 MG or erucamide.
    [0076]
    [0077] The "antioxidant agent" (hereinafter referred to as the "AO agent") is an agent with antioxidant properties which, among others, prevents rancidity of the fats and / or browning of the food, in particular of the meat. agent 10 AO is selected from the group consisting of tocopherol, green tea extract, olive leaf extract, rosemary extract, grape seed extract, coffee extract, dehydrated acerola (eg acerola dehydrated powder with 17% -25). % of vitamin C), extracts of dtricos with a concentration of flavonoids greater than 45%, tomato extract with a concentration of lycopene greater than 5% (eg LYCOSEEN®), fruit extract (eg
    [0078] 15 Polyfence® 2), thymol and mixtures thereof. Preferably, the AO agent is selected from tocopherol, tea extract and mixtures thereof, and more preferably is tocopherol. The tocopherol can be a, p, and mixtures thereof (eg CAS 59-02-9, 16698-35-4, 54-28 4, 119-13-1), preferably being a mixture of α-tocopherol, p-tocopherol and Y-tocopherol.
    [0079] The "antimicrobial agent" (hereinafter referred to as the AM agent) is an active agent against bacteria (gram and / or gram-), fungi or yeasts, so it can be an antibacterial, antifungal or anti-yeast agent. an agent that is active against several of said microorganisms In a preferred embodiment the AM is an antibacterial and / or antifungal agent.
    [0080] 25
    [0081] The "antibacterial agent" (hereinafter referred to as AB) is an agent that is capable of preventing bacterial growth (bacteriostatic effect) or is capable of killing bacteria (bactericidal effect) .In the present invention it is considered that there is a " bacteriostatic effect "when there is a difference in bacterial growth with and without agent AB 30 of at least two logarithmic units. In a particular embodiment the agent AB is selected from the group consisting of anhydrous sodium acetate, nisin, lysozyme, Ag and its salts, Zn and its salts, ethyl Na-dodecanoyl-L-arginate (hereinafter referred to as LAE) , salts of LAE, and glycolipid biosurfactants. Among LAE salts is LAE hydrochloride (hereinafter referred to as LAE-Cl). Among the biosurfactants 35 glycolipids are the rhamnolipids, soporolipids, xylolipids and lipids of mannosyrouthrites. Preferably, agent AB is selected from LAE, salts thereof, preferably LAE-Cl, and mixtures thereof, and more preferably agent AB is LAE or LAE-Cl (e.g. CAS 60372-77-2).
    [0082]
    [0083] The "antifungal agent" (hereinafter referred to as "AF agent") is an agent with 5 fungicidal (mold killing) and / or fungistatic properties (which prevents mold growth) In a particular embodiment the AF agent is selected of the group consisting of mixtures of medium chain mono-, di-, and tri- glycerides, monolaurin, nisin, lysozyme, glycosylated biosurfactants, LAE and its salts, in particular LAE-Cl, and mixtures thereof. AF is selected from the group consisting of mixtures of mono-, 10 di- and tri- glycerides of medium chain, nisin, lysozyme, glycolipid biosurfactants, LAE and its salts, in particular LAE-Cl, and mixtures thereof. invention means "medium chain glycerides" those of chain C8-C12, preferably C8-C10. In a preferred embodiment, the AF agent is LAE, LAE-Cl, C8-C10 mono-, di- and triglycerides (e.g. CAS 91744-32-0).
    [0084] fifteen
    [0085] The food legislation applicable to each country restricts the number of substances that may be in contact with food and its limits. Substances must be suitable for contact with food, not only in its original form, but also after changes in pH, exposure to heat, humidity, etc., or hydrolytic rupture. Thus, in the present invention, all the components of the film of the invention must be suitable for contact with food and for consumption, since the film of the invention is for those applications in which there is contact between the film and a film. food product.
    [0086]
    [0087] The objective of the polystyrene film of the invention is to provide the food product with which it is in contact with an antioxidant or antimicrobial protection, in order to improve the appearance of the product, prolong the useful life of the product, etc. In order to release the minimum amount of active substance so that the film has functionality, it is necessary to replace part of the polystyrene with a polymer compatible with it, with the appropriate polarity and viscosity. In this case, said compatible polymer is EMP with a given content of 30 comonomer. The film of the invention comprises a polymeric matrix (also called plastic resin or resin hereinafter) comprising PS and EMP. Thus, the present invention relates in a first aspect to a polystyrene film for applications in contact with food products (hereinafter referred to as film of the invention) characterized in that it comprises at least one layer comprising:
    [0088] 35-60-75% (p / pt) PS;
    [0089] -10-35% (p / pt) EMP with a comonomer content of 15-40% p / pEMP;
    [0090] - an active substance selected from the group consisting of antioxidant agent and antimicrobial agent;
    [0091] - 0.5% -2% (p / pt) AdM;
    [0092] - 0-15% (w / w) AE with an HLB greater than 8, being 3-15% (w / w) when the active substance is an antimicrobial agent; Y
    [0093] where the relation PS / (EMP + AE) is between 1.2 and 7.5.
    [0094]
    [0095] Said at least one layer comprises an active substance by what is hereinafter referred to as "active layer".
    [0096] 10
    [0097] The percentages used in the present document are given, unless otherwise specified, in percentage by weight with respect to the total weight of the layer (p / pt), whether it is an active layer or not. The percentage by weight is not given with respect to the total weight of the film because the film can have a layer (this being an active layer) or it can have multiple layers 15 (at least one of them being an active layer).
    [0098]
    [0099] The technical characteristics of the film of the invention defined above result in a film in which it has been possible to maintain the functionality of the active substance comprising, even when said substance is normally thermolabile, and which has good processability (eg the polymer mixture allows obtain a homogeneous melt capable of flowing through the extruder without phase separation and transformable by the shaping methods used for the thermoplastics). In addition, the particular composition specified for the active layer allows the active substance to be evenly distributed within the polymer matrix of the layer and to be released to the medium (eg food with which it is in contact), where it exerts its activity ( eg antioxidant or antimicrobial). In this way, the film of the invention comprising an active layer as defined in the present invention efficiently provides antioxidant or antimicrobial protection to the food product that is in contact with said layer.
    [0100]
    [0101] In a preferred embodiment of the film of the invention, the content of PS is 64-70% (p / pt), that of EMP is 16-30% (p / pt) and the ratio PS / (EMP + AE ) is between 1.5 and 4.4. As shown in the Examples, films according to this preferred embodiment provide an antioxidant and antimicrobial protection in a surprisingly effective manner.
    [0102]
    [0103] 35 As shown in the Examples, the migration and antioxidant or antimicrobial activity depend on the composition of the film and it is essential that the film has a composition as defined in the present invention to efficiently provide an antioxidant or antimicrobial activity. In particular, as regards the PS component, it is essential that the active layer (s) have (n) polystyrene crystal and not another polymeric material such as polyethylene (see Example 4). Thus, in a particular embodiment 5 of the film of the invention, the active layer (s) comprise (s) as a polystyrene component only crystal polystyrene (PS), that is, PS is the only material of type polystyrene of the active layer (s) (eg the active layer does not comprise HIPS). In other
    [0104] particular embodiment according to any one of the embodiments is above, the active layer (s) does not comprise (s) cellulose and / or polyethylene, more particularly the film of the invention according to any one of the embodiments is The first aspect of the invention does not comprise cellulose and / or polyethylene. Preferably, the active layer (s) does not comprise any other polymeric material apart from PS and EMP.
    [0105]
    [0106] In a particular embodiment of the invention, PS comprises different types of glass polystyrene, more particularly PS comprises glass polystyrenes with different MFIs (acronym of Melt Flow Index). In a preferred embodiment according to any one of the
    [0107] embodiment is above, PS comprises PS with an MFI of between 10-40 g / 10 min at 200 ° C and 5 Kg (hereinafter referred to as PS1), more preferably 20-30 g / 10 min at 200 ° C and 5 Kg, and / or PS with an MFI of 2-5 g / 10 min at 200 ° C and 5 Kg (hereinafter referred to as 20 PS2), more preferably 2.5-4 g / 10 min at 200 ° C and 5 Kg. As shown in the examples, advantageously the use of these PS1 and / or PS2 provides a high release and activity of the active substance.
    [0108]
    [0109] In another preferred embodiment according to any one of the embodiments is above, PS 25 comprises at least 37% (p / pt) of PS2, which advantageously provides the film of the invention with excellent processability while maintaining its high release and activity of the active substance.
    [0110]
    [0111] It is also essential that the active layer (s) have EMP as, as shown in Examples 1 and 3, in the absence of EMP a large release of the substance is not achieved. activates neither an efficient antioxidant or microbial activity. In a particular embodiment EMP is selected from the group consisting of ethylene vinyl acetate copolymer (EVA), ethylene methyl acrylate copolymer (EMA), ethylene ethyl acrylate copolymer (EEA), ethylene butyl acrylate copolymer (EBA) and mixtures thereof. same. Preferably EMP 35 is EVA. As shown in the Examples, the use of EVA as EMP results in high release and activity of the active substance.
    [0112]
    [0113]
    [0114] In a particular embodiment of the invention, EMP comprises EMPs with different MFIs. In a preferred embodiment according to any one of the embodiments is above, EMP comprises EMP with an MFI of between 15-50 g / 10 min at 190 ° C and 2.16 Kg (hereinafter referred to as EMP1), more preferably 30 -45 g / 10 min at 190 ° C and 2.16 Kg, and / or EMP 5 with an MFI of 2-5 g / 10 min at 190 ° C and 2.16 Kg (hereinafter referred to as EMP2) , more preferably 2.5-4 g / 10 min at 190 ° C and 2.16 Kg. Thus, when the EMP comprises EMP1, it can be EVA1, EMA1, EEA1, EBA1 or mixtures thereof, and when the EMP comprises EMP2, can be EVA2, EMA2, EEA2, EBA2 or mixtures thereof. As shown in the examples, advantageously the use of these EMP1 and / or EMP2 10 provides a high release and activity of the active substance.
    [0115]
    [0116] In another preferred embodiment according to any one of the embodiments is above, EMP comprises at least 5% (w / w) of EMP2, which advantageously gives the film of the invention good processability.
    [0117] fifteen
    [0118] As indicated above, the active substance is uniformly distributed in the polymer matrix of the active layer, and said active substance is able to migrate to the surface of the plastic. To control said migration and protect the active substance from any type of cleaning treatment that is carried out on the film, the active layer 20 comprises 0.5% -2% (w / w) of AdM. Surprisingly, as shown in Example 6, the presence of AdM affects the migration of the active substance, since during the first days the migration of this substance is slower because its size is greater than that of the AdM, and also protects the active substance from the cleaning that occurs in the film, ie prevents or reduces the elimination / loss of active substance due to any cleaning process, whether physical or chemical. In addition, since the AdM is present, the processability of the film is favored since it prevents the molten materials from sticking to the metal parts, facilitates the movement of the melt through the extruder and prevents blockage of the bubble during the collapse of the allowing to separate it into two symmetrical films.
    [0119]
    [0120] In a particular embodiment according to any one of the embodiments is of the previous paragraph, the migrating agent is selected from the group consisting of fatty acid amides, fatty acid esters except glycerol monolaurate (monolaurin), metal stearates, waxes and mixtures thereof. Preferably the AdM is selected from the group consisting of erucamide, oleamide, glycerol monostearate and zinc stearate; and more preferably the AdM is glycerol monostearate and / or erucamide.
    [0121] In those cases in which it is desired that the film provide antioxidant protection to the food product, the active substance will be an antioxidant agent. Thus, in a particular embodiment according to any one of the embodiments is above, the active substance is an antioxidant agent and this is selected from the group consisting of tocopherol, green tea extract, olive leaf extract, rosemary extract, extract of grape seed, coffee extract, dehydrated acerola, titric extract with a flavonoid concentration greater than 45%, tomato extract with a concentration of lycopene greater than 5%, fruit extract, thymol and mixtures thereof. Preferably the antioxidant agent is tocopherol or green tea extract.
    [0122] 10
    [0123] In a particular embodiment according to any one of the embodiments is above, the active substance is an antioxidant agent and the content of the emulsifying agent is 0-5%, preferably 0-3%. The film of the invention is effective both in the absence of AE (see Examples 1 and 2), and in the presence thereof (data not shown). The presence of AE 15 does not imply a great improvement in the release of the AO agent since, as can be seen in Examples 1 and 2, the release of the AO in the absence of AE is close to 100%. Therefore, in a preferred embodiment, the film with antioxidant agent does not have AE, i.e. the content of AE is 0%, thus being an advantageous realization in economic and processing terms (the more elements in the mix the processability becomes more complex).
    [0124] twenty
    [0125] In those cases in which it is desired that the film provide antimicrobial protection to the food product, the active substance will be an antimicrobial agent. So, in a
    [0126] Particular embodiment of the invention, the active substance is an antimicrobial agent, more particularly an agent AB or AF selected from those given in the particular and preferred embodiments given at the beginning of the detailed description of the present invention. These embodiments are applicable to any of the embodiments of the first aspect of the invention in which the active substance is not an antioxidant agent.
    [0127]
    [0128] In a particular embodiment according to any one of the embodiments is from the previous paragraph, the active substance is an antimicrobial agent and the content of the EA is 3-12%, preferably 5-10%. As shown in the examples, with said AE content it is possible to efficiently control the microbial population in the medium in contact with the film of the invention, while in the absence of AE said antimicrobial control is not achieved (see Example 5).
    [0129] 35
    [0130] In a particular embodiment, the agent AE is selected from the group consisting of polyethylene glycol 400 dioleate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene sorbitan monooleate, stearate of ethylene polyoxide 40, sorbitan monolaurate and 5 mixtures thereof. Preferably, the EA is polyoxyethylene sorbitan monooleate.
    [0131]
    [0132] Surprisingly, the films of the invention are antioxidant or microbiologically effective even when low active substance concentrations are incorporated into their composition e.g. less than or equal to 6% p / pt. Thus, in a particular embodiment according to any one of the embodiments is above, the content of the active substance is 0.5-6% (w / w). As shown in the Examples, films with active layers with concentrations as low as 0.9% tocopherol and 1.37% AM agent efficiently provide the medium with antioxidant and antimicrobial activity, respectively.
    [0133]
    [0134] In a preferred embodiment, the polystyrene film of the first aspect of the invention according to any one of the embodiments is above, comprises at least one layer consisting of:
    [0135] - 60% -75% (p / p) of PS;
    [0136] - 10% -35% (p / pt) of EMP with a comonomer content of 15-40% p / pEMP;
    [0137] 20 - 0.5-6% of an active substance selected from the group consisting of antioxidant agent and antimicrobial agent;
    [0138] - 0.5% -2% (w / w) of AdM;
    [0139] - 0% -15% (p / pt) of AE with an HLB greater than 8, being 3-15% (p / pt) when the active substance is an antimicrobial agent;
    [0140] 25 where the relation PS / (EMP + AE) is between 1.2 and 7.5; Y
    [0141] where the total sum of the components is 100% by weight with respect to the total weight of said at least one layer (i.e. of the active layer).
    [0142]
    [0143] As shown in the Examples, films in which the active layer has a composition according to the above paragraphs, are able to release a functional active substance and to provide antioxidant or antimicrobial properties to the medium (eg food product) in contact with said film. Furthermore, the films of the invention have properties that allow a good processability as indicated above, and have mechanical characteristics that result in excellent cutting properties. Said 35 cutting properties allow the films to be sliced at speeds greater than 650 cuts / minute, and more particularly at speeds of up to 1,200 cuts / minute,
    [0144]
    [0145]
    [0146] thus achieving an excellent product stacking without burrs or irregular cuts.
    [0147] They are also highly non-stick films, with antistatic properties, allowing a easy separation of the slices without sticking, and are adjustable for all slicers available in the market.
    [0148] 5
    [0149] Thus in a particular embodiment according to any one of the embodiments is prior according to the first aspect of the invention, the film of the invention has a resistance to traction in machine direction and transverse greater than 20 MPa, and an elongation to break in machine direction and transverse greater than 20%. More particularly, it has tensile strength in machine direction greater than 30 MPa and in transverse direction greater than 20 MPa, and an elongation at break in machine direction greater than 40% and in transverse direction greater than 45%. These mechanical properties are widely known to those skilled in the art and have been obtained according to the UNE-EN ISO 527-3 standard.
    [0150]
    [0151] As indicated above, the film of the present invention may be monolayer or multilayer. If the film is multilayer, the film comprises at least two layers, at least one of which is an active layer.
    [0152]
    [0153] In a particular embodiment according to any one of the embodiments is above, the film is monolayer and has a total thickness of 10-300 microns, preferably 40-80 microns. In other
    [0154] particular embodiment, the film is multilayer and has a total thickness of 20-300 microns, preferably 30-80 microns. In both embodiments, monolayer and multilayer, the thickness of each active layer is at least 10 microns.
    [0155]
    [0156] The disposition of the multilayer film layers must be such as to allow contact of at least one active layer with the food product (ie the active layer is at least one of the outer layers of the film), so as to provide antioxidant protection or antimicrobial to said product. Thus, in a particular embodiment the film is multilayer and the active layer is an outer layer of said film, i.e. it can be in contact with the food product. In another particular embodiment, the film is multilayer and comprises at least one active layer and at least one layer without active substance (hereinafter referred to as "non-active layer"). The composition of the layer without active substance may be such that provide beneficial properties for the processability of the film or for its slicing.This is the case of a film in which the non-active layer comprises high-impact polystyrene (HIPS) and glass polystyrene.So, in a particular embodiment, the multilayer film comprises at least one active layer according to any one of the embodiments is described in the first aspect of the invention and at least one non-active layer comprising crystal polystyrene and HIPS. More particularly, said non-active layer comprises 60-90% w / w, preferably 65-75% w / w, of crystal polystyrene and 10-40% w / w, preferably 25-35% w / w of HIPS, more preferably, said non-active layer consists of 60-90% w / w, preferably 65-75% w / w, of crystal polystyrene and 10-40% w / w, preferably 25-35% w / w of HIPS, so that its composition is 100% p / pt.
    [0157]
    [0158] Preferably, the film of the invention according to any one of the embodiments is multilayer above, comprises three layers, where each of the two outer layers is an active layer 10 as defined in any one of the embodiments is above, and where the intermediate layer is a non-active layer as defined in any one of the
    [0159] Realization is previous. More preferably, the three-layer film consists of the three layers defined in this paragraph.
    [0160]
    [0161] As shown in Example 2, the multilayer films defined in the previous paragraphs show excellent antioxidant and cutting properties, which makes them suitable for use as interleavers
    [0162]
    [0163] Finally, in a particular embodiment according to any one of the embodiments is described in the first aspect of the invention, the film of the invention is tube-shaped.
    [0164]
    [0165] The film of the present invention can be used to prepare a slice separator film, since as indicated above it has excellent cutting properties and is slicable by slicing machines at a speed greater than 650 cuts / minute, and more particularly up to 1,200 cuts / minute. Also, thus, said slicer separator provides the active substance to each slice that is in contact with it through its active layer. Thus, a second aspect of the invention relates to a slicing separator comprising a film according to any one of the embodiments of the first aspect of the invention. More particularly, the separator consists of a film according to any one of the embodiments described in the first aspect of the invention.
    [0166]
    [0167] In addition to its use as a slice separator, the film of the invention can be used to make a wrap or food package. Thus, a third aspect of the invention relates to a wrapping or food packaging characterized in that it is made from or comprises a film according to any one of the embodiments described in the first aspect of the invention. As indicated above, the active layer of the film must be in
    [0168]
    [0169]
    [0170] contact with the food product to provide antioxidant or antimicrobial protection. In a particular embodiment, said food package consists of film according to any one of the embodiments described in the first aspect of the invention. The food package can be in the form of a tray, bag, bag in box, doy-pack, flow-pack, etc. The food wrap may have the shape of band, tube, etc.
    [0171]
    [0172] Taking into account all of the above, in a fourth aspect, the present invention relates to the use of a film according to any one of the embodiments described in the first aspect of the invention for the packaging of food products or as a film separator of food products , particularly separator of slices of food products. As indicated above, when using the film of the invention an antioxidant or antimicrobial protection is efficiently provided to the food product in contact with it.
    [0173] The microbiological risks of food products are still one of the main sources of foodborne diseases. Listeriosis is the most critical food transmission disease of the European Union and the USA, presenting a high mortality rate that stands at around 13%. The fact that L.
    [0174] monocytogenes can grow at refrigeration temperatures (2-4 ° C), causes the presence of this pathogen in products ready for consumption with a relatively long shelf life, such as products derived from fishing, cooked meat products, fermented sausages and cheeses, is a subject of special concern for food safety. On the other hand, the presence of lactic acid bacteria in food products causes changes in the sensory attributes of the same. Surprisingly, the film of the present invention provides excellent antimicrobial properties against lactic acid bacteria and Listeria (see Examples 3-6). So do the separators of slices, packages and wrappings that comprise it.
    [0175]
    [0176] Finally, in a fifth aspect, the present invention relates to a method (method of the invention) for producing the film of the invention, characterized in that it comprises the following steps:
    [0177] a) provide a polymeric composition comprising:
    [0178] - 60-75% (p / pt) PS,
    [0179] -10-35% (p / pt) EMP with a comonomer content of 15-40% p / pEMP,
    [0180] - an active substance selected from the group consisting of an antioxidant agent and an antimicrobial agent,
    [0181] - 0.5% -2% (p / pt) AdM,
    [0182]
    [0183]
    [0184] - 0-15% (p / pt) AE with an HLB greater than 8, being 3-15% when the active substance is an antimicrobial agent,
    [0185] where the relation PS / (EMP + AE) is between 1.2 and 7.5; Y
    [0186] b) forming a film with at least one layer comprising said polymeric composition.
    [0187] The particular embodiments of PS, PS1, PS2, EMP, EMP1, EMP2, AE, AdM, active substances and PS / ratio (EMP + AE) given for the first aspect of the invention are applicable to the fifth aspect of the invention. Likewise, the realization is given in relation to the type of film (monolayer or multilayer).
    [0188]
    [0189] In a particular embodiment of the method of the invention, the AE and / or the active substance are added to the composition of a) in the form of a concentrate or masterbatch selecting the most suitable matrix according to its melting point, polarity and viscosity. So, in a
    [0190] preferred embodiment, the concentrate or masterbatch AE is prepared in PS, preferably in PS1, and / or the concentrate or masterbatch of active substance is prepared in PS or in EMP, preferably in PS1 or EMP1. Preparing the masterbatch in these components, a very good stability of the EA and of the active substance and its homogeneous distribution in the polymer matrix is achieved. In a particular embodiment the masterbatch comprises 15% -40% of EA or active substance, preferably 20-35%, by weight based on the weight of the masterbatch.
    [0191]
    [0192] In a particular embodiment of the method of the invention according to any one of the
    [0193] embodiment is previous, in stage b) the film is formed by coextrusion, extrusion-blowing, extrusion of double or triple bubble film, extrusion-flat film or cast, thermoforming, lamination, or molding-blowing.
    [0194]
    [0195] When the active substance is added to the polymer composition in the form of a concentrate, and the film is formed by any type of extrusion, said active substance is subjected to two extrusion processes, one for the concentrate and the other for the final film. Surprisingly, in spite of said double extrusion process, and thanks, at least, to the particular characteristics of the polymeric composition, the active substance migrates towards the surface of the film, is released and maintains its functionality.
    [0196]
    [0197] The active substance, the AE and the AdM can be added to the polymer composition by making a physical mixture in an on-line mixer, before entering the hopper of the extruder, or without making said premixing. Thus, in a particular embodiment of the method of the invention
    [0198]
    [0199]
    [0200] according to any one of the embodiments is above, the active substance is added to the plastic resin by making a physical pre-mix in a mixer conditioned in line, before being formed. In another particular embodiment, the active substance is added without making said pre-mixing.
    [0201] 5
    [0202] Finally, the fifth aspect of the invention also refers to a film obtainable by the method of the invention as defined in any one of the embodiments above. This film has excellent cutting properties and antioxidant or antimicrobial activity according to the active substance that it comprises. This film as well as the film of the first aspect of the invention can be used as a slice separator, and for preparing wraps or food containers, as indicated in the second, third and fourth aspects of the invention.
    [0203]
    [0204] Examples
    [0205] Below are detailed concrete examples of embodiment of the invention that serve to illustrate the invention without limiting the scope thereof.
    [0206]
    [0207] EXAMPLE 1: Film with antioxidant activity - EMP component
    [0208] Two monolayer films with the composition indicated in Table 1 were prepared, where 20 components are hereinafter abbreviated as "comp.", The content ("cont.") Of each of them is given as a percentage by weight based on to the total weight of each layer (% p / pt). In the case that the film is monolayer, that% is the same as if it were given based on the total weight of the film. The EMP used was EVA.
    [0209] Table 1: Composition
    [0210]
    [0211]
    [0212]
    [0213]
    [0214]
    [0215] The production process of the film was by blown extrusion. In this process, the resin pellets are fed through a hopper to an extruder, aqd, heat and friction convert the pellets into a melt that is forced through a ring to form a bubble. The bubble is then flattened by the collapse of the calender, is pulled through the pressure rollers and transported over the free rollers to a rewinder that produces the finished film rolls.
    [0216]
    [0217] EVA2 has been purchased at the DuPont commercial house (ELVAX®265A), while the PS1 has been purchased at the Versalis commercial house (N3910). Also, the PS2 has been purchased at the Styrolution store (PS 165N / L). HIPS has been purchased at the Styrolution store (HIPS 486N). Glycerol monostearate has been purchased in the Palsgaard commercial house (Einar 204). The active substance is incorporated by means of a masterbatch that can be done in both PS1 and EVA1. In the same way, the additive AE is introduced in the process of obtaining the film through a masterbatch made in PS1. The
    [0218] masterbatch were prepared at a concentration of 30% EA or active substance (% by weight based on the total weight of the masterbatch).
    [0219]
    [0220] In the rest of the examples these compounds PS1, PS2 and EVA2 are used, and the same process of production of the film, unless otherwise indicated.
    [0221]
    [0222] In the present case, the active substance was an antioxidant, in particular it was a concentrate rich in natural tocopherols from non-GMO vegetable oil at a concentration of tocopherols of 90% of the commercial house BTSA (Nutrabiol® T90) with the following numbers CAS: 59-02-9 / 16698-35-4 / 54-28-4 / 119-13-1, and the masterbatch of antioxidant was made in PS1.
    [0223]
    [0224] 1.1.- Liberation of the antioxidant agent
    [0225] A sample of specific dimensions of each of the films under study is taken and introduced in a certain amount of methanol, to reach a given ppm, during the indicated times. After this time, the sample is analyzed by HPLC and the amount of Tocopherol released at each time is determined. For each time a sample is prepared that is analyzed at a given time, that is, a single sample is not prepared from which an aliquot is taken for each time. In this way, as many samples as programmed times have been prepared and analyzed.
    [0226]
    [0227] In this case, 150 mg of the film was introduced in 3 ml of methanol to achieve a
    [0228]
    [0229]
    [0230] 500 ppm concentration of tocopherol in the methanol extract, considering that all the tocopherol migrated to the solvent, and samples were taken in days 1, 3 and 6. The results are shown in Table 2.
    [0231]
    [0232] 5 Table 2.- Percentage of tocopherol released per day
    [0233]
    [0234]
    [0235]
    [0236]
    [0237] The results show that the film with EMP, in this case with EVA, is able to release the tocopherol as the days pass, however the film without EMP, in this case without EVA, is not able to release the tocopherol.
    [0238] 10
    [0239] 1.2.- Antioxidant activity in vitro - DPPH test
    [0240] The DPPH test allows to evaluate the ability to sequester free radicals from antioxidant substances.
    [0241]
    [0242] 15 0.1 g of film were placed in tubes containing 2 ml of DPPH solution (1,1-diphenyl-2-picrylhydrazyl) in methanol (50 mg / l). The tubes were kept in darkness and in constant agitation for 30 minutes. The absorbance of the sample was measured at 515 nm in a spectrophotometer (UV-1700 Pharma Spec, Shimadzu) using methanol as a blank to remove the absorbance of the solvent at that wavelength.
    [0243] twenty
    [0244] As the DPPH present in the sample is reduced by the antioxidants present in the film, the solution loses coloration proportional to the presence of antioxidant.
    [0245]
    [0246] 25 The antioxidant activity of the samples was expressed as the percentage of inhibition of oxidation (PI) according to the following formula:
    [0247]
    [0248]
    [0249] where Amuestra is the absorbance e a sama and conro is the absorbance of the DPPH solution. The higher the PI value, the greater the antioxidant capacity.
    [0250]
    [0251] 30 The test was carried out in triplicate. Table 3 shows the values of the mean of the
    [0252]
    [0253]
    [0254] results of the three trials.
    [0255]
    [0256] Table 3: Percentage of inhibition of oxidation
    [0257]
    [0258]
    [0259]
    [0260]
    [0261] The results show that the film with EMP, in this case with EVA, has an antioxidant activity of almost 100%, while the antioxidant activity of the film without EMP, in this case without EVA, is much lower, approximately 15%.
    [0262]
    [0263] EXAMPLE 2: Film with antioxidant activity - Multilayer
    [0264] Two trilayer films were prepared with the composition shown in Table 4.
    [0265]
    [0266] Table 4: Composition of three-layer films
    [0267]
    [0268]
    [0269]
    [0270]
    [0271] Layers A and C are the outer layers and layer B is between them (intermediate layer). Thus, layers A and C, which may be in contact with the food, comprise the antioxidant agent.
    [0272]
    [0273] The thickness of the film of the invention was 60 microns and the thickness of layer A = B = 10 microns. The thickness of the control film was 60 microns, where the thickness of the layer A = B = C = 20 microns.
    [0274] The film was obtained by a blown extrusion process as in Example 1 with the proviso that the components of each layer are fed to a different extruder and the Bonding of the layers occurs in the extrusion head before forming the bubble.
    [0275]
    [0276] 2.1.- Liberation of the antioxidant agent
    [0277] The test to determine the amount of tocopherol released by the film was carried out as explained in Example 1.1. In this case, films of dimensions 40x40 mm were introduced in 5ml of methanol to achieve a tocopherol concentration of 79.46 ppm in the methanol extract, considering that all the tocopherol migrated to the solvent, and samples were taken on days 0, 1 , 2, 3, 6, 9, 15 and 21. The results are shown in Table 5.
    [0278]
    [0279] 10 Table 5: Percentage of tocopherol released per day
    [0280]
    [0281]
    [0282]
    [0283]
    [0284] Thus, it is seen that the multilayer film (in this case three layer) of the invention, like the monolayer, is capable of releasing tocopherol as the days pass.
    [0285]
    [0286] 15 This film has excellent cutting properties (resistance to traction in machine direction> 30MPa and in transverse direction> 20MPa and elongation at break in machine direction> 40% and in transverse direction> 45%) which makes it ideal for be used as interleaver in slicing machines that work at cutting speeds much higher than 650 cuts / minute achieving excellent product stacking without 20 burrs or irregular cuts. The cutting properties were characterized following the ISO 527-3
    [0287]
    [0288] 2.2.- Antioxidant activity in vitro - TROLOX Test
    [0289] The TROLOX test allows to evaluate the capacity to sequester free radicals of the 25 antioxidant substances. This test was carried out in the following way:
    [0290]
    [0291] The film of dimensions 110 mm x 110 mm is cut into small pieces, weighed with accuracy and crushed with ultraturrax. Mix with 20 ml of methanol in 50 ml falcon tubes and vortex for 3 minutes and allow to incubate at room temperature for 3 hours. Subsequently, it is re-vortexed for 3 minutes and centrifuged at 2,300 rpm for 10 minutes. The supernatant is collected for the colorimetric determination.
    [0292] 5
    [0293] Before performing the colorimetric determination, a dilution test of the sample with DPPH is performed to know in which range it will enter the calibration. Five serial dilutions are also made starting from the initial dilution and 0.9 ml of sample are taken on each dilution, on which 0.9 ml of DPPH is added. The samples are incubated for 2.5 h 10 in darkness and finally measured at 515 nm.
    [0294]
    [0295] The calibration line is made with Trolox (0-60 ^ M) and the results are shown in Table 6 as meqTROLOX / 100 g of sample.
    [0296]
    [0297] 15 Table 6: Antioxidant capacity
    [0298]
    [0299]
    [0300]
    [0301]
    [0302] Thus, it is seen that the multilayer film (in this case three layer) of the invention, presents antioxidant activity since it is capable of consuming 215 meq of TROLOX per 100 g of sample while the control film is not able to consume any meq of the substance.
    [0303] twenty
    [0304] 2.3.- Antioxidant activity in vivo - Test Challenge
    [0305] The three-layer film of the invention with tocopherol as active substance which, according to the studies carried out in vitro From section 2.2 I present antioxidant activity, it was used to evaluate the impact it has on the quality of a meat product (salami) during its useful life.
    [0306]
    [0307] A chopped cured product (salami) was used to ensure the uniformity of the product. The product is packaged to the ford using as slicer separator (interleaver) the antioxidant film or the control film of Table 4.
    [0308] 30
    [0309] An accelerated life study was conducted in order to obtain a validation of the activity of the films. The product was stored at room temperature (22 ° C) to accelerate the test, since the product should be stored in refrigeration at 8 ° C, in displays under commercial lighting conditions. During the useful life of the product, the
    [0310]
    [0311]
    [0312] Perform sampling at days 1, 6, 13, 20, 27 and 41 to determine the evolution of product quality. In particular, the oxidation levels (TBARS assay) and their organoleptic characteristics were analyzed.
    [0313]
    [0314] 5 The TBARS index (substances reactive to thiobarbituric acid) was used as an indicator of the lipid oxidation level of salami. The TBARS index was determined following an adaptation of the method proposed by Buege and Aust (Buege, J. A. and Aust, S. D. (1978) Microsomal Lipid Peroxidation. Methods in Enzymology, 52: 302-310). 2 g of salami were homogenized for 30 s in a ULTRA-TURRAX® mixer using 20 ml of 10 solution of 1.2 M HCl, 0.1% (w / v) of propyl gallate and 0.1%, p / v of EDTA. The homogenate was centrifuged at 5,000 rpm for 10 min. The supernatant was injected into a Futura System continuous flow analyzer (Alliance Instruments). A solution of 1.2 M HCl, 0.327% thiobarbituric acid and 0.5% Brij-35 was also injected into the system. The system consists of a 90 ° C bath that accelerates the reaction and a colorimeter set at 531 15 nm that allows detecting the reaction product, malondialdehyde (MDA). The calibration line was obtained using 1,1,3,3-tetraethoxypropane as standard. The results were expressed as mg MDA / kg salami.
    [0315]
    [0316] The size of the interleaver it was 90x90 mm and the weight of the 7 g salami slices. twenty
    [0317] The results obtained were those shown in Table 7.
    [0318]
    [0319]
    [0320]
    [0321]
    [0322] During the test, it was possible to detect the antioxidant effect of the three-layer film of the invention in the salami. Samples of sliced salami packaged using the film of the three-layer invention as interleaver and preserved at room temperature (22 ° C) under lighting conditions (870 lux on average, 12 h light 12 h dark) showed lower values of oxidation during the useful life of the product that the control batch samples. Significantly lower TBARS values (mg MDA / kg product) were detected in the batches with the film of the three-coat invention compared to the control batch from day 13 of conservation until the end of the study (t41).
    [0323] 5
    [0324] A comparison between lots, I detect a less rancid aroma and flavor in the batches with the film of the three-layer invention compared to the control batch. On the other hand, no differences were detected in the color of the product between the types of film studied (instrumental and sensory measurement). From the results obtained, it can be concluded that under the conditions of the test 10 (product, environmental conditions, batches of manufacture) the film of the three-coat invention allowed to delay the lipid oxidation of the salami.
    [0325]
    [0326] EXAMPLE 3: Film with antibacterial activity - Component EVA
    [0327] Three monolayer films were prepared with the composition specified in Table 8.
    [0328] fifteen
    [0329] Table 8: Composition
    [0330]
    [0331]
    [0332]
    [0333]
    [0334]
    [0335]
    [0336]
    [0337]
    [0338] The antibacterial agent used was Mirenat® D from the commercial company VEDEQSA, which has between 53-57% ethyl Na-dodecanoyl-L-argininate hydrochloride (LAE-Cl) (CAS No. 60372-77-2). The Mirenat® D was incorporated into the film through a masterbatch performed 5 in the EVA1 component. EVA1 was purchased at the DuPont commercial house (ELVAX®240A).
    [0339] Tween80® was acquired in the commercial house Quimidroga (Polisorbato80.PS80). The rest of the components are the same as that specified in Example 1.
    [0340]
    [0341] 3.1.- Release of the AB agent
    [0342] 10 A sample of specific dimensions of each of the films under study is taken and introduced in a certain amount of water, to reach a given ppm, during the indicated times. After this time the sample is analyzed by HPLC and the amount of LAE released at each time is determined. Each time corresponds to a sample, that is, as many samples are analyzed as programmed times.
    [0343] fifteen
    [0344] In this case, 100 mg of film was introduced in 15 ml of water, which resulted in 117 ppm of LAE, considering that all the LAE migrated to the solvent, and samples were taken on days 0, 1,2, 3, 6, 9, 15 and 28. The results are shown in Table 9.
    [0345]
    [0346] 20 Table 9: Percentage of LAE released per day
    [0347]
    [0348]
    [0349]
    [0350]
    [0351] The presence of the EMP, in this case EVA, facilitates the release of the LAE, reaching a release percentage of more than 80%, while if there is no EMP, in this case EVA,
    [0352]
    [0353]
    [0354] in the formulation the maximum percentage of liberation is only 50%
    [0355]
    [0356] 3.2.- Antimicrobial activity
    [0357] The antimicrobial activity of the films was evaluated using the broth method that allows to determine the antimicrobial activity in conditions in vitro The culture broth method allows to monitor the behavior of the microorganisms under study during storage under refrigeration conditions. Briefly, culture broth tubes (MRS / TSBYE) are inoculated with the selected strains at 2 levels (101 and 105 CFU / g) and a film sample is placed in these tubes to study the inhibitory effect of the films. The weight of the sample to be added will be determined in function of the equivalent ppm of LAE (mg LAE / kg culture broth) that you wish to study. The samples are stored at a temperature of 8 ° C for a period of 35 days or until the stationary phase of growth is reached.
    [0358]
    [0359] These methods were used to evaluate the antibacterial activity of AB (antibacterial) films against lactic acid bacteria (BAL) and / or against Listeria monocytogenes.
    [0360] BAL were used as indicators of the deterioration of cooked meat products. Specifically, BAL isolated from deteriorated cooked meat products were used
    [0361] (Lactobacillus sakei Y Leuconostoc mesenteroides). On the other hand, L. monocytogenes It was used as an objective pathogen, due to its prevalence in meat products. The strains used were also isolated from meat products.
    [0362]
    [0363] In this case, the test was carried out with L. monocytogenes and with 117 ppm of LAE. As can be seen in Figure 1, the film of the present invention (with EVA) shows bactericidal activity at both a concentration of 101 bacteria (Fig. 1A) and a concentration 105 (Fig. 1B). The study was conducted at two concentrations, a very high and unhealthy for humans, which could correspond to a peak of contamination, and another lower, to demonstrate the antimicrobial capacity of the films regardless of the concentration of microorganism present. With this example, it can be observed that although a peak of Listeria very high the film of the invention would be able to reduce it to minimum values, being able to avoid future problems of intoxication.
    [0364]
    [0365] Figure 1 also shows that the EMP component is essential for the film to show such bactericidal activity since with the film with no EMP the bacterial growth is the same as the control independently of the initial concentration of Listeria
    [0366]
    [0367]
    [0368] EXAMPLE 4: Film with antibacterial activity - Component PS
    [0369] Three monolayer films were prepared with the composition specified in Table 10, as indicated in Example 3. In the film without PS, low density polyethylene (LDPE) (from Dow Chemical, grade LDPE410E) was used instead of .
    [0370] 5
    [0371] Table 10: Composition
    [0372]
    [0373]
    [0374]
    [0375]
    [0376] 4.1.- Release of agent AB
    [0377] 10 The test was carried out as explained in section 3.1, taking samples on the days indicated in Table 11. The results obtained appear in Table 11.
    [0378]
    [0379]
    [0380] Table 11: LAE release results
    [0381]
    [0382]
    [0383]
    [0384]
    [0385] The presence of the PS facilitates the release of the LAE reaching a release percentage of almost 80%, while if there is no PS the maximum percentage of release is only about 40%.
    [0386]
    [0387] 4.2.- Antimicrobial activity
    [0388] The test was carried out as in section 3.2, with L. monocytogenes and with 117 ppm of LAE.
    [0389] 10
    [0390] As shown in Fig. 2, the film with PS (rhombus) has a bactericidal effect, while the film with LDPE (triangle) has no effect whatsoever, since the bacterial growth is the same as with the film control (square), regardless of the initial concentration of Listeria (comparison panels A and B).
    [0391] fifteen
    [0392] Thus, it is essential that the layer with the active substance comprises PS.
    [0393]
    [0394] EXAMPLE 5: Film with antibacterial activity - Component AE
    [0395] Three monolayer films were prepared with the composition specified in Table 12:
    [0396] twenty
    [0397] Table 12: Composition
    [0398]
    [0399]
    [0400]
    [0401]
    [0402]
    [0403]
    [0404]
    [0405]
    [0406] 5.1.- Release of the AB agent
    [0407] The test was carried out as explained in section 3.1, taking samples on the days indicated in Table 13. The results obtained appear in Table 13.
    [0408] 5
    [0409] Table 13: LAE release results
    [0410]
    [0411]
    [0412]
    [0413]
    [0414] The presence of the AE facilitates the release of the LAE reaching a release percentage of almost 80%, while if there is no AE the maximum percentage of release is only 10 approximately 7%.
    [0415] 5.2.- Antimicrobial activity
    [0416] The test was carried out as in section 3.2, with 117 ppm of LAE and with L.
    [0417] monocytogenes at a concentration of 102 (Fig. 3.A) or 106 (Fig. 3.B) or with BAL at a concentration of 105 (Fig.4).
    [0418]
    [0419] As to Listeria, As shown in Fig. 3, the film with AE (diamond) has a bactericidal effect, while the film without AE (triangle) has no effect whatsoever, since the bacterial growth is the same as with the film control (square), regardless of the initial concentration of Listeria (comparison panels A and B).
    [0420] As for BAL, as shown in Fig.4, the film with AE (diamond) has a bacteriostatic effect compared to the control film (square), while the film without AE (triangle) has no type of effect against BAL.
    [0421]
    [0422] EXAMPLE 6: AdM Component
    [0423] Three monolayer films with the following composition were prepared (Table 14), as indicated in Example 3.
    [0424]
    [0425] Table 14: Composition
    [0426]
    [0427]
    [0428]
    [0429]
    [0430]
    [0431]
    [0432]
    [0433] 6.1.- Release of the active substance
    [0434] The test to determine the amount of LAE released by the film was carried out as explained in Example 3.1. In this case, 100 mg of film was introduced into 25 ml of water such that it resulted in 117 ppm of LAE and samples were taken on days 1, 2, 3, 6, 9, 15 and 20. The results are shown in Table 15.
    [0435]
    [0436] In order to evaluate the role of AdM in films subjected to a cleaning process (for example with ethanol to sterilize the surface of the sample), two samples were prepared 10 more like the previous ones, but they were subjected to a cleaning process Chemistry with ethanol before introducing them into the water, where they were maintained one day before determining the amount of LAE released by HPLC. The values obtained for these washed samples appear between parentheses in Table 15.
    [0437]
    [0438] 15 Table 15: Percentage of LAE released
    [0439]
    [0440]
    [0441]
    [0442]
    [0443] As seen in Table 15, there are no significant differences in the release of LAE in the presence or absence of AdM. However, after submitting the samples to a chemical cleaning process with ethanol (see data in parentheses in Table 15), it is observed that the absence of AdM causes the loss of 31% of the active substance, while in the film with AdM only loses 14% of said substance (after cleaning 29% is released)
    [0444]
    [0445]
    [0446] LAE when no cleaning was released 60% in the absence of AdM and 43% in the presence of AdM). Thus, AdM is shown to act as a protective physical barrier against the elimination or loss of active substance.
    [0447]
    [0448] Furthermore, in Table 15 it is seen that the AdM prevents the migration of the active substance to be too fast in the first days. This is a great advantage since the first days are the most critical for microbiological control, since in them the active substance begins to act against bacteria during its latency period.
    [0449]
    [0450] 6.2.- Antimicrobial activity
    [0451] The test was carried out as in section 3.2, with 117 ppm of LAE and with L.
    [0452] monocytogenes at a concentration of 105 with the exception that the surfaces of the films were cleaned with ethanol.
    [0453]
    [0454] As shown in Fig. 5, the film with AdM (diamond) has a bactericidal effect, while the film without AdM (triangle) has a bacteriostatic effect comparing it with the control film (square) due to the elimination of part of the LAE during the chemical cleaning process of the surface.
    [0455]
    [0456] EXAMPLE 7: Film with antifungal activity
    [0457] The antifungal activity in vitro of the films developed was studied in front of Penicillium
    [0458] commune by the agar diffusion method. It is a qualitative method that allows to determine the antifungal activity of the films by the appearance of a halo of inhibition or absence of growth on the contact surface between the film and a petri dish with agar inoculated with the target microorganism.
    [0459]
    [0460] Briefly, in the agar diffusion method, a base medium of contrast is used on which a layer of soft culture medium inoculated with a cocktail of the microorganism targeted by the study is deposited. Once the medium is solidified, a piece of film with dimensions of 100 mm x 100 mm is deposited and the plate is incubated (in the present case for 11 days at 23 ° C). The positive antifungal activity results in a halo of inhibition or absence of mold growth on the surface or around the deposited film.
    [0461]
    [0462] In the present test the following films were used, whose composition appears in Table 16.
    [0463] Table 16.- Composition
    [0464]
    [0465]
    [0466]
    [0467]
    [0468] As shown in Fig. 6, in the control film (without fungicidal agent, panel A) the mold grows throughout the plate, while in the films according to invention 1 (with Glyceride 8-10 5 atoms C, panel B ) and 2 (with LAE, panel C) the mold does not appear on the surface of the plate in contact with the film of the invention. Thus, it is demonstrated that the film of the invention has fungistatic or fungicidal activity, that is, it is capable of slowing down or inhibiting the growth of the mold under study. Note that there is a contaminating fungus (brownish) that also does not grow on the surface of the plate in contact with the film of the invention.
    [0469] 10
    [0470]
    [0471]
    4
    权利要求:
    Claims (1)
    [0001]
    1. - Polystyrene film for applications in contact with food products characterized in that it comprises at least one layer comprising:
    5 - 60-75% (w / w) crystal polystyrene (PS);
    - 10-35% (p / pt) ethylene copolymer with polar monomers (EMP) with a comonomer content of 15-40% p / pEMP;
    - an active substance selected from the group consisting of an antioxidant agent and an antimicrobial agent;
    10 - 0.5% -2% (p / pt) migration agent (AdM);
    - 0-15% (p / pt) of emulsifying agent (AE) with an HLB greater than 8, being 3-15% when the active substance is an antimicrobial agent,
    where the relation PS / (EMP + AE) is between 1.2 and 7.5.
    2. Film according to the previous claim, where the content of PS is 64-70% (w / w), the content of EMP is 16-30% (w / w) and the ratio PS / ( EMP + AE) is between 1.5 and 4.4.
    3. Film according to any one of the preceding claims, wherein EMP is selected from the group consisting of ethylene vinyl acetate copolymer (EVA), ethylene methyl acrylate copolymer (EMA), ethylene ethyl acrylate copolymer (EEA), ethylene butyl acrylate copolymer (EBA) and mixtures thereof.
    4. - Film according to the preceding claim, wherein EMP is EVA.
    25
    5. Film according to any one of the preceding claims, wherein PS is the only polystyrene of said at least one layer.
    6. - Film according to any one of the preceding claims, wherein PS 30 comprises PS with an MFI (Melt Flow Index) between 10-40 g / 10 min at 200 ° C and 5 Kg (PS1) and / or PS with an MFI of 2-5 g / 10 min at 200 ° C and 5 Kg (PS2).
    7. - Film according to any one of the preceding claims, wherein EMP comprises EMP with an MFI of between 15-50 g / 10 min at 190 ° C and 2.16 Kg (EMP1) and / or EMP 35 with an MFI of 2-5 g / 10 min at 190 ° C and 2.16 Kg (EMP2).
    8. Film according to any one of the preceding claims, wherein the content of the active substance in said at least one layer is 0.5-6% (w / w).
    9. Film according to any one of the preceding claims, wherein the emulsifying agent 5 is selected from the group consisting of polyethylene glycol 400 dioleate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene monostearate (20). ) sorbitan, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene sorbitan monooleate, ethylene polyoxide stearate 40, sorbitan monolaurate and mixtures thereof.
    10
    10. Film according to the preceding claim, wherein the emulsifying agent is polyoxyethylene sorbitan monooleate.
    11. Film according to any one of the preceding claims, wherein the active substance is an antioxidant agent and the content of the emulsifying agent is 0-5%, preferably 0-3%.
    12. - Film according to any one of the preceding claims, wherein the substance is an antioxidant agent and this is selected from the group consisting of tocopherol, green tea extract, olive leaf extract, rosemary extract, seed extract of grape, coffee extract, dehydrated acerola, extract of dtricos with a concentration of flavonoids greater than 45%, tomato extract with a concentration of lycopene greater than 5%, fruit extract, thymol and mixtures thereof.
    13. Film according to the preceding claim, wherein the antioxidant agent is tocopherol or green tea extract.
    14. - Film according to any one of claims 1-10, wherein the active substance is an antimicrobial agent and the content of the emulsifying agent is 3-12%, preferably 5-10%.
    15. Film according to any one of claims 1-10 and 14, wherein the active substance is an antimicrobial agent and this is an antibacterial agent selected from the group consisting of anhydrous sodium acetate, nisin, lysozyme, Ag and its compounds. salts, Zn and its salts, ethyl Na-dodecanoyl-L-arginate (LAE), salts thereof, LAE hydrochloride, glycolipid biosurfactants and mixtures thereof.
    16. - Film according to the preceding claim, wherein the antibacterial agent is LAE hydrochloride.
    17. - Film according to any one of claims 1-10 and 14, wherein the active substance is an antimicrobial agent and this is an antifungal agent selected from the group consisting of C8-C10 mono-, di-, tri-glycerides , monolaurin, nisin, lysozyme, glycolipid biosurfactants, LAE and its salts, LAE hydrochloride and mixtures thereof.
    18. Film according to the preceding claim, wherein the antifungal agent is C8-C10 mono-, di-, tri-glycerides or LAE hydrochloride.
    19. Film according to any one of the preceding claims, wherein the migration agent is selected from the group consisting of fatty acid amides, fatty acid esters, metal stearates, waxes and mixtures thereof.
    fifteen
    20. Film according to the preceding claim, wherein the migration agent is selected from the group consisting of erucamide, oleamide, glycerol monostearate (MG), zinc stearate, waxes and mixtures thereof, preferably MG and / or erucamide.
    twenty
    21. Film according to any one of claims 1-20, which is monolayer.
    22. Film according to any one of claims 1-20, which is multilayer.
    23. Film according to the preceding claim, wherein the film comprises at least one layer as defined in any one of claims 1-20 and at least one layer without active substance.
    24. - Film according to claim 23, comprising three layers, wherein each of the two outer layers is a layer as defined in any one of claims 1-20, and wherein the intermediate layer is a layer without substance.
    25. Film according to claim 23 or 24, wherein the layer without active substance comprises crystal polystyrene and high impact polystyrene.
    35
    26. - Film according to the preceding claim, wherein the layer without active substance comprises 60-90% glass polystyrene and 10-40% high impact polystyrene.
    27. - Film separating slices characterized in that it comprises a film according to any one of claims 1-26.
    28. - Wrap or food packaging characterized in that it is made from or comprises a film according to any one of claims 1 to 26.
    29. Use of a film according to any one of claims 1-26 for the packaging of food or as a separator of food slices.
    30. Method for producing a film according to claim 1 characterized in that it comprises the following steps:
    15 a) provide a polymeric composition comprising:
    - 60-75% (p / pt) of PS,
    -10-35% (p / pt) of EMP with a comonomer content of 15-40% p / pEMP,
    - an active substance selected from the group consisting of an antioxidant agent and an antimicrobial agent,
    20 - 0.5% -2% (p / pt) of AdM,
    - 0-15% (p / pt) of AE with an HLB greater than 8, being 3-15% when the active substance is an antimicrobial agent,
    where the ratio PS / (EMP + AE) is between 1.2 and 7.5; Y
    b) forming a film with at least one layer comprising the polymer composition of a). 25
    31. - The method of the preceding claim, wherein the emulsifying agent and the active substance are added to the composition of a) in the form of a concentrate or masterbatch.
    32. - The method according to claim 30 or 31, wherein the film is formed by co-extrusion, extrusion-blowing, extrusion of double or triple bubble film, flat extrusion or cast, thermoforming, lamination, or molding-blowing.
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    同族专利:
    公开号 | 公开日
    WO2019086734A1|2019-05-09|
    AU2018359723A1|2020-05-14|
    EP3702406A1|2020-09-02|
    EP3702406A4|2021-07-28|
    ES2711023B2|2019-10-17|
    CA3084724A1|2019-05-09|
    AR113558A1|2020-05-20|
    JP2021500455A|2021-01-07|
    BR112020008373A2|2020-11-03|
    UY37946A|2019-05-31|
    RU2020116445A|2021-11-29|
    US20200269557A1|2020-08-27|
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    ES201731261A|ES2711023B2|2017-10-27|2017-10-27|Polystyrene active film|ES201731261A| ES2711023B2|2017-10-27|2017-10-27|Polystyrene active film|
    UY0001037946A| UY37946A|2017-10-27|2018-10-23|ACTIVE POLYSTYRENE FILM|
    AU2018359723A| AU2018359723A1|2017-10-27|2018-10-24|Active polystyrene film|
    BR112020008373-9A| BR112020008373A2|2017-10-27|2018-10-24|polystyrene film for applications in contact with food products, their use and method for their production, wrapping or packaging for food.|
    PCT/ES2018/070691| WO2019086734A1|2017-10-27|2018-10-24|Active polystyrene film|
    JP2020523387A| JP2021500455A|2017-10-27|2018-10-24|Active polystyrene film|
    EP18874741.4A| EP3702406A4|2017-10-27|2018-10-24|Active polystyrene film|
    CA3084724A| CA3084724A1|2017-10-27|2018-10-24|Active polystyrene film|
    US16/759,395| US20200269557A1|2017-10-27|2018-10-24|Active polystyrene film|
    RU2020116445A| RU2020116445A|2017-10-27|2018-10-24|ACTIVE POLYSTYRENE FILM|
    ARP180103120A| AR113558A1|2017-10-27|2018-10-26|ACTIVE POLYSTYRENE FILM|
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