EP3962740A1

EP3962740A1 - Method for producing a multi-layer composite film, multi-layer composite film and use thereof

Info

Publication number: EP3962740A1
Application number: EP20723394.1A
Authority: EP
Inventors: Jürgen Michael Schiffmann
Original assignee: Kuhne Anlagenbau GmbH
Current assignee: Kuhne Anlagenbau GmbH
Priority date: 2019-05-03
Filing date: 2020-04-30
Publication date: 2022-03-09
Also published as: WO2020225140A1; DE102019111460A1; US20220203658A1; BR112021021757A2

Abstract

The present claim relates to a method for producing a multi-layer composite film comprising the step of co-extruding at least three layers (a), (b) and (c), from which the layer (a) forms an outer surface of the composite film; the layer (c) forms a surface of the composite film that comes into contact therewith or faces the product to be packaged; and the layer (b) is arranged between the layer (a) and the layer (c). The method also comprises the step of bi-axially drawing the co-extruded composite film. Layer (a) contains a thermoplastic resin or is made thereof. Layer (b) contains a polyvinyl chloride (PVdC)- resin or is made thererof. Layer (c) contains a resin, preferably sealable, in particular a heat-sealable resin or is made therefrom. As a result, there is no cross-linking of the composite film by means of radio-active radiation, in particular by means of beta, gamma, x-ray and/or electron radiation, during the production of the composite film and after.

Description

description

Process for the production of a multilayer composite film, multilayer

Composite film and its use

The invention relates to a method for producing a multilayer composite film according to claim 1, a multilayer composite film according to claim 10 or 11 and the use of the composite film according to claim 20. Prior art

Multi-layer composite films are known which provide a polyamide resin as the main resin and EVOH as a gas barrier layer, the properties required for the intended use, for example as heat-shrinkable packaging film for food, being achieved exclusively by means of the raw material combinations used. The use of higher percentages of the raw materials polyamide, EVOH and PET leads to relatively stiff films. In addition, especially when using PA and EVOH, the tendency of these raw materials to recrystallize can impair the dimensional stability of the film. The use of EVOH as a layer component also has the disadvantage that its barrier properties against oxygen permeation decrease over time due to the action of permeable moisture from the outside and inside. Therefore, to maintain a sufficient oxygen barrier, the EV OH-containing layer must be protected by embedding in layers with a good water vapor barrier function, for example in the form of a sandwich arrangement, which disadvantageously increases the number of layers required and the complexity of the overall composite . In addition, composite films that use polyamide in one or more layers have the disadvantage of undesirable cold or post-shrinkage. The use of polyamide in the outer layer can also lead to an undesirable tendency to roll, known as curling. For example, the publication DE 10 2006 046 483 A1 discloses a multi-layer food casing or film for food packaging in which a central EVOH-based gas barrier layer is embedded in two polyolefin layers as a water vapor barrier and which has a PET layer for the purpose of heat resistance, puncture resistance and shrinkage .

For example, document EP 1 857 271 B1 disclose a 7-layer film and document DE 10 2006 036 844 B3 a food casing or film for food packaging in which the EVOH layer is embedded between two PA layers , which in turn are embedded between two PO layers, and in which the outer layer consists of PET.

On the other hand, multilayer composite films are known which are crosslinked by radiation and use PVdC as a barrier material. The radiation crosslinking integrated or downstream in the film production process through radioactive irradiation or irradiation with electrons achieves essential properties such as sufficiently high shrinkage, good puncture resistance and heat resistance, which prevent the oxygen, gas and aroma properties originally already present in PVdC - best supplement. As the following table 1 shows, the use of radiation-crosslinked PVdC can result in cold shrinkage compared to other conventional ones

Foils are completely avoided.

Table 1: Cold shrinkage, measured after 24 hours in water at a temperature of 20 ° C, with conventional multilayer films based on EVOH vs. Radiation-crosslinked PVdC (MD = machine direction; TD = cross direction) (ASTM 2732)

However, radiation crosslinked composite films often have the disadvantage that, due to the interaction of the raw materials and the radiation crosslinking, the appearance is not satisfactory in terms of cloudiness, gloss and coloring (brown or yellowish tint). The haze in films based on radiation-crosslinked PVdC is significantly increased compared to other conventional films, as Table 2 below shows.

Table 2: Haze, measured with conventional multilayer films based on EVOH vs. radiation crosslinked PVdC (ASTM D1003)

In addition, the further processing of the radiation-crosslinked composite films is limited with a view to the relatively low or limited number of cycles on further processing machines due to the sub-optimal heat resistance and the sometimes too low rigidity of the film, as Table 3 below shows.

Table 3: Stiffness, measured as the modulus of elasticity in conventional multilayer films based on EVOH vs. Radiated PVdC (data in MPa; MD = machine direction; TD = transverse direction) (DIN EN ISO 527)

The use of a radiation cross-linked film with PVdC as a barrier layer also has the fundamental disadvantage that the oxygen barrier to be achieved is fundamentally lower than that which can be achieved with EVOH. In contrast, the oxygen barrier in films with PVdC remains stable over the long term, regardless of external influences and regardless of the influence of moisture, as Table 4 below shows.

Table 4: Oxygen permeability at 20 ° C, measured on various barrier plastics (according to Kyoichiro; from: Joachim Nentwig, Kunststoff-Folien, 3rd edition, 2006, Carl Hanser Verlag; Table 26)

However, incorrect or poorly metered beam crosslinking can lead to a disadvantageous decrease in the sealability of the film. With regard to EVA in particular, the sealability of the film can be completely lost due to radiation cross-linking. In addition, radiation crosslinked films cannot be recycled, but have to be disposed of in a laborious manner. Object of the invention

It is therefore an object of the present invention to provide a composite film and a method for its production which avoid as far as possible at least one of the deficiencies discussed above in the composite films known from the prior art. In particular, it is an object to provide a composite film which has at least one, preferably several of the following properties: high shrinkage, high further processability (high cycle rates), high puncture resistance, high heat resistance, good optical properties in terms of low haze and / or a low color cast, recyclability and a long-term, uninfluenceable or stable oxygen barrier. In particular, the presence of a slight cloudiness of the composite film is advantageous.

Disclosure of the invention

The object is achieved by the method according to the invention according to claim 1.

For the first time, a method for producing a multilayer composite film is proposed, the method comprising at least the following steps:

a step of co-extruding at least three layers (a), (b) and (c) of which

the layer (a) forms a surface of the composite film to the outside; the layer (c) forms a surface of the composite film which faces or comes into contact with an item to be packaged; and the layer (b) is arranged between the layer (a) and the layer (c); and

a step of bi-axially stretching the composite film co-extruded in this way; wherein layer (a) contains or consists of a thermoplastic resin; wherein the layer (b) contains or consists of a polyvinylidene chloride (PVdC) resin; wherein the layer (c) contains or consists of a resin, preferably a sealable, in particular heat-sealable resin;

wherein the thermoplastic resin of layer (a) contains or consists of a polyester, preferably a polyethylene terephalate (PET), a polylactic acid (PLA), a polyamide (PA), or any mixture thereof; and wherein any crosslinking of the composite film by means of radioactive radiation, in particular by means of beta, gamma, X-ray and / or electron radiation, is omitted during the production of the composite film and / or afterwards.

The use of non-radiation cross-linked composite films with PVdC has the advantage over certain other materials used as oxygen barriers that the barrier property against water or water vapor and especially against oxygen is constant over a long period of 3 to 6 months or more. As a result, the stability of the barrier over time is improved compared to the use of an ethylene-vinyl alcohol copolymer (EVOH) in particular as a barrier material in an inner or intermediate layer, which is a considerable advantage especially when the packaged goods, in particular a food, have a long shelf life.

The thermoplastic resin of layer (a) of the composite film according to the invention contains or consists of a polyester, preferably a polyethylene terephthalate (PET) or a polylactic acid or a polylactide (PLA), a polyamide (PA), or any mixture thereof.

The provision of polyamide in layer (a) ensures high heat resistance, high strength, in particular puncture resistance, and sufficient shrinkage. These advantages are achieved in particular if the layer (a) contains PET instead of the polyamide or consists of PET. By providing PET instead of PA in layer (a), the cold shrinkage or post-shrinkage that can occur when using PA as a layer component due to post-crystallization is effectively reduced or even avoided (see table below 9). Unlike PA, PET is brought into a crystallized state during bi-axial stretching as part of the manufacturing process. In addition, the use of PET in layer (a) effectively prevents a tendency to curl, as is usual with partially crystallized PA. PA in the outer layer is also characterized by an excellent printability of the composite film. In addition, compared to polyolefin-based raw materials such as PE or PP, PLA offers significantly better barrier protection, especially after stretching, especially after biaxial stretching. Furthermore, PA and PLA are far superior to polyolefin-based raw materials in terms of processability and recyclability.

Furthermore, in addition to the heat resistance of the outer layer (a) when using the raw materials provided according to the invention for the layer (a), polyester, preferably a polyethylene terephthalate (PET), a polylactic acid (PLA), a polyamide (PA), or any mixture thereof, is also used increased rigidity and thus also improved process stability during stretching, more precisely in the biaxial stretching of the bubble-shaped film. And because of the sufficient rigidity of the composite film according to the invention, higher cycle rates and thus improved processability (bagging) can be achieved. The improved rigidity of the film according to the invention is from the following

Table 5 can be seen.

Table 5: Stiffness, measured as the modulus of elasticity of the multilayer film according to the invention in comparison to conventional multilayer films based on EVOH and radiation crosslinked PVdC (data in MPa; MD = machine direction; TD = transverse direction; * = composite film according to the invention according to Table 10, Example 1) (DIN

EN ISO 527)

When using the raw materials according to the invention in layer (a), the raw material-related heat resistance or the high Vicat softening temperature and the associated high rigidity even at high temperatures, combined with the fundamentally higher rigidity of the raw materials used compared to the in Radiation-crosslinked films used raw materials, surprisingly a significantly higher processability (cycle rates) compared to comparable radiation-crosslinked composite films, as can be seen from Table 6 below.

Table 6: Comparison of the number of cycles for E V OH-based and PVDC-based films (bagging or production of bags) (data in cycles per minute; * = composite film according to the invention according to Table 10, Example 1)

The Vicat softening temperature according to DIN EN ISO 306, in conjunction with the rigidity, plays a decisive role in the further processing of the films produced, since in the subsequent processes, such as B. the bagging, often high temperatures act on the foils and these become very soft at a lower Vicat softening temperature and can therefore only be further processed with moderate cycle rates despite good heat resistance (with regard to sticking). This is essentially due to the insufficient rigidity of the film at elevated temperatures.

This occurs especially with radiation crosslinked films, since the main raw material (80 to 90% layer content) is EVA and this raw material has an extremely low Vicat softening temperature. The EVA types used have a V icat softening temperature which is usually between 45 and 70 ° C, but not more than 85 ° C. Ideally, raw materials are therefore used specifically in layer (a) which have a Vicat softening temperature which is at least above 100 ° C. (see Table 7 below).

Table 7: Vicat softening temperature (VST) of different raw material types (data in ° C; DIN EN ISO 306)

Furthermore, the composite film according to the invention has a lower haze or a higher transparency and a higher gloss and thus improved optical properties compared to radiation-crosslinked composite films, as can be seen from Table 8 below.

Table 8: Haze, measured on the multilayer film according to the invention in comparison with conventional multilayer films based on EVOH and radiation-crosslinked PVdC; (MD = machine direction; TD = transverse direction; * = composite film according to the invention according to Table 10, Example 1) (ASTM D1003)

The composite film according to the invention can have a sealing layer which, despite or precisely because of the temperature introduced from the outside, begins to seal earlier than the outer layer in order to ensure that the film to be welded seals inside before it sticks to the outer layer on the sealing tool (sealing bar) .

According to the invention, by completely dispensing with radiation cross-linking, the risk of incorrect or poorly dosed radiation cross-linking is excluded. This avoids the risk of a radiation-related deterioration in the sealability of the composite film. In addition, the fact that there is no radiation crosslinking means that the composite film remains recyclable. Advantageous embodiments are the subject of the dependent claims.

In a preferred embodiment, the thermoplastic resin of layer (a) of the composite film according to the invention can be a material with a melting temperature or a melting point of 170 ° C. or higher, preferably 175 ° C. or higher, preferably 180 ° C. or higher.

With the choice of a resin with such a high melting temperature or such a high melting point as a layer component of layer (a), high cycle rates can be achieved due to the higher heat resistance or due to the significantly higher Vicat softening temperature (DIN EN ISO 306) Manufacturing can be achieved. In this case, despite very high temperatures on the sealing bar, sticking of the film to the sealing bar or of films or film parts to one another is advantageously avoided.

Table 9: Cold shrinkage, measured after 24 hours in water at a Tempe temperature of 20 ° C, in the multilayer film according to the invention compared to conventional multilayer films based on EVOH and radiation-crosslinked PVdC (data in%; MD = machine direction; TD = transverse direction; * = composite film according to the invention according to Table 10, Example 1) (ASTM 2732)

Particularly when layer (a) contains or consists of polyamide or PET, and neither the composite film nor individual layers are radiantly crosslinked, it has surprisingly been found that the composite film has excellent transparency or low haze and excellent gloss.

In a further advantageous embodiment, the thermoplastic resin of layer (a) can have a density of 0.94 g / cm ³ or more, preferably 0.96 g / cm ³ or more, preferably between 0.96 and 2 g / cm ³ , in particular between 0.96 and 1.5 g / cm ³ . If a resin or polymer with a high density, in particular PET or a PA with a correspondingly high density, is used as layer component for layer (a), a high puncture resistance of the entire composite film and high heat resistance of layer (a) are advantageously achieved. In addition, a resin from the material groups PA or PET with a high density in layer (a) brings about appealing optical properties, such as transparency and gloss, of the composite film. Furthermore, with such an outer layer (a) with a high density, improved further processing in the sense of high cycle rates can be ensured. In a further preferred embodiment, the thermoplastic resin of layer (a) can have a sealing temperature (measured at 1 bar, air atmosphere, 23 ° C.) which is equal to or higher than the sealing temperature of the resin of layer (c) (measured at 1 bar , Air atmosphere, 23 ° C). The thermoplastic resin of layer (a) can in particular be one of the polymer materials mentioned above for layer (a) or a mixture of at least two of these polymer materials.

By choosing a thermoplastic resin for layer (a) with a sealing temperature that is the same or higher than the sealing temperature of the resin of layer (c), it is advantageous to avoid sticking of the film to the sealing bar or of films or film parts to one another.

In a further preferred embodiment, the composite film can have a haze (ASTM D1003) of at most 15%, preferably at most 12%, preferably at most 10%, preferably at most 7%, in particular at most 5%. In this way, the desired optical properties of the composite film according to the invention are realized. Correspondingly, the visual appearance of the resulting composite film and the recognizability / testability of the goods packed with it by the buyer of the goods are improved without the packaging having to be opened. The above-discussed haze of the composite film can in particular be combined with the above-discussed feature of the same or higher sealing temperature of the thermoplastic resin of layer (a) compared to the resin of layer (c).

It is particularly advantageous if, according to the invention, the choice of a thermoplastic resin for layer (a) with a sealing temperature equal to or higher than the sealing temperature of the resin in layer (c) is combined with the low haze values of the multilayer film described above.

Additionally or alternatively, the composite film can have a stiffness (DIN EN ISO 527), expressed as a modulus of elasticity, measured in the machine direction, of at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, in particular at least 450 MPa. Additionally or alternatively, the composite film can have a stiffness (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the transverse direction, ie in a direction which is perpendicular or transverse to the machine direction, of at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, in particular at least 450 MPa.

Additionally or alternatively, the composite film can have a stiffness (DIN EN ISO 527), expressed as a modulus of elasticity, measured in the machine direction, of at most 700 MPa, preferably at most 650 MPa, preferably at most 600 MPa, preferably at most 550 MPa, in particular at most 500 MPa . Additionally or alternatively, the composite film can have a rigidity (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the transverse direction, of at most 700 MPa, preferably at most 650 MPa, preferably at most 600 MPa, preferably at most 550 MPa, in particular at most 500 MPa .

According to the invention, the layer (a) or the composite film according to the invention containing it can in particular be characterized by one of the following features or any combination of the following features:

The thermoplastic resin of layer (a) can have a sealing temperature (measured at 1 bar, air atmosphere, 23 ° C.) which is equal to or higher than the sealing temperature of the resin of layer (c);

The thermoplastic resin of layer (a) can have a density of 0.94 g / cm ³ or more, preferably 0.96 g / cm ³ or more, preferably between 0.96 and 2 g / cm ³ , in particular between 0, 96 and 1.5 g / cm ³ ;

• the thermoplastic resin of layer (a) is a material with a melting temperature or a melting point of 170 ° C or higher, preferably 175 ° C or higher, preferably 180 ° C or higher, preferably between 170 and 300 ° C, preferably between 175 and 300 ° C, in particular between 180 and 300 ° C; The haze of the composite film (ASTM D1003) can be limited to a maximum of 15%, preferably a maximum of 12%, preferably a maximum of 10%, preferably a maximum of 7%, in particular a maximum of 5%;

The rigidity of the composite film (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the machine direction or transverse direction, can be at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, in particular at least 450 MPa; and or

The stiffness of the composite film (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the machine direction or transverse direction, can be limited to a maximum of 700 MPa, preferably a maximum of 650 MPa, preferably a maximum of 600 MPa, preferably a maximum of 550 MPa, especially a maximum of 500 MPa his.

Within the scope of the present invention, a combination of at least two of the features disclosed above with reference to the features of layer (a) is also possible, whereby further advantageous properties can be achieved.

In a preferred embodiment, the resin of layer (c) can be a polyolefin (PO), preferably a polyethylene (PE) and / or a polypropylene (PP), an ethylene-vinyl acetate copolymer (EVA), an ionomer (IO) Ethylene-methyl methacrylate copolymer (EMMA), an ethylene-methacrylic acid copolymer (EMA), or any mixture of the same or consist thereof.

By providing a polyolefin (PO), preferably a polyethylene (PE) and / or a polypropylene (PP), or EVA, an ionomer (IO), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-methacrylic acid -Copolymers (EMA), or any mixture thereof, for example a mixture of PO and EVA, as the resin of the layer (c), an excellent sealability is ensured. In the case of the layer component EVA in particular, dispensing with the radiation crosslinking leads to the retention of the excellent sealability, which would otherwise be lost or at least restricted by radiation crosslinking. In addition, it is advantageous in terms of high shrinkage and not too high rigidity to provide a polyolefin as a component of layer (c). Layer (c) preferably contains a high proportion of a polyolefin or consists of a polyolefin.

In addition, the layer (a) can have a thickness in the range from 0.5 to 20 μm, preferably 1 to 10 μm; and / or the thickness of layer (a) can be at most 30%, preferably at most 10%, in particular at most 5%, of the thickness of the entire composite film.

The fact that the thickness of the layer (a) is limited to a value in the range from 0.5 to 20 μm, preferably 1 to 10 μm, ensures that only a small amount of the resin or resin mixture forming the layer (a) is in the composite film is inserted or applied. This restriction of the amount of material in layer (a) avoids compromises in terms of suppleness and the associated damage to other packaging or the shrinkage of the resulting composite film, which can otherwise occur if too much material is used in layer (a). In addition, the provision of a thin outer layer (a) ensures that the resulting composite film is extremely flexible.

It is also provided that none of the layers of the composite film which are arranged between layer (a) and layer (c) contain a polyamide (PA).

Due to this restriction, a higher dimensional stability is achieved with lower rigidity at the same time. In addition, a lower cold shrinkage is achieved.

Furthermore, it is provided that none of the layers of the composite film, which are arranged between layer (a) and layer (c), contain an ethylene-vinyl alcohol copolymer (EVOH). The composite film according to the invention can advantageously completely dispense with the use of an ethylene-vinyl alcohol copolymer (EVOH) as a layer component in the inner layers by providing PVdC in layer (b). This prevents the decrease in the barrier function due to the external influence of moisture on the composite film, which occurs as a barrier material with EVOH. In this way, a sufficient barrier function with long-term stability can be ensured despite or precisely because of the waiver of EVOH.

According to the invention, an “inner layer” is understood to mean a layer within the composite film according to the invention which is arranged between layer (a) and layer (c).

Compared to the alternative case using EVOH in an inner layer, in which a correspondingly more complex layer structure with an increased total number of layers is required so that sandwich layers can be provided to protect the embedded EVOH layer, the additional "protective layers" can be applied according to the invention. be waived. This simplifies the overall structure and the production method of the composite film. In addition, the manufacturing costs decrease.

In addition, by not using EVOH and PA in the inner layers, as described above, a relatively stiff composite film can be avoided if these materials are used in larger percentages of the layer material. Furthermore, the disadvantage of these materials can be avoided that there is a recrystallization of the composite film and thus an impairment of the dimensional stability.

In addition, the composite film can have a (hot) shrinkage of at least 20%, preferably at least 25%, in particular at least 50%, in each case in the longitudinal and in the transverse direction, measured in water at 90 ° C., preferably within 1 second after immersion, but at least within 10 seconds after immersion. Additionally or alternatively, the composite film can have a total shrinkage based on the area of at least 40%, preferably at least 50%, in particular at least 100%, measured in water at 90 ° C., preferably within 1 second after immersion, at least but within 10 seconds of being immersed.

According to the invention, to determine the heat shrinkage, the sample is immersed in water at 90 ° C. for a predetermined, in particular the aforementioned period of time, and immediately cooled to room temperature with water after removal. The length of a pre-marked section after this treatment is measured and related to the measured length of the same section of the sample before the treatment. The resulting length ratio ("shrunk" to "not shrunk"), given in percent, defines the shrinkage. Depending on the direction of the length measurement, the shrinkage results in the longitudinal (MD) and in the transverse direction (TD). The total shrinkage is calculated by adding the shrinkage in the longitudinal and in the transverse direction. Multiple determinations, such as triple or five-fold determinations, of the length measurements, and the formation of the corresponding mean values therefrom, advantageously increase the accuracy of the determination. According to the invention, the shrinkage and the total shrinkage can be determined in accordance with ASTM 2732 in particular.

By means of the method according to the invention, composite films can advantageously be produced which consequently have a high degree of shrinkage both in the longitudinal direction (longitudinal / machine direction) and in the transverse direction (transverse direction). Even high demands on the resulting composite film, which are placed on a shrink film for packaging a foodstuff such as meat, fish or cheese, for example, are thus met. According to the invention, the composite film can furthermore have the following layer structure, counted from the outside in, with at least seven layers, wherein: a first layer from the outside as a layer component a polyethylene terephthalate (PET), a polyamide (PA), a polylactic acid (PLA), or any mixture thereof;

a second layer from the outside as a layer component an adhesion promoter (HV);

a third layer from the outside as a layer component a polyolefin (PO), preferably a polypropylene (PP) or a polyethylene (PE), an ethylene vinyl acetate copolymer (EVA), an ionomer (IO), an ethylene methyl methacrylate Copolymer (EMMA), an ethylene methacrylic acid copolymer (EMA), or any mixture thereof;

a fourth layer from the outside as a layer component an adhesion promoter (HV);

a fifth layer from the outside as a layer component polyvinylidene chloride (PVdC);

a sixth layer from the outside as a layer component an adhesion promoter (HV); and

a seventh layer from the outside as a layer component a polyolefin (PO), preferably a polyethylene (PE) or a polypropylene (PP), an ethylene-vinyl acetate copolymer (EVA), an ionomer (IO), an ethylene-methyl methacrylate Copolymer (EMMA), an ethylene methacrylic acid copolymer (EMA), or any mixture thereof;

may contain or consist of.

In addition to the advantages mentioned above, which this specific composite structure realizes, a high heat resistance of the composite film is achieved. In addition, the composite film is not too stiff.

In addition to the above-described method according to the invention, its direct product is also claimed in claim 10, which achieves the object. The advantages of the method discussed above apply analogously to this. Furthermore, the object according to the invention is achieved in terms of production technology by the composite film according to claim 11. The advantages and modifications of the method according to the invention discussed above also apply analogously to the composite film according to the invention.

Thus, a multilayer composite film is claimed which is preferably produced by means of a blow molding process and biaxially stretched, and in particular produced by the process according to one of Claims 1 to 9. The composite film comprises at least three layers (a), (b) and (c), of which

the layer (a) forms a surface of the composite film to the outside; the layer (c) forms a surface of the composite film which faces or comes into contact with an item to be packaged; and the layer (b) is arranged between the layer (a) and the layer (c). Layer (a) contains or consists of a thermoplastic resin. Layer (b) contains or consists of a polyvinylidene chloride (PVdC) resin. Furthermore, the layer (c) contains or consists of a resin, preferably a sealable, in particular heat-sealable resin. The thermoplastic resin of layer (a) contains or consists of a polyester, preferably a polyethylene terephalate (PET), a polylactic acid (PLA), a polyamide (PA), or any mixture. There is no crosslinking of the composite film by means of radioactive radiation, in particular by means of beta, gamma, X-ray and / or electron radiation, during the production of the composite film and / or afterwards.

Advantageous embodiments are the subject of the dependent claims. Thus, the features discussed for the above method according to the invention can also be used for the advantageous limitation of the composite film according to the invention, as is reproduced in claims 12 to 19.

Finally, the use of a composite film according to one of Claims 10 to 19 or a casing produced therefrom for packaging an object, preferably a food or luxury food, in particular a food containing meat, fish or cheese, is claimed. With the use of the composite film according to the invention according to claim 20, the advantages of the composite film according to the invention can ideally be used especially in the packaging of light, oxygen, temperature and / or aroma-sensitive goods, such as food in particular. The composite film according to the invention offers ideal protection for sensitive packaging goods, in addition to the advantages described above.

Embodiments

Table 10: Layer structures of exemplary composite films according to the invention with seven layers, not cross-linked by radiation: Layer components and layer thicknesses (total thickness 50 μm each)

However, the invention is not limited to the embodiments mentioned, in particular not to the total thickness of the layer structure and the thickness ratios of the individual layers, as are given in Table 10. The invention thus also expressly encompasses the layer sequences of Examples 1 to 3 of Table 10, but with layer thicknesses other than those indicated in Table 10 and in each case different total thicknesses. Further disclosure and alternatives

The method according to the invention and the composite film according to the invention can preferably be carried out or produced using the so-called double-bubble and in particular the triple-bubble method, for which the applicant provides suitable systems, which are known to the person skilled in the art . The multilayer composite film can, for example, be coextruded from the respective resin melts by means of a nozzle blow head set up by the applicant for the production of composite films with three or more layers, preferably with thermal separation of the individual layers, cooled with water cooling by the applicant, reheated, biaxially by means of an enclosed compressed air bubble stretched and finally heat-set in a further step in a defined temperature regime. The composite film according to the invention can be a composite film which has a barrier against gas diffusion, in particular oxygen diffusion, and / or against water vapor diffusion.

The composite film of the present invention can advantageously be achieved on a device or system from the same applicant for the production of tubular food films for food packaging, such as, for example, shrink films or shrink bags, in the jet blowing process, if one also uses the same as described in patent DE 199 16 428 B4 Applicant disclosed device for rapid cooling of thin thermoplastic tubes after their extrusion. A corresponding further development according to patent specification DE 100 48 178 B4 can also be taken into account for this purpose.

The tubular film produced from the plastic melt in the die head is subjected to intensive cooling during which the amorphous structure of the thermoplastics from the plastic melt is retained. The tubular film extruded vertically from the plastic melt in the die head initially migrates into the cooling device without touching the wall, as described in detail in the publications DE 199 16 428 B4 and DE 100 48 178 B4. With regard to single The full content of the contents of the documents DE 199 16 428 B4 and DE 100 48 178 B4 is referred to in full to avoid repetition of the procedures, the structure and the mode of operation of this cooling device, also referred to as calibration device.

The tubular film then passes through supports in the cooling device, against which the film is supported as a result of a differential pressure between the interior of the tubular film and the coolant, a liquid film being retained between the film and the supports so that the tubular film cannot stick. The diameter of the supports influences the diameter of the tubular film, which is why this cooling device by the same applicant is also referred to as a calibration device.

According to the invention, polyvinylidene chloride (PVdC) is understood to mean a thermoplastic formed from vinylidene dichloride (1,1-dichloroethene) analogously to PVC. PVdC decomposes near the melting point of approx. 200 ° C.

According to the invention, polyamide (PA) can be a substance selected from a group consisting of PA from e-caprolactam or poly (s-caprolactam) (PA6), PA from hexamethylene diamine and adipic acid or polyhexamethylene adipamide (PA6.6), PA from e-Ca- prolactam and hexamethylenediamine / adipic acid (PA6.66), PA made from hexamethylenediamine and dodecanedioic acid or polyhexamethylene dodecanamide (PA6.12), PA made from 11-aminoundecanoic acid or polyundecanamide (PA11), PA made from 12-laurolactam or poly ( co-laurin lactam) (PA 12), or a mixture of these PA or a mixture of these PA with amorphous PA or with other polymers. The general notation PAx.y is synonymous with PAx / y or PAxy.

For the purposes of this application, polyolefin (PO) can be a substance selected from a group consisting of PP, PE, LDPE, LLDPE, polyolefin plastomer (POP), ethylene-vinyl acetate copolymers (EVA), ethylene-methyl methacrylate copolymers (EMMA ), Ethylene methacrylic acid copolymers (EMA), ethylene acrylic acid copolymers (EAA), Copolymers of cycloolefins / cycloalkenes and 1-alkenes or cycloolefin copolymers (COC), ionomers (IO) or a mixture or a mixture thereof. Furthermore, PO can be a mixture of the above POs with ionomers.

In the context of the present invention, polyester can be used as a layer component for layer (a). Polyesters are polymers with ester functions in their main chain and can in particular be aliphatic or aromatic polyesters. Polyesters can be obtained by polycondensation of corresponding dicarboxylic acids with diols. Any dicarboxylic acid which is suitable for forming a polyester can be used to synthesize the polyester, especially terephthalic acid and isophthalic acid, as well as dimers of unsaturated aliphatic acids. Diols can be used as the further component for the synthesis of the polyester, for example: polyalkylene glycols, such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, diethylene glycol, polyethylene glycol and polytetra methylene oxide glycol; 1,4-cyclohexanedimethanol, and 2-alkyl-1,3-propanediol.

PET, which stands for the polyester polyethylene terephthalate, is particularly preferred. PET can be obtained by polycondensation of terephthalic acid (1,4-benzene dicarboxylic acid) and ethylene glycol (1,2-dihydroxyethane).

Another preferred polyester are the polylactides or polylactic acids (PLA), which can be contained as a layer component in the layers for which a polyester is provided as a layer component. These polymers are biocompatible / biodegradable and, in addition to low moisture absorption, have high melting temperatures or high melting points and good tensile strength.

In the context of the present invention, EVOH stands for EVOH as well as a mixture of EVOH with other polymers, ionomers, EMA or EMMA. In particular, EVOH also includes a mixture of EVOH and PA or of EVOH and ionomer. The adhesion promoters (HV) stand for adhesive layers that ensure good bond between the individual layers. HV can be based on a base material selected from a group consisting of PE, PP, EVA, EMA, EMMA, EAA and an ionomer, or a mixture thereof. According to the invention, EVA, EMA or EMMA, each with a purity of> 99%, preferably> 99.9%, are particularly suitable as adhesion promoters (HV).

According to a further, preferred embodiment, layers that have HV as a layer component can also be a mixture of PO and HV or a mixture of EVA, EMA, EMMA and / or EAA and HV or a mixture of ionomer and HV or a mixture of a plurality of Show HV.

For the purposes of this invention, further processability (number of cycles) means the speed (units per unit of time) with which the composite film produced according to the invention can be further processed into usable packaging units, such as shrink bags for food. This can include, for example, the formation of a bag shape, the application of sealing seams and, in a broader sense, possibly also the filling with the goods to be packaged and the closing of the filled packaging.

For the purposes of this invention, the designation of a material as a “layer component” means that a layer of the food film according to the invention at least partially comprises this material. The term “layer component” in the context of this invention can in particular include the fact that the layer consists entirely or exclusively of this material.

The composite film according to the invention is preferably flat or tubular. The composite film is preferably a foodstuff film or food casing. The composite film is also preferably suitable for use as a heat-shrinkable packaging material. In the context of this application, “crosslinking by radiation” or “radiation crosslinking” means crosslinking by means of radioactive radiation, preferably “crosslinking by means of beta, gamma, x-ray and / or electron radiation”. According to the invention, the omission of radiation crosslinking includes an integrated and a downstream radiation crosslinking in the production of the composite film.

Claims

Expectations

A process for producing a multilayer composite film, the process comprising at least the following steps:

a step of co-extruding at least three layers (a), (b) and (c) of which

a step of bi-axially stretching the composite film co-extruded in this way; wherein layer (a) contains or consists of a thermoplastic resin; wherein the layer (b) contains or consists of a polyvinylidene chloride (PVdC) resin;

wherein the layer (c) contains or consists of a resin, preferably a sealable, in particular heat-sealable resin;

wherein the thermoplastic resin of layer (a) contains or consists of a polyester, preferably a polyethylene terephthalate (PET) or a polylactic acid (PLA), a polyamide (PA), or any mixture thereof; and wherein any crosslinking of the composite film by means of radioactive radiation, in particular by means of beta, gamma, X-ray and / or electron radiation, is omitted during the production of the composite film and / or afterwards.

Method according to claim 1, characterized in that

the thermoplastic resin of the layer (a) has a melting temperature of 170 ° C or higher, preferably 175 ° C or higher, preferably 180 ° C or higher; and or

the thermoplastic resin of the layer (a) has a sealing temperature which is equal to or higher than the sealing temperature of the resin of the layer (c); and or the thermoplastic resin of the layer (a) has a density of 0.94 g / cm ³ or more.

3. The method according to claim 1 or 2, characterized in that the resin of

Layer (c) a polyolefin (PO), preferably a polyethylene (PE) and / or a polypropylene (PP), an ethylene-vinyl acetate copolymer (EVA), an ionomer (IO), an ethylene-methyl methacrylate copolymer (EMMA) , an ethylene methacrylic acid copolymer (EMA), or any mixture thereof, or consists of it.

4. The method according to any one of claims 1 to 3, characterized in that the layer (a) has a thickness in the range from 0.5 to 20 μm, preferably 1 to 10 μm; and or

the thickness of the layer (a) is at most 30%, preferably at most 10%, in particular at most 5%, of the thickness of the entire composite film.

5. The method according to any one of claims 1 to 4, characterized in that none of the layers of the composite film which are arranged between the layer (a) and the layer (c) contains a polyamide (PA).

6. The method according to any one of claims 1 to 5, characterized in that none of the layers of the composite film, which are arranged between the layer (a) and the layer (c), contains an ethylene vinyl alcohol copolymer (EVOH).

7. The method according to any one of claims 1 to 6, characterized in that the

Composite film has a shrinkage of at least 20%, preferably at least 25%, in particular at least 50%, in each case in the longitudinal and in the transversal direction, measured in water at 90 ° C., preferably within 1 second after immersion, but at least within 10 seconds after immersion; and or

that the composite film has a total shrinkage based on the area of at least 40%, preferably at least 50%, in particular at least 100%, measured in water at 90 ° C, preferably within 1 second after immersion, but at least within 10 seconds after Immerse yourself on points.

8. The method according to any one of claims 1 to 7, characterized in that the composite film has the following layer structure, counted from the outside in, with at least seven layers, wherein:

a first layer from the outside as a layer component a polyethylene terephthalate (PET), a polyamide (PA), a polylactic acid (PLA), or any mixture thereof;

a second layer from the outside as a layer component an adhesion promoter (HV);

- A third layer from the outside as a layer component a polyolefin (PO), preferably a polypropylene (PP) or a polyethylene (PE), an ethylene-vinyl acetate copolymer (EVA), an ionomer (IO), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene methacrylic acid copolymer (EMA), or any mixture thereof;

- A fourth layer from the outside as a layer component an adhesion promoter (HV);

a seventh layer from the outside as a layer component a polyolefin (PO), preferably a polyethylene (PE) or a polypropylene (PP), an ethylene Vinyl acetate copolymer (EVA), an ionomer (IO), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-methacrylic acid copolymer (EMA), or any mixture thereof;

contains or consists of.

9. The method according to any one of claims 1 to 8, characterized in that the composite film has a haze of at most 15%, preferably at most 12%, preferably at most 10%, preferably at most 7%, in particular at most 5%; and or

the composite film has a stiffness, expressed as modulus of elasticity, measured in the machine direction, of at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, especially at least 450 MPa; and or

the composite film has a rigidity, expressed as the modulus of elasticity, measured in the transverse direction, of at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, in particular at least 450 MPa; and / or the composite film has a stiffness, expressed as the modulus of elasticity, measured in the machine direction, of at most 700 MPa, preferably at most 650 MPa, preferably at most 600 MPa, preferably at most 550 MPa, in particular at most 500 MPa; and or

the composite film has a stiffness, expressed as the modulus of elasticity, measured in the transverse direction, of at most 700 MPa, preferably at most 650 MPa, preferably at most 600 MPa, preferably at most 550 MPa, in particular at most 500 MPa.

10. Multi-layer composite film produced by the method according to one of claims 1 to 9.

11. Multi-layer composite film, preferably produced by means of a blow molding process and biaxially stretched, in particular produced by the process according to one of claims 1 to 9;

wherein the composite film comprises at least three layers (a), (b) and (c), of which

the layer (a) forms a surface of the composite film to the outside; the layer (c) forms a surface of the composite film which faces or comes into contact with an item to be packaged; and the layer (b) is arranged between the layer (a) and the layer (c); wherein layer (a) contains or consists of a thermoplastic resin; wherein the layer (b) contains or consists of a polyvinylidene chloride (PVdC) resin;

wherein the thermoplastic resin of layer (a) contains or consists of a polyester, preferably a polyethylene terephthalate (PET) or a polylactic acid (PLA), a polyamide (PA), or any mixture thereof; and wherein any crosslinking of the composite film by means of radioactive radiation, in particular by means of beta, gamma, X-ray and / or electron radiation, is omitted during the production of the composite film and thereafter.

12. The composite film according to claim 11, characterized in that the thermoplastic resin of the layer (a) has a melting temperature of 170 ° C or higher, preferably 175 ° C or higher, preferably 180 ° C or higher; and / or the thermoplastic resin of layer (a) has a sealing temperature which is equal to or higher than the sealing temperature of the resin of layer (c); and / or the thermoplastic resin of layer (a) has a density of 0.94 g / cm ³ or more.

13. The composite film according to claim 11 or 12, characterized in that the resin of layer (c) is a polyolefin (PO), preferably a polyethylene (PE) and / or a polypropylene (PP), an ethylene-vinyl acetate copolymer (EVA) , an ionomer (IO), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-methacrylic acid copolymer (EMA), or any mixture thereof contains or consists of them.

14. Composite film according to one of claims 11 to 13, characterized in that the layer (a) has a thickness in the range from 0.5 to 20 μm, preferably 1 to 10 μm; and or

15. Composite film according to one of claims 11 to 14, characterized in that none of the layers of the composite film which are arranged between the layer (a) and the layer (c) contains a polyamide (PA).

16. Composite film according to one of claims 11 to 15, characterized in that none of the layers of the composite film which are arranged between layer (a) and layer (c) contains an ethylene-vinyl alcohol copolymer (EVOH).

17. Composite film according to one of claims 11 to 16, characterized in that the composite film has a shrinkage of at least 20%, preferably at least 25%, in particular at least 50%, in each case in the longitudinal and in the transversal direction, measured in water 90 ° C, preferably within 1 second after immersion, but at least within 10 seconds after immersion; and or that the composite film has a total shrinkage based on the area of at least 40%, preferably at least 50%, in particular at least 100%, measured in water at 90 ° C, preferably within 1 second after immersion, but at least within 10 seconds after Immerse yourself on points.

18. Composite film according to one of claims 11 to 17, characterized in that the composite film has the following layer structure, counted from the outside to the inside, with at least seven layers, wherein:

a second layer from the outside as a layer component an adhesion promoter (HV);

a fourth layer from the outside as a layer component an adhesion promoter (HV);

a seventh layer from the outside as a layer component a polyolefin (PO), preferably a polyethylene (PE) or a polypropylene (PP), an ethylene-vinyl acetate copolymer (EVA), an ionomer (IO), an ethylene-methyl methacrylate copolymer ( EMMA), an ethylene methacrylic acid copolymer (EMA), or any mixture thereof;

contains or consists of.

19. Composite film according to one of claims 11 to 18, characterized in that the composite film has a haze of at most 10%, preferably at most 5%; and or

the composite film has a rigidity, expressed as the modulus of elasticity, measured in the transverse direction, of at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, in particular at least 450 MPa; and / or the composite film has a stiffness, expressed as a modulus of elasticity, measured in the machine direction, of at most 700 MPa, preferably at most 650 MPa, preferably at most 600 MPa, preferably at most 550 MPa, in particular at most 500 MPa; and or

20. Use of a composite film according to one of claims 10 to 19 or of a casing produced therefrom for packaging an object, preferably a food or luxury food, in particular a food containing meat, fish or cheese.