MXPA00001335A - A hose film on the basis of polyamides - Google Patents

Abstract

The invention concerns hose films on the basis of polyamides which can be used for production of hose films orientated in two axes usable in manufacture of paste-like and viscous products which may be subjected to heat treatment in temperature range 70-125°C. A hose film on the basis of polyamides, including polyamide 6, aliphatic copolyamide, aromatic polyamide, containing hexamethylenediamine and teraphthalic acid units and a copolymer, including olefin units, is claimed which additionally contains a ionomer resin. As aliphatic copolyamide, it contains a copolymer of polycaprolactam, polyhexamethylenediamine and adipic acid. As copolymer including olefin units, it contains a mixture of graft copolymers on the basis of derivatives of carboxylic and polycarboxylic acids. The components are present in following amounts (weight parts):Polyamide 6:77-83;copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid:7-13;aromatic polyamide, containing hexamethylenediamine and terephthalic acid units:3-7;ionomer resin:3-6;mixture of graft copolymers on the basis of derivatives of carboxylic and polycarboxylic acids:0.1-5.

Description

SLEEVE FILM ON THE POLYAMIDE BASE Field of the Invention The invention concerns film sleeves based on polyamides and that can be used for the production of film sleeves oriented in two axes that will be used in the manufacture of similar products. pastes and viscose that can be subjected to a heat treatment within the temperature range of 70-125 ° C. The invention relates in particular to the manufacture of film sleeves for the production of sausages and also of processed cheeses, packaged in the form of sausages, which are packaged as a rule, in the softened state or viscous liquid state. BACKGROUND OF THE INVENTION There are many types of polymeric film, used in the manufacture of products similar to pasta or packaged processed products. The composition for receiving a layer for sausages includes polycaprolactants with a molecular weight in the range of 1000-4000, 1,6-hexamethylene diisocyanate and 1,4-butanediol in the following ratio of components (parts by weight): -30, 50-40, 24.84-27.0 (SU, AI, 1034597).

For the production of the component layer of a composition heated to 60-50 ° C with subsequent temperature increase of up to 240 ° C. The product received is emptied into a polytetrafluoroethylene film. After 5 hours the drained plate is granulated, heated again and extruded. However, it is necessary to carry out a treatment of a known composition before extrusion, which requires a lot of time. In addition, the film has a thickness that is not less than 0.05 mm and is suitable only for use with special machines. The moisture content in the layer is 0.03%, which is sufficient to stop the layer in the coating process in a stretched and elastic condition, but during cooking the water contents in the layer are increased by such way, that it negatively influences the mechanical characteristics of the layer. The layers based on polyamide can be better subjected to stretch and shrinkage, have long durability, and are also suitable not only for filling by a machine but also for hand operated filling. A film is known, used in the manufacture of pasta-like food products, in particular sausages and cheese, which contains at least one aliphatic polyamide and at least one ionomeric resin and / or at least one modified ethylene copolymer and vinyl acetate (DE, Al, 2850181). As polyamides in the known film sleeve, the polycaprolactams, the polyamino-enantamide, the polyhexamethyleneadipamide and / or the polyhexamethylene-sebacinamide are used as separate substances or as a mixture with one another, and also the copolymers of the above polyamides and polyaminoundecaneamide or polylaurylolactams. The thickness of the received film sleeve is around 0.050 mm, which is satisfactory only for machine filling; The permeability of water is within the range of 12-28 g / m3 in one day and the oxygen permeability is of the order of 15 to 30 cm3 / m2 per day bar. This film is made in the following way: the components are mixed plasticized to 280 ° C and molded, preferably by extrusion of a sleeve with blowing. After the biaxial stretching with the multiplicity of elongation and transverse stretching in a range of the order of 1: 1.5 to 1: 4. After the sleeve is set f ~ thermally for the stabilization of sizes. However, the known technical decision does not allow to receive thinner films for hand operated filling and to provide the necessary film strength at the time of cooking. When cutting the layer, its propensity to break was indicated.

For the preparation of cooked sausages, a meat filling must be filled on its cover under a significant pressure of the order of 03-6 bars For the hand-operated filling of stuffing meat for sausage, during which the filling pressure is negligible, this layer can hardly be used, as after finishing the work cycle of preparation can be formed folds or fractures of the sausages. The closest known technical decision to the claimed one is a film sleeve in a polyamide base, used in the manufacture of pasta-like and viscous food products (sausage cover), including polyamide 6, aliphatic copolyamide, aromatic polyamide, which It contains hexamethyl diamine and units of terephthalic acid, and copolymer including olefin units (EP, Al, 0722664).

This film sleeve contains (% by weight): a) polyamide 6 b) aliphatic polyamide (5-50% of the overall weight of all polymers in one layer). As the aliphatic copolyamide, the copolyamide is used with e-caprolactam units of hexamethylenediamine and of acetalic acid (polyamide 6 / 6.9) and / or polyamide 6.12 as copolyamide of hexamethylenediamine and dodecainic acid. b) up to 20% aromatic polyamide, partially aromatized by hexamethylenediamine and units of terephthalic acid or isophthalic acid (PA 6-T or PA 6-7) c) up to 20% of copolymer with polyolefin olefin units, modified by groups of carboxyl, in particular copolymer of ethylene and of methacrylic acid. The film sleeve can wrap dyes and / or pigments in small quantities. The manufacture of one layer and multiple layer sausage layers includes mixing and melting at a temperature of about 240 ° C of components of the mixture in a special extruder to produce a homogeneous molten mixture, extruding the latter through ring injectors with blowing, the molding of an integrated sleeve, which is then stretched in longitudinal and transverse directions under air pressure. A received film is fixed through additional heat treatment. The film sleeve received according to the known technology (prototype) gives a shrinkage of 5 up to 25% (at 80 ° C) in shared and transverse directions, and has a thickness of 0.033-0.056 mm, which can be manufactured as multiple layers. The water permeability of the sausage layer changes from 11.5 to 13.1 g / m per day, and the oxygen permeability varies from 13.6 to 18.5 cmVm2 ars per day. The multilayer film sleeve contains a minimum of one layer of the polyamide blend. Other layers consist mainly of polyamides (for example polyamide 6), mixtures of polyamides, polyolefins (for example, polyethylene or polypropylene) also of polyolefins, which contain binding functional groups. In addition, the layers may be made of copolymers with units of ethylene-unsaturated monomers (eg, vinylacetate, vinyl alcohol, acrylic and methacrylic acid) and also vinyl chloride or acrylonitrile copolymers, ionomer resins or mixtures of the aforementioned polymers. A cover usually consists of 3-5 layers. This cover can be manufactured by co-extrusion through ring injectors, which are specially designed according to the number of layers. Multilayer covers are compared to the single layer that shows more water and vapor permeability and oxygen permeability. There is a lack of both single-layer and multi-layer film sleeves, claimed in EP 0722664. The high permeability to water and steam and the oxygen permeability of air, which these parameters are of priority for ready-made sausage products. , since they define the safety of a ready product and the loss of its weight. Furthermore, the durability of a layer for viscous products and sterilized sausages, which require stability under the technological rules on the temperature of up to 125 ° C, is insufficiently high. SUMMARY OF THE INVENTION The problem to be solved by the invention consists in the creation of a film sleeve that will be used in the manufacture of pasta-like and viscous food products, which have low permeability to water and steam and oxygen permeability, and also increased resistance characteristics under a heat treatment. The problem is solved by the claimed invention. A film sleeve on the basis of polyamides, including polyamide 6, aliphatic copolyamide, aromatic polyamide containing hexamterylenediamine and units of terephthalic acid and copolymer, including olefin units, according to the invention, additionally contains ionomeric resin, as aliphatic copolyamide contains polycaprolactam copolymer and polyhexamethylene diamine and adipic acid, and as copolymer including olefin units contains a mixture of copolymers grafted on the basis of carboxylic acid and polycarboxylic derivatives with the following component ratio (parts by weight): Polyamide 6 77 -83 Copolymer of polycaprolactam and polyhexamethylene diamine and of adipic acid 7-13 Aromatic polyamide, containing hexamethylenediamine and terephthalic acid units 3-7 Ionomeric resin 3-6 Mixture of grafted copolymers based on carboxylic and polycarboxylic acid derivatives 0.1 The film sleeve may contain zinc salt of ethylenemethacrylic acid copolymer as ionomeric resin. In the claimed film sleeve the copolymer of polycaprolactam and polyhexamethylenediamine and adipic acid can be used (polyamide 6 / 6,6 with elements of the formulas -N- (CH 2) 5 -CO-, -N- (CH 2) - NH-, -CO- (CH2) 4-C0-) with amounts of monomer parts correspondingly with% by weight of 85, 7.5 and 7.5. The film sleeve can contain as a mixture of copolymers grafted on the basis of carboxylic and polycarboxylic acid derivatives where the mixture with the contents of grafted units is of the order of 0.3 to 0.9% by weight. The film sleeve can be made as multiple layers, and at least one layer has the following composition, (parts by weight): Polyamide 6 77-83 Polycaprolactam copolymer and polyhexamethylenediamine acid and adipic acid 7-13 Aromatic polyamide, containing hexamethylenediamine and terephthalic acid units 3-7 Ionomeric resin 3-6 Mixture of copolymers grafted on the basis of carboxylic and polycarboxylic acid derivatives 0.1-5 in this embodiment of the invention in the layers of the multilayer film sleeve are carried out of polyamides, or of mixtures of polyamides , or of polyolefins or polyolefins containing related functional groups, or of copolymers with units of unsaturated ethylene monomers, or of vinylidenechloride copolymers or of acrylonitrile or ionomer resins or mixtures of these polymers. DETAILED DESCRIPTION OF THE INVENTION The film sleeve may contain, if necessary, additional dyes, pigments and / or processing aids. The participation of these components is low, so that the basic characteristics of the film remain constant. Next, the components of the film sleeve are designated as follows: 1) - polyamide 6, 2) - Copolymer of polycaprolactam and polyhexamethylenediamine and of adipic acid 3) - Aromatic polyamide, containing hexamethylenediamine and terephthalic acid units 4 ) - Ionomeric resin 5) - Mixture of grafted copolymers based on carboxylic and polycarboxylic acid derivatives. Examples of graft copolymers which are used are acrylic polymer with grafted units of maleic anhydride, linear low density polyethylene with grafted maleic anhydride units and ethylene-propylene rubber with grafted maleic anhydride groups. The mixture of grafted copolymers based on acid derivatives carboxylic and polycarboxylics allows some other easier and more accessible processed copolymers to enter the structure of this film sleeve, for example, the polycaprocaramide copolymer and polyhexamethylenediamine copolymer and adipic acid instead of the copolymer polycaprolactam and polyhexamethylenediamine and acelaic acid used for the manufacture of known film sleeves. Due to the preferential use of the set of components of the film sleeve in the ratio of the order of 79 to 81% of the total weight of a component 1), of 9 to 11% of a component 2), of 4 to 6% of a component 3), from 4 to 5% of a component, 4) from 0.5 to 1.5 of a component 5), the properties that are achieved have no separate components of the film or known structures of film sleeves, such as: water and vapor permeability and oxygen permeability, and, in addition, the film has a thermal stability up to 125 ° C and is not subject to breaks in thermal processing (cooking). Example 1 A mixture of 1) 80 parts by weight of the granulated polycaprolactam (polyamide 6) with relative viscosity of 4 (measured by 1 g of polycaprolactam granulated in 100 ml of 96% sulfuric acid at 20 ° C) 2) 10 parts by weight of the copolymer of polycaprolactam and polyhexamethylenediamine and of adipic acid (polyamide 6/6, 6) with relative viscosity from 3.32 (measured for 1 g of polycaprolactam granulated in 10 ml of 96% sulfuric acid at 20 ° C). 3) 5 parts by weight of the aromatic polyamide with hexamethylenediamine units of terephthalic acid (Selar PA 3426, DuPont de Nemour, Inc.) (foundry index 90 g for 10 minutes at 275 ° C and 10 kg load). 4) 4 parts by weight of the ionomer resin - ethylene and methacrylic acid copolymer with 2-20% methacrylic acid having a melt index of 2.5 g for 10 minutes at 190 ° C and 2.16 kg of a charge and with a type of an ion - Zn (Serlin -N 1652 of DuPont). 5a) 0.5 parts by weight of linear low density polyethylene with grafted units of maleic anhydride (Fusabond E, DuPont) (foundry index of 3.0 g at 280 ° C for 10 minutes and 2.16 kg of a filler) . The components 1-5 in the amounts specified above are carefully mixed and loaded into the coal bunker of an extruder where the mixture of granules is homogenized at 255 ° C until homogeneous casting is received. The casting is delivered in a ring head of the extruder, in the passage through which a primary sleeve is produced. Upon exiting the extruder a primary sleeve is sharply cooled and then heated for plasticizing. Then it goes to the biaxial stretching that is done with compressed air. Then the molded sleeve is directed to the furnace for thermal fixation where the stabilization process is. The sleeve is then cooled, and delivered to the receiver, where it is wound into a fiber drum in a combined form. Example 2 To receive a multi-layer sleeve the following polymer blends are applied. Mix 1; 1) 80 parts by weight of the usual granular polycaprolactam (polyamide 6) (as in example 1) 2) 10 parts by weight of the copolymer of polycaprolactam and polyhexamethylenediamine and of adipic acid (polyamide 6 / 6.6) (according to example 1) 3) 5 parts by weight of the aromatic polyamide with hexamethylenediamine and acid units terephthalic (according to example 1) 4) 4 parts by weight of the ionomer resin - ethylenemethacrylic acid copolymer with 2-20% methacrylic acid (according to example 1) 5a) 0.5 parts by weight of the polymer acrylic with grafted units of maleic anhydride (according to example 1). 5b) 0.5 parts by weight of linear low density polyethylene with grafted maleic anhydride units (according to example 1) Mixture II: 70 parts by weight of low density polyethylene with a melting index of 0.2 g during minutes at 190 ° C and 2.16 kg. of a filler and 30 parts by weight of a linear low density polyethylene modified by maleic anhydride with a melt index of 3 g for 10 minutes at 190 ° C and load of 2.16 kg. Mixture III: Mixture III is prepared similarly to Mixture 1. Mixtures 1, II, III are plasticized in three simple extrusion threads at 240 ° C until homogeneous alloys are produced, then fed into ring injectors. of 3 layers and coextruyen in a sleeve. The sleeve is processed oriented in two axes and a sleeve of thermally fixed film. At a general thickness of the film of 0.055 mm the layers have the following thickness: Outer layer (mixture 1): 0.030 mm Average layer (Ii mixture): 0.015 mm Inner layer (mixture III): 0.010 mm Examples 3-10 of the film sleeve compositions are presented in Table 1. Table 1 The properties of the film sleeves claimed in accordance with the compounds used in Examples 1-10 are presented in Table 2 Table 2 NOTE: The data is presented for a movie > by thickness of 0.04 mm. The conditions in the tests: In batches 1,2V = 50 mm / min, C - speed of stretching, in batches 3,4 for 24 hours at 23 ° C and the relative humidity of air of 80%; in heading 5 for 4 hours, in heading 6 in water at 80 ° C and 125 ° C, percentage over 1000 sausage bars. The film sleeve produced according to the invention meets the requirements necessary for use, in particular in the manufacture of cooked sausages and processed cheeses. The thickness of a film for the filling by filling meat machine for sausage is 0.037-0.040 mm, for filling operated by hand is 0.030-0.033 mm. The film sleeve remains resistant, also at high temperatures of around 125 ° C it has a high elasticity and is soft to the touch, contiguous to the content even after it is completely cooled, it will not lead practically to the precipitation of jelly or fat between the meat stuffing of the sausage and the layer; its durability to the 'filling and precision of caliber of the sausages made in these environments, does not diminish. There is no adhesion of food products to the film sleeve. The distinctive feature of the film sleeve is a low permeability to water, steam and oxygen, which defines a high degree of safety of a ready product (ability for oxidation and loss of weight), and also thermal stability. The durability of the layer is maintained during the heat treatment, the percentage of sausage bars spoiled at the time of cooking is not greater than 1% over 1000 ready bars. INDUSTRIAL APPLICATIONS This invention can be used more effectively in the industry of production of auxiliary materials for the food industry.

Claims (6)

1. A film sleeve based on polyamides, including polyamide 6, aliphatic copolyamide, aromatic polyamide, containing hexamethylenediamine and terephthalic acid and copolymer units, including olefin units, characterized in that it additionally contains an ionomer resin , as aliphatic copolyamide contains copolymer of polycaprolactam and polyhexamethylenediamine and adipic acid, and as a polymer including olefin units contains a mixture of copolymers grafted on the basis of derivatives of carboxylic and polycarboxylic acids with the following component ratio (parts by weight): Polyamide 6 77 - 83 Copolymer of polycaprolactam and polyhexamethylenediamine acid and of adipic acid 7-13 Aromatic polyamide, which contains hexamethylenediamine and terephthalic acid units 3-7 Ionomeric resin 3-6 Mixture of grafted copolymers based on carboxylic and polycarboxylic acid derivatives 0.1-5

2. The film sleeve on the basis of polyamides according to claim 1, characterized in that it is an ionomer resin containing zinc salt of ethylene-methacrylic acid copolymer.

3. The film sleeve on the basis of polyamides according to claim 1, characterized in that it contains the copolymer with a quantity of parts of monomer units accordingly, as polycarboxylamino and polyhexamethylenediamine copolymer and adipic acid, correspondingly 85, 7.5 and 7.5% by weight.

4. The film sleeve on the basis of polyamides according to claim 1, characterized in that as a mixture of copolymers grafted on the basis of carboxylic and polycarboxylic acid derivatives contains the mixture with the content of grafted units of the order of 0, 3 to 0.9% by weight.

5. The film sleeve on the basis of the polyamides according to claim 1, characterized in that it is carried out as multiple layers and at least one layer has the following composition: (parts by weight): Polyamide 6 77-83 Copolymer of polycaprolactam and of polyhexamethylene diamine and of adipic acid 7-13 Aromatic polyamide, containing hexamethylenediamine and units of terephthalic acid 3-7 Ionomeric resin 3-6 Mixture of graft copolymers based on carboxylic and polycarboxylic acid derivatives 0.1-5

6. The film sleeve on the basis of the polyamides according to Claim 5, characterized in that in these other layers of the film sleeve of multiple layers are made of polyamides, or of mixtures of polyamides, or of polyolefins, or of polyolefins containing crosslinking functional groups, or of copolymers with units of unsaturated ethylene monomers, or of vinylidene chloride or acrylonitrile copolymers or ionomer resins or the mixtures of these polymers. SUMMARY Sleeve film based on polyamides, which refers to polyamide-based sleeve films that can be used for the production of sleeve films with two-axis orientation that can be used in the manufacture of pulp and viscous products that can be subjected to to thermal treatment in a temperature range of 70 - 125 ° C. A sleeving film based on polyamides, including polyamide 6, aliphatic copolyamide, aromatic polyamide, which contains units of hexamethylenediamine and tetraphthalic acid and a copolymer, including olefin units, is claimed to also contain an ionosilicate resin. As an aliphatic copolyamide, it contains a copolymer of polycaprolactam, polyhexaethylenediamine and adipic acid. As a copolymer including olefin units, it contains a mixture of copolymers grafted on the base derived from carboxylic and polycarboxylic acids. The components are present in the following quantities (parts by weight): Polyamide 6: 77-83; Copolymer of Polycaprolactam and polyhexamethylenediamine and adipic acid: 7-13: Aromatic polyamide, which contains units of hexamethylenediamine and tetraphthalic acid: 3-7; Isomer resin: 3-6; Mix of grafted copolymers based on carboxylic and polycarboxylic acid derivatives: 0-5.