The laminated packaging material, a method of manufacturing a laminated material and a packaging container produced from it

 

The invention relates to a laminated packaging material comprising the inner layer of paper or cardboard and gazoballonnyj layer of the polyamide mixture comprising the condensation polymer methoxyaniline and adipic acid, and the second crystalline or semi-crystalline polyamide, printed on one side of the inner layer by covering the joint extrusion. The invention also relates to a method of manufacturing the laminated packaging material and a packaging container produced from the laminated packaging material. 3 S. and 11 C.p. f-crystals, 5 tab., 3 Il.

The present invention relates to a laminated packaging material comprising the inner layer of paper or cardboard and gazoballonnyj layer of a polyamide, comprising the condensation polymer methoxyaniline and adipic acid (Nylon-MXD6), printed on one side of the inner layer together with at least one layer thermovalve plastics, by covering the joint extrusion.

The present invention also relates to a method of manufacturing the laminated packaging material according to the invention, as well as the packaging container, proiso know the use of the laminated packaging material disposable nature for packaging and transportation of liquid food products. Typically, these laminated packaging materials consist of a rigid form, but the folding of the inner layer consisting, for example, of paper or paperboard, to achieve the high mechanical rigidity of the form. Impervious to liquid coating of plastic applied on both sides of the inner layer and effectively protect the inner layer from absorbing the liquid fibers from moisture. These outer layers are usually composed of a thermoplastic, preferably polyethylene, which, in addition, improves the sealing properties of the packaging material to the packaging material can be turned into a finished package with the given geometry.

However, the laminated packaging material consisting only of paper or cardboard and is impervious to liquid plastic, not enough density properties against gases, in particular gaseous oxygen. This is a major flaw in the packaging of many foods, shelf-life, taste and nutrient content which is rapidly deteriorating in contact with gaseous oxygen. Examples of such food products are fruit juices, vitamin C content in which snigees the crystals barrier to gases, in particular gaseous oxygen, a layer having good properties for the delay gaseous oxygen, for example, aluminum foil ("Alifoil"), EVOH (ethylene vinyl alcohol) or PVOH (polyvinyl alcohol), on the other side of the inner layer, which is intended for the treatment of the inside of the finished package.

In General, preferably the production of packaging containers for the so-called "extended storage life on the shelf" (ESL) when stored refrigerated, that is, to maintain the vitamin-C content and quality of the Packed product over about 6 weeks of storage at a temperature of 8oWith about 8 weeks of storage at 7oAnd about 10 weeks of storage at 4oC.

However, the known hashbarger have certain disadvantages. For example, in some cases, from the point of view of cost, environment and waste, it was assumed that it is possible to replace the aluminum foil used as gatbering material in food packaging. Barrier polymer such as EVOH and PVOH, respectively, are very sensitive to moisture and quickly lose their barrier properties against oxygen gas, when exposed to moisture environment. This, among other things, the which is impervious to moisture. Alternatively EVOH and PVOH, respectively, can be combined with one or more known, approved for food applications polymers for the formation of a continuous, well-integrated layers of high getbasename properties, which are also stored in a wet environment. However, the production of packaging materials, including gaseous layers of EVOH and PVOH, respectively, leads to an increase in cost and material and production of the desired multi-layer laminate, such as gazoballonnyj layers must be surrounded by at least one, often two protective outer layers of plastic on each respective side of the laminate.

U.S. patent 4777088 discloses a packaging laminate for the production of packaging for juice, consisting of an inner layer of paper or cardboard with gazoballonnym layer which is applied thereto and includes a nylon (not disclosed in detail), and layer ionomer binder, namely Surlynprinted on gazoballonnyj layer as an intermediate binder layer with the internal (inside the package) polyolefin layer.

EP 0520767 discloses a packaging laminate, sostojatsja DuPont Corp, USA), and a binder layer applied between them.

The main disadvantage of these known packaging laminate is, however, that they do not have good enough getbasename properties for ESL package at an economical thickness of the polymer layer.

Condensation polyamide polymer from methoxyaniline and adipic acid, called "Nylon-MXD6", is a semi-crystalline polyamide and has special properties in comparison with other conventional polyamides, such as, for example, high tensile strength, bending strength and modulus of elasticity, a higher glass transition temperature, low water absorption and good gazoballonnyj properties, against, for example, gaseous oxygen.

U.S. patent 5164267 (withdrawn) describes a laminated composite consisting of a sheet of substrate on the basis of celluloide material, the laminated multilayer film containing at least one layer based on a polyamide obtained by polycondensation of aliphatic dicarboxylic acids with Xylenediamine, for example, Nylon-MXD6, while multi-layer film caused by joint extrusion on a substrate with a polyolefin layer in contact with the substrate.

inutah of paper or paperboard for liquid food products, because this material forms a fragile layer that splits easily, for example, when forming or bending of the packaging material, and therefore provides a poor barrier to gases and liquids. In addition, Nylon-MXD6 in gazobetona layer also has an adverse effect on the sealing properties in the process of sealing the packaging material in a packaging container, which leads to packages having a low tightness.

JP-A-06305086 describes a laminate of polyamide film biaxial drawing and paper layer, in which the polyamide film contains at least two polyamide layer, and at least one of the layers contains Nylon-MXD6. Film biaxial extrusion laminated to the paper layer by means of dry lamination using adhesives, or by lamination by extrusion. Such film biaxial drawing, therefore, previously produced by various processes, such as, for example, blown film, and then laminated to the other layers.

The obtained laminate in JP-A-06305086 quite different from the laminate under item 1 of the formula of the present invention. To promote adhesion between the paper layer and polyamide layer should be used advisatory in turn requires more and/or different materials in the laminate, and thus, leads to increased production costs and a greater detrimental effect on the environment both from the point of view of working conditions, and environmental conditions. In addition, the adhesion between the paper layer and the polyamide layer is likely to deteriorate in such a laminate, since the surface of pre-produced film will be oxidized and/or cured and will not easily stick to the extruded binder layer. In particular, the method is more complicated and less economical to produce such a laminate, as it requires additional pre-production film biaxial drawing.

Brief description of the invention Therefore, the present invention is to provide a new, cost-effective, environmentally friendly and well-integrated laminated packaging material of the type described in the introduction possessing good getbasename properties, in particular against gaseous oxygen, as well as good barrier properties against liquids, and good mechanical properties such as flexibility and adhesive strength between the layers.

An additional object of the present invention consists in thedat for storage of fruit juices with increased storage life on the shelf, for about 6-10 weeks when stored refrigerated.

These objectives are achieved according to the present invention through the laminated packaging material comprising the inner layer of paper or cardboard and gazoballonnyj layer of a polyamide, comprising the condensation polymer methoxyaniline and adipic acid (Nylon-MXD6), printed on one side of the inner layer together with at least one layer thermovalve plastics, by covering the joint extrusion, in which gazoballonnyj layer also includes a second crystalline or semi-crystalline polyamide.

By mixing Nylon-MXD6 with other crystalline or semi-crystalline polyamide, such as PA-6 or PA-6/66, properties can be adjusted, it is possible to obtain improved elongation at break and improved sealing properties. The elongation at break of Nylon-MXD6 is only about 2.3%, while for the standard RA-6 it is usually 400-600%. However, too high content of RA-6 will lead to bad gas properties, because they decrease exponentially relative to the number of PA-6. Examples used polyamides in this context are polyamide-6 ( polyamide is an immiscible composition, that is, a two-phase mixture, for which the DSC measurement shows two separate point or melting interval, that is, shows two melting peak, instead of just one with Nylon-MXD6 as a matrix. Such immiscible compositions have the advantage of further improved coloradobrianna properties, as well as improved tensile strength.

To achieve optimum properties in respect gazoballonnyj properties, mechanical properties, durability, sealing and resistance to the formation of a swelling number of Nylon-MXD6, included in the mixture in gazobetona layer according to the present invention, comprises more than 50 weight. % and less than 100 weight. %, preferably 60-90 weight. % and more preferably 70 to 80 weight. %.

According to one preferred variant implementation of the invention, the second polyamide is a "malono-ceramic hybrid (NCH), which is a molecular composite consisting of crystalline polyamide, such as PA-6, PA-66, PA-6/66 or RA-12, as well as evenly distributed silicate layers. NCH is formed in the polymerization process by dispersion of ceramic mineral in the monomer and polymerization, which creates the morphology of very small, well disperse the output and excellent mechanical properties. Such polyamides are described, for example, in "Journal of Applied Polymer Science", Vol.49, 1259-1264 (1993), and Vol. 55, 119-123 (1995). The advantage of the RA-6 is its low cost, whereas NCH based on PA-6, PA-66 or PA-6/66 has the advantage that gives the best gazoballonnyj properties than its corresponding base polymers. In addition, NCH is the best barrier for moisture than pure RA-6, better than about two times. Example NCH suitable for the mixtures according to the present invention, based on PA-6 and commercially available from UBE Industries (Grade 1022 CM1).

Through this blending of Nylon-MXD6 with NCH based on, for example, RA-6, receive optimal gazoballonnyj properties, and mechanical properties. The ratio of Nylon-MXD6 (which is relatively expensive) can be reduced without deterioration gazoballonnyj properties to the same value, as in the case of use of pure PA-6. At the same time, you will receive a mixture of substantially greater elongation at break and, thus, more resistant to cracking when forming and bending, providing uniform gas-tight barrier layer. A mixture of 75 wt.% Nylon-MXD6 and 25 wt.% NCH-PA6 has an elongation at break of more than 200%.

In addition, when using NCH as the second component of the mixture of Nylon-MXD6 sijaitsevalta outward from the vertical plane between the corners of the package. Increased resistance to swelling when using NCH, perhaps partly a consequence of the stiffness properties of the NCH material. The modulus of elasticity NCH-PA6 is, for example, about 830-880, whereas for RA-6 it is only 580-600 N/mm2. In addition, flavobacteria properties NCH approximately two times better properties of PA-6. It is very important to reduce the swelling effect, as buyers in some countries discriminate against vsdata appearance packing containers, thinking that distended appearance appears due to fermentation, etc. food.

According to the second preferred variant implementation of the present invention provides even more ekonomichnyi environmentally friendly packaging laminate, which improved gazoballonnyj properties, at the same time may be provided as a packaging laminate, better adapted for the production of packaging containers having improved seal. These tasks are achieved with the use of polyamide gatbering layer by covering the joint extrusion, directly on the inner layer of paper or cardboard without intermediate adhesive or binder polymer layer. In affect, and the view of natural sources, re-use, and cost. The expression "extruded floor" thus implies both the extrusion and applying a layer of extruded plastics on the substrate, which is different from the so-called "extrusion-lamination", that is, the lamination of pre-produced film on a substrate by extrusion of the binder of the intermediate layer between the substrate layer and the layer of pre-produced film. It was shown that gazoballonnyj properties of a laminate having a three-layer structure with gazoballonnym layer of a mixture of Nylon-MXD6, a binder layer and polyolefin layer covering the inner side of the inner layer by co-extrusion, improved compared to a laminate having a five-layer structure with additional polyolefin layer in contact with a cardboard layer and a binder layer between the polyolefin layer and gazoballonnym layer.

In addition, when the joint extrusion of three-layer structure at one stage, the outer polyolefin layer of the three layers can ekstrudirovaniya at a lower temperature than when the joint extrusion of the double-wall structure having two outer polyolefin layer on the cardboard. is the usual case (it is desirable to include in the process as little as possible extruders), you must ekstradiroval two outer layers at the same temperature. To promote adhesion between the layer of LDPE and cardboard preferred temperature is about 320oC. However, for the outer layer of LDPE laminate can be ekstradiroval at lower temperatures (280oC) LDPE, extrudable at such low temperatures, less prone to oxidation and is more suitable for subsequent heat sealing in the process of transformation of the packaging laminate in a paper container. The risk of getting the "plastic" taste of the Packed product will be excluded if the polyethylene ekstragiruyut at lower temperatures. In the five-layer structure, the temperature of the extrusion somewhere between should be chosen as a compromise to balance adhesion to cardboard against termosvarivaemaya outer LDPE layer, since the two LDPE layer come from a single extruder.

It has been proven that gazoballonnyj layer containing a mixture of Nylon-MXD6 and RA-6 or NCH, well glued to the inner layer of paper or paperboard in such high linear velocities, which are necessary for the production of economical laminates. It is not always obvious, because in this respect, various polyamides have different properties. RA-ewout, that plastic layer is glued to the cardboard with a strength greater than the cohesion in the cardboard. Thus, the gap that appears when testing on a break occurs in a cardboard layer, but not between layers. This can be seen when the surface is "broken" plastic cover layer of paper fibers. Similarly, layers NCH or a mixture of PA-6 and NCH is not glued to the cardboard, while the Nylon-MXD6 somewhat stuck. However, the relationship between Nylon-MXD6 and paper can easily be destroyed, because the layer of Nylon-MXD6 is brittle and not flexible and will crack and flake off from the cardboard, when the laminate is bent or twisted.

Compared with lamination gatbering layer on the inner layer with an intermediate layer of polyethylene, it has also been proven that the application gatbering layer directly on the inner layer leads to improved barrier to gaseous oxygen by approximately 30-40%. This may be due to the equilibration of moisture between the inner layer and gazoballonnym layer by direct application. When gazoballonnyj layer is in direct contact with the paper or cardboard layer, the result will be such that the moisture from adhesibility layer. The result is a lower moisture content will remain in the polyamide layer, resulting gazoballonnyj properties are better kept in gazobetona layer in this particular case.

This unexpected increase coloradobrianna properties does not cover all of the polyamides. This is true only for Nylon-MXD6 and possibly due to the fact that gazoballonnyj properties of Nylon-MXD6 reduced at relatively high humidity, as is usually the case when packaging liquid food products.

Gazoballonnyj layer can of course be applied to any desired thickness, but according to a preferred variant implementation of the invention, which is particularly suitable for packaging containers for fruit juices with increased storage life on the shelf, gazoballonnyj layer deposited on the inner layer in the amount of approximately 3-30 g/m2more preferably 4-12 g/m2and more preferably 5-8 g/m2. The reason for this is that when the amounts of deposition of below 5 g/m2can cause a lot of instability in the process for applying and barrier properties. When the amounts of deposition of about 8 g/m2the packaging laminate becomes less economical.

Worn polyolefin layer, attached to getbasename layer via a layer of adhesive polymer applied between gazoballonnym layer and the polyolefin layer. The polyolefin layer may contain various types of polyolefins, for example polyethylene, ultra low density (ULDPE), low density polyethylene (LDPE), linear density polyethylene (LLDPE) and metallocene polyethylene (m-PE), or mixtures thereof. In particular, m-RE and a mixture of m-D and some of visherskiy types of polyethylene provide an exceptionally tight seal when TermoSanitari packaging material in the finished packaging containers that are favorable gas-tight packaging container. The gas impermeability of the packaging container, thus, depends on the permanence of the packaging material itself and how tight seals are obtained in the production of packaging containers from the packing material.

The layer of adhesive polymer located between gazoballonnym layer and polyolefin layer consists, for example, of polyolefin modified with carboxylic acid groups, for example of polyethylene grafted with maleic acid anhydride, such as some types of Admer

The purpose of the two outer polyolefin layer consists, on the one hand, the protection of the packaging material from moisture and liquids from the outside, but on the other hand, in the key functionality of the material printed by the traditional, so-called heat sealing, with mutually facing layers of plastic while providing heat and pressure can be connected together by means of surface melting. TermoSanitari provides a mechanically strong, gigaplane tight connection in the process of making a packing material in the packing containers. To ensure sealing with good tightness, the inner polyolefin layer is applied in the amount of approximately 15-35 g/m2preferably about 25-30 g/m2and the outer polyolefin layer in the amount of approximately 12-20, preferably 15-20 g/m2. In the presence of LDPE in the inner layer should be at least about 25 g/m2preferably at least about 30 g/m2. The inner polyolefin layer 13 can also be applied as two or more separate polyolefinic layers consisting of the same or different types of polyolefins, if the and packing material from the side of the inner layer, which in the finished packing container should be facing outwards, can be provided with an appropriate seal decorative and/or informative for the identification of the packaged product.

According to a third preferred variant implementation of the invention provides a packaging laminate having improved sealing properties in the process of turning into a packaging container. It was found that it is important to have a certain minimum thickness/density of the two outer thermoplastic layers of the laminate to achieve optimal durable, gas-tight seals and reduced swelling. This, in particular, it is obvious for a laminate with a three-layer barrier film co-extrusion. In such a three-layer laminate included less recovering plastics, and increases the risk of swelling. It is observed that for increasing the durability of the seals and reduce bloating the number of the sealing polymer in the inner layer, that is, low-density polyethylene (LDPE) on the inner side of the packaging laminate should be at least 25 g/m2when the polyamide barrier layer and the binder layer is applied in amounts of about 6 and about 3 g/m2accordingly, toga, there must be a certain relationship between the total number recovering polymer on the inner side of the cardboard and the amount of polymer on the outer side of the cardboard. Due to the improved seal strength and tightness of sealing compounds in relation to liquids and gases in the future receive a packing container with improved retention of vitamin C in the packaged product. In the laminate can penetrate less moisture through the seal, which leads to increased resistance to bulging of the container walls. By proper regulation of the quantities of the outer polyolefin layers so that the amount of LDPE in the inner layer comprised of at least 25 g/m2preferably 30 g/m2and the number in the outer layer was less than 20 g/m2preferably about 16 g/m2, the barrier layer is applied in the amount of 5-8 g/m2and the binder layer is applied in the amount of 3-6 g/m2you can save improved properties. This effect can also be seen for five-layer laminates, however, these quantities are not as significant as for the three-layer laminates. Quite suddenly, however, a three-layer laminate has an improved durability of the seals and improved high number recovering polyolefin laid on the inner side of the inner layer towards the product.

According to the fourth preferred variant implementation of the invention provides an economical packaging laminate having extended the storage life on the shelf together with the properties of the retention of aroma and taste, the so-called properties of netslaves.

Material Nylon-MXD6 in itself also has an excellent "aromatherapie properties, i.e. barrier properties towards aromatic and flavoring substances, the so-called properties of netslaves.

Also improve gazoballonnyj properties of this preferred laminate and retention of vitamin C in the packaging laminate product. These tasks are achieved through the packaging laminate having a first barrier layer deposited on the inner side of the cardboard material of the inner layer, and a second barrier layer comprising a blend of Nylon-MXD6 and a second semi-crystalline polyamide, additionally marked inward and to the packaged product, and a relatively thin binder layers and the polyethylene layer in contact with the product, between the inner barrier layer and packaged product. Because fewer polyolefin polymers applied as the Usovo and aromatic substances from the product in the packaging material. Aromatic and flavoring substances will be transported in a relatively thin layer in contact with the product, but when they reached the barrier layer from a mixture of Nylon-MXD6 and the second crystalline or semi-crystalline polyamide, their further migration will be prevented and, accordingly, less of these substances will be absorbed in the polyolefin layers. Because the inner plastic layer is quite thin in this preferred packaging laminate, it will be insufficient for formation of a sealing connection with the conversion and the sealing of the laminate in the packing container. Therefore, use of additional sealing layers of thermoplastic polymer on the inner side of the inner layer, on the other side of the innermost barrier layer, i.e. between the first and second barrier layers. When sealing a fairly thin layer in contact with the product, and the inner barrier layer will be "welded across the thickness, i.e. the polymers in these layers will be melted and the heat will reach and melt the intermediate layers thermostatically polymers. Thus, more heat sealable polymer is This the preferred packaging laminate is highly effective for extending the storage life on the shelf will be, of course, also have the advantage that gazoballonnyj layer is in direct contact with the cardboard, providing gazoballonnyj layer is improved by 30-40% due to the low moisture content in gazobetona layer.

According to an additional object of the invention is provided a method of manufacturing a packaging laminate according to the invention, as set forth in paragraph 14 of the claims.

The laminated packaging material according to the invention is preferably produced by the one-stage process of joint extrusion, in which all polymer layers on the inner side of the inner layer applied thereto through co-extrusion. Heat sealable polymer may be applied to the outer side of the inner layer, i.e. the side of the inner layer, facing to the side facing away from the barrier layer, before or after the specified one-stage process of joint extrusion. One important advantage of the joint extrusion is that the heat from the molten polymer will be better preserved in the extruded multilayer film, while the extruded film will not affect the substrate to which it is applied by extrusion, such obrasilo is that saves an additional step of the extrusion process, thus providing more time efficient and more economical process.

To obtain sufficient adhesion between the multilayer jointly extruded film and cardboard material, the surface must be activated by pre-treatment such as corona treatment and/or processing of flame or ozone. Such processing methods for surface activation are well known in the prior art. Preferably cardboard material pretreated by processing the flame and/or corona treatment, which treatment is most preferred flame, while just extruded film is preferably treated with ozone before applying it to the cardboard.

Configuration stable packaging container produced from the laminated packaging material of the present invention, is disclosed in the accompanying paragraph 16 of the claims. Packaging container according to the invention can be provided with an opening device, the opening/closing device known specialist in the field of packaging for liquid food products.

Primuses productive packaging material, demonstrating good gazoballonnyj properties, in particular against gaseous oxygen, even when exposed to a humid environment. The packaging material according to the invention also has good internal cohesion, to resist delamination when using the packaging material for the production of packaging containers for liquid food products, in particular fruit juices with the so-called extended period of storage, i.e. for cold storage for up to 4-12 weeks.

A brief description of the accompanying drawings the Present invention will now be described in more detail using embodiments and with reference to the accompanying drawings, in which: Fig. 1A, 1b and 1C views in cross section of the laminated packaging material according to the invention; Fig.2A, 2b and 2C schematically show the method of execution of packaging material described in accordance with Fig.1, and Fig. 3 is a side view in perspective of the traditional stable configuration of the packaging container produced from the laminated packaging material according to the invention.

Detailed description of the invention Referring to Fig. 1A shows in cross section a preferred luiziana hard, but flexible inner layer 11 of paper or cardboard. On one side of the inner layer 11 applied gazoballonnyj layer 12 polyamide of a mixture of Nylon-MXD6 and RA-6 or preferably Nylon Clay Hybrid (NCH) on the basis of the RA-6. The amount of Nylon-MXD6 polyamide fibre mixture is preferably 60-90% by weight of the mixture, more preferably 70-80% by weight, and the amount of polyamide mixture in gazobetona layer is preferably 5-10 g/m2.

It has been proven that gazoballonnyj layer 12 containing a mixture of Nylon-MXD6 and RA-6 or NCH, very well glued to the inner layer 11 of paper or cardboard. It was proved that, compared with lamination gatbering layer 12 on the inner layer 11 with an intermediate layer of polyethylene, application gatbering layer 12 directly on the inner layer 11 leads to a 30-40% improvement in barrier to gaseous oxygen.

On the side gatbering layer 12, is turned to the side, facing away from the inner layer 11 deposited polyolefin layer 13, which is attached to getbasename layer 12 by a layer 14 of adhesive polymer applied between gazoballonnym layer 12 and the polyolefin layer 13. The polyolefin layer 13 is preferably a LDPE or m-RE, or their mixture and put in kolichestvennogo by grafting maleic anhydride, and applied in an amount of about 3-6 g/m2. The outer layer 15 on the opposite side of the inner layer is also preferably a LDPE or m-RE, or a mixture of these two polymers and applied in amounts of preferably at least 15 g/m2.

Referring to Fig. 1b shows a view in cross section of another preferred laminated packaging material 10b according to the present invention. Packaging material 10b contains the configuration hard, but flexible inner layer 11 of paper or cardboard. On one side of the inner layer 11 applied gazoballonnyj layer 12 polyamide of a mixture of Nylon-MXD6 and RA-6 or preferably Nylon Clay Hybrid (NCH) based on PA-6. The amount of Nylon-MXD6 polyamide fibre mixture is preferably 60-90% by weight of the mixture, more preferably 70-80% by weight, and the amount of polyamide mixture in gazobetona layer is preferably 5-10 g/m2.

On the side gatbering layer 12, is turned to the side, facing away from the inner layer 11 deposited polyolefin layer 13, which is attached to getbasename layer 12 by a layer 14 of adhesive polymer applied between gazoballonnym layer 12 and the polyolefin layer 13. The polyolefin layer 13 preferably is of the . Adhesive layer 14 is made of polyethylene, modified by grafting maleic anhydride, and applied in an amount of about 3-6 g/m2. The outer layer 15 on the opposite side of the inner layer is also preferably a LDPE or m-RE, or a mixture of these two polymers and applied in amounts of preferably at least 15 g/m2.

Gazoballonnyj layer 12 attached to the inner layer by an intermediate layer of adhesive polymer layer 16 and a polyethylene layer 17 and the adhesive polymer layer 16 is adjacent to gazoballonnym layer 12 and made of the same polymer and approximately the same thickness as the adhesive polymer layer 14, and the polyethylene layer 17 made of the same polymer and approximately the same thickness as the layer 13.

Referring to Fig.1C shows a view in cross section of another preferred laminated packaging material 10C according to the present invention. Packaging material 10C contains the configuration hard, but flexible inner layer 11 of paper or cardboard. On one side of the inner layer 11 applied gazoballonnyj layer 12 polyamide of a mixture of Nylon-MXD6 and RA-6 or preferably Nylon Clay Hybrid (NCH) on the basis of the RA-6. The amount of Nylon-MXD6 in icesto polyamide mixture in gazobetona layer is preferably 5-10 g/m2.

On the side gatbering layer 12, is turned to the side, facing away from the inner layer 11 deposited polyolefin layer 13', which is attached to getbasename layer 12 by a layer 14 of adhesive polymer applied between gazoballonnym layer 12 and the polyolefin layer 13'. The polyolefin layer 13' is preferably a LDPE or m-RE, or their mixture, and put in the quantity, preferably comprising at least 15-20 g/m2. Adhesive layer 14 is made of polyethylene, modified by grafting maleic anhydride, and applied in an amount of about 3-6 g/m2. The outer layer 15 on the opposite side of the inner layer is also preferably a LDPE or m-RE, or a mixture of these two polymers and applied in amounts of preferably at least 15-20 g/m2.

On the side of the polyethylene layer 13', turned to the side, facing away from the inner layer 11 deposited second layer 12' having barrier properties against gases and aromatic substances by means of an intermediate bonding layer 17'. Alternatively, in the case of joint extrusion of all layers in a single operation extruding, plastic layers 13' and 17' actually nanese the t of the inner layer 11, caused the innermost polyolefin layer 18, which is attached to getbasename layer 12' by means of a layer 14' of adhesive polymer applied between gazoballonnym layer 12' and the polyolefin layer 18. The inner layer 18 should be quite thin, to prevent too large yield of aromatic and flavoring substances of the packaged product in the packaging material. Preferably, this layer should be applied in an amount of about 6 to 12 g/m2preferably at most 10 g/m2and more preferably in an amount of about 7-9 g/m2.

The adhesive polymer layers 16' and 14' include the same polymer as the adhesive polymer layer 14, and should have a thickness of 3-5, preferably 4 g/m2whereas polyethylene layer 17' comprises the same polymer and has approximately the same thickness as the inner polyethylene layer 18.

The advantage of the laminated packaging material according to Fig.1C is that the polyolefin layers 14' and 18 on the inner side of the laminate with gas and aromata-barrier layer 12' to prevent the transfer of non-polar substances from the packaged product in the packaging material, as a thin polyolefin layer becomes saturated with the second laminate.

The sealing properties of the laminate will still be wonderful, since the intermediate polyolefin layers 13' and 17' together with adhesive layer 16' provides lots of heat sealable polymer, which offsets the amount of heat sealable polymer that is not in the inner polymeric layer 18. Under the application of heat and pressure along the sealing zones of the barrier layer 12' becomes welded across the thickness, thus involving massive layers 13' and 17' in the operation of sealing the sealing.

When using two gazoballonnyj layers of polyamide mixture of Nylon-MXD6 and RA-6 or preferably NCH gazoballonnyj properties will be further improved. In addition, the rigidity of the laminate will increase due to the relative rigidity of the polyamide layers and that they are separated from each other by layers of less rigid materials (creating the so-called I-beam effect), which can improve the appearance of the package, or even to allow the execution of the inner layer is less rigid. The swelling effect will be reduced accordingly in this material due to the high hardness of the packaging laminate.

Fig. 2A schematically shows a production method of the laminated packaging material tajnosti, where the surface is activated by a corona treatment and/or processing a flame, preferably processed by the flame. Layers 12, 13 and 14 together ekstragiruyut 22 in this order through the production of three-layer film in the supply node 22, and the film 24 is fed through the cylinder 23 through an air gap between the head and cardboard material. The surface layer 12 is directed to the surface of the cardboard, preferably activated in the air gap by means of the handle 25 ozone. Jointly extruded and still hot, molten multilayer film 24 serves together with a cardboard canvas roller clamp 26, thus sticking by pressure and heat from the polymer layers. It is important that the number of jointly extruded polymer is high enough to maintain sufficient heat before it will come into contact with a cardboard material. This is the usual case, if three layers 12, 13 and 14 together ekstragiruyut on the canvas. However, the joint extrusion only layers 12 and 14, for example, will be less preferred because of the two-layer jointly extruded film is then cooled down very quickly and will not be warm to prick the layer by covering extrusion, turned to the side, facing away from gatbering layer 12, either before or after covering the joint extrusion shown in Fig.2A.

Fig.2b schematically shows a production method of the laminated packaging material according to Fig.1b.

In addition to the described three-layer structure on the inner layer 11 described in Fig.1A, it is also possible without leaving the scope of the present invention to provide a laminate structure containing four and five layers of laminated inner layer 11. The four-layered structure then has a layer in contact with the adhesive layer between the inner layer and gazoballonnym layer 12. In the case of a five-layer structure, as shown in Fig.1b, the polyolefin layer 17 and the adhesive layer 16 is applied between the inner layer 11 and gazoballonnym layer 12, and the polyolefin layer 17 is then located adjacent the inner layer 11. These multilayer structures, however, are more expensive to manufacture because it is used more material. This method, moreover, is less favourable to the environment than the production method of three-layer structures as described in Fig.2A.

Preferably the laminate according to Fig.1b is produced through co-extrusion is the real inner layer 11 is moved and passes 21 surface activation, where the surface is activated by a corona treatment and/or processing a flame, preferably processed by the flame. The layers 17, 16, 12, 14 and 13 together ekstragiruyut 22 in this order, thereby providing a multilayer film 24' through the cylinder 23, and the layer 17 is directed to the surface of the cardboard. Jointly extruded and still hot, molten multilayer film 24' is treated to activate the surface with ozone 25 and then served with a cardboard canvas roller clamp 26, thus sticking them together by pressure and heat from the polymer layer.

Alternative five layers on the inner side of the inner layer can be applied in two stages, i.e. first through the joint extrusion of the layers 17, 16, 12 and 14 on the cardboard in the first stage and then covering extrusion layer 13 layer 14 in the second stage, or by first extruding a layer 17 on the inner layer in the first stage and then the joint extrusion of the four layers 16, 12, 14 and 13 on the newly deposited layer 17 in the second stage. These alternative methods will, however, enable a more difficult and less efficient process of lamination.

The polyolefin layer 15 may be caused to poreo layer 12, either before or after applying the extrusion shown in Fig.2b.

Fig.2C schematically shows a production method of the laminated packaging material according to Fig.1C.

According to one variant of implementation for the case when will be provided seven-supply node, the laminate according to Fig.1C is produced through co-extrusion of the seven layers 12, 14, 13', 17', 16', 12', 14' and 18 on a cardboard canvas 11 in a manner analogous to the methods of Fig.2A and 2b.

According to a preferred variant of execution of the layers 12, 14 and 13' together ekstragiruyut on a cardboard canvas in the first stage, and layers 17', 16', 12', 14' and 18 cover the joint extrusion layer 13' in the second stage. Thus, the canvas cardboard material of the inner layer 11 is moved and passes 21 activate the surface, where the surface is activated by a corona treatment and/or preferably processed by the flame. Layers 12, 14 and 13' together ekstragiruyut in the supply node 22 in that order, producing a three-layer film 24" supplied through the cylinder 23 through an air gap between the head and cardboard material. The surface layer 12 of the multilayer film 24" towards the surface of the cardboard. Just before he is to contact the local extruded and still hot, molten treated with ozone multilayer film 24 serves together with a cardboard canvas roller clamp 26, thus sticking them together by pressure and heat from the polymer layer.

In the second stage layers 17', 16', 12', 14' and 18 cover the joint extrusion 22' on the laminate produced in the first stage in the form of a five-layer film 24"'. Alternate multilayer film of only four layers 16', 12', 14' and 18 ekstragiruyut on the laminate produced in the first stage. Jointly extruded and still hot, molten multilayer film 24"' may handle to activate the surface ozone and served with covered cardboard canvas 11' by a roller clamp 26', thus sticking them together by pressure and heat from the polymer layer.

The polyolefin layer 15 may be applied by covering the joint extrusion on the side of the inner layer, facing to the side, facing away from gatbering layer 12, either before or after applying the extrusion shown in Fig.2C.

Laminated packaging material 10 of the present invention can be produced gigaplane, stable configuration package 30 having good barrier properties is ararauna process form, fill and seal packaging material in the form of a sheet or fabric in the finished packing 30. An example of such a conventional packaging container shown in Fig.3.

Packaging container according to the invention can be provided with an opening device 31, and such opening/closing device commonly known in the field of packaging liquid food products.

The process of making the laminated packaging material in the packaging containers can be achieved by, for example, the first connection of the longitudinal edges of the laminated packaging material 10 in the form of a sheet, a pipe, which fill the desired content, then a separate package 30 is shared by several transverse joints of pipe below the level of content. Packing 30 is separated from each other by cutting in the areas of the transverse sealing and get the desired geometrical configuration, usually parallelepipedal by the end of the process flexion-education and sealing. Alternative packing 30 may be provided by bend-forming sheets in cardboard blank, which is then filled and closed with the formation of the finished package.

For specialname, but various modifications and changes can be made without leaving the scope of the concept of the invention defined in the attached claims. For example, the structure of the material, shown in Fig.1, usually not limited to the shown number of layers, and this number may be more or less, and may be freely changed in accordance with the desired use of the packaging material.

Example 1 Comparison of barrier properties: different polyamide coloradoonline layers
The measurements were carried out on the finished structures of the packaging material, i.e. jointly extruded 5 layer structures (g/m2):
LDPE (13)/cardboard/ LDPE (10)/binder (5)/PA (barrier) (6)/binder (5)/LDPE (25).

Coating weight of the barrier layer 6 and 10 g/m2respectively. RE: standard RA-6 brand V company UBE Industries Selar PA3508: amorphous polyamide.

The permeability of oxygen gas RA when using only gazobetona layer is about the same as Selar PA at 0% RH, but higher at high relative humidity. Selar RA or RA as only hashbarger, thus, is not of interest from the economic point of view for ESL packaging.

Methodology the test program the samples) =5 (see table. 1 in the end of the description).

Conclusions: the mixture of Nylon-MXD6/PA6 has the best coloradoonline properties than amorphous RA. A mixture of Nylon-MXD6 with malono-ceramic hybrid (NCH-PA6) has the best coloradoonline properties than the corresponding mixture of Nylon-MXD6/PA6 with standard brands RA. Although the value of hashbarger were obtained for the laminate with 100% Nylon-MXD6 gazoballonnyj layer, the laminate cannot be used in practice as gazoballonnyj layer will crack and flake and will allow oxygen to penetrate into the packaging container made from it. A mixture of Nylon-MXD6 with 80 wt.% Nylon-MXD6 has the best gazoballonnyj properties than the corresponding 60% of the mixture. Although it is not shown in these examples, it was found in other tests, the optimal balance between getbasename properties and mechanical properties of packaging from the laminate obtained in the presence of about 70-80 wt.% Nylon-MXD6 in the mixture. If more than 90 wt.% Nylon-MXD6 barrier layer becomes more brittle and inflexible and, therefore, more prone to cracking and delamination.

Example 2
The quality of the mixture of Nylon-MHR - polyamide:
The influence of different melting temperatures in the preparation of Nylon-MHR-RA mixture
To obtain two-phase carried the measurement, these polymers should be mixed with a low melting temperature within a relatively short time of mixing and the use of low shearing forces. In practice, the granules of different polymers are mixed dry, and then melt mixed in the extruder feeding the polymer to the extrusion head. A two-phase mixture provides the best coloradoonline properties than the single-phase mixture type.

The following observation was made in experiments on a small scale with the same extrusion equipment and head. The permeability tests were performed on single-layer extruded film (20010% microns).

Methodology: Mocon oxtran, the method 1000 flat samples, test gas: 100% oxygen, T= 23oC, t=24 h, RH: 50%, 1 ATM, n (number of samples)=5 (see tab. 2).

Conclusion: the film produced at a lower melting temperature of the mixture had more than 100% best coloradoonline properties than film with a high melting point of the mixture, showing that the mixing at a higher temperature provides a mixture of more mixed type.

Example 3
Comparison of barrier properties: 3-layer structure against five-layer
The dimension of the structures homostructure (g/m2):
LDPE(16)/cardboard/LDPE(15)/binder (5)/RA-mix(7)/
binder(5)/ LDPE(20).

3-layer structure (g/m2):
LDPE(16)/cardboard/RA-mix(7)/binder(5)/LDPE(20).

the polyamide mixture: 7 g/m2, 75% MXD6+25% PA6-NCH.

Methodology: Mocon oxtran, the method 1000 flat samples, test gas: 21% oxygen, T=23oC, t=24 h, RH: 80%, 1 ATM, n (number of samples)=2 (see tab. 3).

Conclusion: the 3-layer structure provided on 40% of the best coloradobased than 5-layer structure.

Example 4
The effect of the weight ratio between the outer polyethylene layers and their weight densities
Swelling was measured in two separate tests after 10 weeks of storage when cooled, each test contains 10 packs filled with orange juice, the width between the walls of the packaging container has exceeded 78 mm the Values shown in the table represent the number of millimeters, exceeding or falling below the value for reference package which has the structure:
LDPE (16)/cardboard/ LDPE (15)/ binder (5)/ EVOH (5)/ binder (5)/ LDPE (20).

Similar structure with gazoballonnym layer of 75:25 Nylon-MXD6 blends with RA NCH has almost the same properties of bulges as EVOH reference sample (measured in other tests).

The frequency of leaks of isbale for 15 minutes, n (number of packages)=160.

Test laminates (g/m2):
LDPE (16)/cardboard/75: 25 MXD6:PA6NCH (6)/binder (3)/ LDPE (X). Next, see table. 4A, 4B.

Conclusion: there is less leakage when the amount of polymer (barrier+binder+LDPE) on the inner side is high.

Conclusion: the Swelling is reduced, when the amount of polymer on the outside is low, but on the inside is high.

To maintain the level of swelling three-layer laminate at the same level or below the level of the reference five-layer laminate amount of LDPE in the inner layer should be at least 25 g/m2preferably at least 30 g/m2. Outer LDPE layer should be less than at least 20 g/m2preferably about 16 g/m2. At a density less than 16 g/m2the printing application of the external decorative layer may deteriorate.

Test results of the swelling showed that when applying a thick inner layer on the continuous outer layer getting smaller the swelling. Unexpectedly, however, while maintaining the internal number is high and external low number of three-layer structure shows less bloating than patellifolia inside the double-wall cardboard laminate above, a total of 45 g/m2(despite the fact that the total internal polymer in the five-layer laminate is 50 g/m2).


Claims

1. The laminated packaging material containing an inner layer of paper or cardboard and gazoballonnyj layer constituting the polyamide mixture containing the condensation polymer methoxyaniline and adipic acid and a crystalline or semi-crystalline polyamide with a mass ratio of 60-90: 40-10, preferably 70-80:30-20 respectively, deposited on one side of the inner layer together with at least one layer of heat sealable plastic-polyethylene by means of co-extrusion.

2. The laminated packaging material under item 1, characterized in that the polyamide blend is a two-phase immiscible composition, for which the DSC measurement shows two melting interval.

3. The laminated packaging material under item 1 or 2, characterized in that the crystalline or semi-crystalline polyamide is a polyamide-6.

4. The laminated packaging material according to any one of paragraphs.1-3, characterized in that the crystalline or semi-crystalline polyamide having presented the point characterized in that gazoballonnyj layer applied directly by joint extrusion of the inner layer of paper or cardboard without any intermediate lamination or adhesive layer.

6. The laminated packaging material according to any one of the preceding paragraphs, characterized in that gazoballonnyj layer applied in the amount of approximately 4-12 g/m2more preferably 5-8 g/m2.

7. The laminated packaging material according to any one of the preceding paragraphs, characterized in that the other side gatbering layer, facing away from the inner layer attached to the plastic layer by an intermediate layer of adhesive polymer of polyethylene grafted with maleic acid anhydride.

8. The laminated packaging material according to any one of paragraphs.1-7, characterized in that the other side of the inner layer, facing away from gatbering layer, optionally covered with an outer layer of polyethylene.

9. The laminated packaging material according to any one of paragraphs.1-8, characterized in that the outer plastic layer is applied in the amount of 15-20 g/m2and the amount of polyethylene in the inner layer is at least 25 g/m2preferably 30 is first gazoballonnyj layer and the second gazoballonnyj layer, printed on one side of the inner layer, both gazoballonnyj layer consist essentially of a polyamide mixture of condensation and the second crystalline or semi-crystalline polyamides.

11. The laminated packaging material according to p. 10, characterized in that the innermost layer of polyethylene applied in an amount of about 7-9 g/m2.

12. The production method of the laminated packaging material, which together ekstragiruyut a multilayer film including gazoballonnyj layer and a layer of heat sealable plastic under item 1, the pre-treated surface of the paper or cardboard for its activation, pre-treated with ozone contact surface of the multilayer film and then glued pre-treated surface with each other by application of pressure.

13. The method according to p. 12, characterized in that the paper or cardboard is treated to activate the surface by corona discharge or flame, and the side of the layer in contact with the paper or cardboard multilayer film is treated with ozone.

14. Hard to form a packaging container for storing liquid food products which are sensitive to gaseous oxygen for an extended period generowania packaging material according to any one of paragraphs.1-11.

 

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