Laminated packaging material, method of producing laminated packaging material and packaging container made from said material
SUBSTANCE: invention relates to production of packaging materials for food products and beverages, particularly barrier films, laminated packaging materials and packaging containers. The barrier film has a base polymer film and a barrier layer containing an inorganic oxide deposited on the base film via gas-phase deposition. The layer of inorganic oxide is additionally coated with a healing layer of cross-linked organopolysiloxane which is covalently bonded with the inorganic layer. The laminated packaging material has a barrier film. The packaging container is made from said barrier film.
EFFECT: packaging material has good barrier properties with respect to oxygen and water vapour, improved strength and softness.
23 cl, 9 dwg, 5 ex
The invention relates to a barrier film for packaging food or beverages, including basic polymer film and deposited on the main film barrier layer containing inorganic oxide deposited from the gas phase. This invention also relates to laminirovannom packaging material for packaging of food products and beverages, including such barrier film, and packaging containers produced from the laminated packaging material. In addition, this invention relates to a method of manufacturing a barrier film according to the invention.
To increase shelf life, i.e. the period of time during which the food product before use can be stored in a tightly sealed and stored in a packaging container, the packaging of food products and beverages, it is important to minimize the influence of gases, vapors and light passing through the packing material is Packed food product from the environment surrounding the packing container. The packaging process can be performed in sterile conditions, i.e. the food product and the packaging material as it protects from bacteria, getting filled packing container in a clean environment, thus the correct choice and selection of the composition of the packaging material causes in the possibility of storing food for a very long period of time, even when it is stored at room temperature. One of the important storage for a long period of time factors are gazoballonnyj properties filled and hermetically sealed packaging container, which, in fact, largely depend on gazoballonnyj properties of the laminated packaging material as such. Oxygen has a detrimental effect on the nutritional value, accelerating the degradation of the food product. In addition, when stored for a long period of time in order Packed content remained the same volume and humidity, as with the original packaging, an important factor is satisfactory barrier properties of the laminated packaging material in relation to water vapor.
Depending on storage duration and type of the packaged product are also important barrier against transfer of odorous polar and nonpolar substances. In particular, such properties are extremely significant for fruit juices. The integrity of the laminated material, the inner adhesion between layers of the laminated material after storage for a long period of time and under adverse climatic conditions, is very important for the overall operate the operating qualities of the laminated packaging material.
In the prior art to provide such functional characteristics related to gazoballonnym properties, in particular kisloroddonornymi properties, barrier properties against water vapor and sweetbriers properties, have been proposed various film and laminated packaging materials. Such films and soft laminated materials are used as wrapping materials, containers and bags for packing of various food products. In particular, liquid or flowable food products such as milk and representing the juices drinks or tomato paste can be packaged in such soft materials using processes high-speed continuous filling, forming and hermetic sealing. With this method continuously unwinding the roll of the laminated material is formed into the shape of a continuous tube, sterilized and filled food product is hermetically sealed and Packed. Hermetic sealing is carried out by heating the outer polymeric layers of the laminated material, so that such external hermetically sealed by heat layers irreversibly joined to each other while applying pressure with the formation of a hermetically sealed package or container in the form of POTUS is I.
Similar rigid or semi-rigid containers of the disposable type for single use for liquid food products are often made from laminated packaging material with an inner layer of paper or cardboard. One such common packaging containers sold under the trade name Tetra Brik Aseptic® and is used mainly for liquid food products, such as milk, fruit juices, etc. Such packaging containers Tetra Brik Aseptic®, as a rule, also manufactured using modern high-speed packaging machines of that class which are formed, filled and hermetically sealed packaging containers obtained from a roll or from prefabricated blanks of packaging material. For example, packaging containers from a roll is made so that the roll into a tube by connecting with each other both axial ends of the roll in the overlap. Tube fill with the desired liquid food product and is divided into individual packaging containers recurring cross zapaivanie tube at a distance from each other below the level of the contents in the tube. Packaging containers is separated from the tube, producing an incision in the transverse hermetic spinach, and ask for them desired GE the metric configuration, usually geometrical configuration of a parallelepiped, bending along the prepared kinks on the cardboard packaging material. The main advantage of the ideas this continuous packaging process, including the formation, filling and hermetic sealing of the tube, is that the roll can be continuously sterilized immediately before the formation of the tube, thereby causing the possibility of sterile packaging process, so that the filled packaging container can be stored for a long period of time even at room temperature without the risk of microbial growth in the filling of the packaging container product. Another important advantage of the packaging process of the Tetra Brik® is the possibility of carrying out a continuous high-speed packaging with the help of modern packaging machines, which has a significant impact on economic efficiency.
Packaging material for such a well-known rigid packaging container is usually a laminated material including surround the inner layer of paper or paperboard and outer, impermeable to fluid layers of thermoplastics. To make the packaging container of light - and gas-tightness, in particular gas-tightness with respect to oxygen, voltage is emer, for sterile packaging and packaging of fruit juices, laminated material for packaging containers typically contains at least one additional layer, most often representing an aluminum foil.
The use of laminated packaging materials with gas-tight barrier layer of aluminum foil for some purposes, for example for packaging food products, which are designed for cooking, heating or defrost in the microwave, is associated with some disadvantages. In these cases, the laminated packaging material must be removed before the food product is exposed to microwaves. Another disadvantage of using aluminum foil is that it is quite expensive compared to many other barrier materials.
Polymer film coated with a deposited from the gas phase inorganic oxides of nanometer thickness are widely used in industries related to food packaging, as protects from the effects of oxygen and/or water vapor barrier layers. Especially interesting is associated with the food packaging industry are glassy layers of nanometer thickness substances with the formula Si xor SiOxCythat can be applied in any way reactive evaporation. Other points representing inorganic oxide barrier substances used in the food packaging industry, are aluminum oxide (AlOx). In addition, a thin metallic layers of nanometer thickness are often used to create a laminated packaging material of the barrier layer that prevents oxygen and water vapor, such as containing aluminum metallized layers. However, compared with aluminum foil such coatings have the worst barrier properties and less softness.
A typical problem of all kinds of deposited from the gas phase layers associated with the emergence of small-diameter holes, cracks and other defects with sizes in the range from nanometers to micrometers. Such defects cause residual penetration of nutrients, especially oxygen, through containing layer of SiOxthe laminated packaging material, which is typically greater than 0.1 cm3/m2/day/ATM, and water vapor, which is typically greater than 0.1 g/m2/day. To some extent these cracks and defects initially present in the material from the top of the mixture sadeniemi gas phase coating, but mostly they appear as a consequence of thermal and mechanical stresses that arise during operations associated with the manipulation and processing of the laminated material when forming the film or the laminated material, as well as during thermocline conducted for the hermetically sealed packaging, and, of course, manipulation and distribution of filled and sealed packaging containers. Particularly significant heat stress thin deposited from a gas phase barrier layer reported by extrusion lamination using hot molten polymer, and the process associated with termocline. In short, to save a layer intact and to provide the desired barrier properties of the resulting filled and sealed packaging container, it is necessary that all kinds of deformation of the thin deposited layer does not exceed a certain limit. Although in many cases this limit is satisfactory, there is a need to improve the operational reliability in relation to the barrier properties of such films.
One possible way of overcoming, to some extent, this problem is to use the basic polymer films about the Yan smooth and uniform surface to reduce the number of defects in the oxide layer. However, this approach does not improve the quality of the coating on the outer surface of the inorganic layer.
For soft wrapping materials and materials for packages, as well as the more rigid laminated packaging materials of paper or cardboard, the requirements for softness and durability inorganic barrier material during the stretching of the film or the laminated material is very high. In particular, in the case of cardboard or packaging containers made of cardboard barrier material is exposed to extreme conditions under which happen bending and flexing of thick laminated cardboard several times in the same place of the laminated material. This happens in some parts formed by bending the packaging container, e.g., in the so-called K-folds, where the laminated material to obtain the upper and lower parts of the packaging container in the form of a parallelepiped bend more than once. Thus, there is a need to improve the durability and softness like caused by deposition from the gas phase inorganic layers, and their barrier properties.
DISCLOSURE of INVENTIONS
In view of the above objective of the present invention is to overcome or reduce the above problems./p>
The main purpose of this invention is to provide film for packaging food or beverages with improved barrier properties, which precipitated from the gas phase layer comprising deposited on the core layer polymer inorganic oxide.
Additional main purpose of this invention is the provision of a film for packaging food or beverages with improved strength and softness, having deposited from the gas phase layer comprising deposited on the core layer polymer inorganic oxide.
The specific objective of this invention is to provide film for packaging food or beverages with improved barrier properties against oxygen and water vapor, as well as improved strength and softness, having deposited from the gas phase inorganic layer of silicon oxide (SiOxor SiOxCy)deposited on the core layer polymer.
Another specific object of this invention is the provision of a film for packaging food or beverages with improved barrier properties against oxygen and water vapor, as well as improved strength and softness, having deposited from the gas phase with a layer of aluminum oxide (AlOx)deposited on the core layer polymer clay is A.
An additional objective of this invention is to provide a soft laminated packaging material for sterile packaging of food or drink for long-term storage with improved barrier properties and improved strength and elasticity, including the barrier film containing precipitated from the gas phase layer of inorganic oxide deposited on a base layer of polymer.
Another additional objective of the present invention is the provision of a rigid laminated packaging material or semi-rigid laminated packaging material for sterile packaging of the food or drink for long-term storage with improved barrier properties, strength and softness, and good integrity of the packaging container due to good adhesion between the barrier layer and the adjacent layer of polymer comprising a barrier film containing precipitated from the gas phase layer of inorganic oxide deposited on a base layer of polymer.
The invention is also aimed at the creation of the packaging container is filled with food product or drink, and made of a laminated packaging material comprising the barrier film.
In addition, this invention is directed to R. is this the method of manufacturing an improved barrier film according to the invention.
According to the present invention achieve these goals through the use of a barrier film, soft laminated packaging material and laminated packaging material for rigid or semi-rigid containers for food or beverage, and packaging container and method are such as defined in the attached claims.
Thus, these objectives according to the present invention achieve by applying an additional coating layer of inorganic oxide deposited from the gas phase, and the coating consists of stitched organopolysiloxane, linked by covalent bonds with the layer of inorganic oxide, and acts as a healing his (defects) layer.
The existence of such custom made has been out layer has particularly positive effects on strength, softness and barrier properties of deposited from the gas phase coating of silicon oxide, although positive effects are expected for any of inorganic oxides with chemical properties similar to those possessed by silicon oxides, such as oxides of aluminum, magnesium oxides, titanium oxides, and the oxides of other metals. When using metallic layers also achieve positive effects in terms of strength and barrier properties to the extent that it is some metallized layer contains a metal oxide on the surface layer and includes the Oh-group. For example, this often happens in the case of layers of aluminum caused by chemical reaction deposition from the gas phase. Typically, a thin coating of pure metal or a mixture of metal oxide metal cause the barrier properties against water vapor and they are used when the required function is to prevent the penetration of water vapor in the laminated film or laminated packing material and through them. Most preferably, the metal of the metallized coating consisted of aluminum (Al), mixed with aluminum oxide (AlOx), in particular on the surface of the metallized layer. Such metallized layers of metal and metal oxide in addition give a metallic appearance and often also represent a barrier to light.
A coating of cross-linked organopolysiloxane associated with a layer of inorganic oxide covalent bonds, evenly and densely distributed on the interfacial boundary between the layer deposited from the gas phase inorganic oxide and a layer of organopolysiloxane.
Preferably, containing inorganic oxide coating applied by physical deposition from the gas phase (PVD) or reactive deposition from the gas phase (CVD), and preferably a plasma-chemical deposition from the gas the phase (PECVD), in which the vaporous metal or silicon compound is applied to the substrate in an oxidizing conditions, thus forming a layer of amorphous metal oxide or a layer of silicon oxide.
This type of coating causes gazoballonnyj properties with the coating film, and also, to some extent, the barrier properties against water vapor, and such coatings are transparent, which in some cases may prefer.
Particularly preferred coating is a coating of silicon oxide with the formula SiOxCywhere in the formula the carbon atoms are connected by covalent bonds, and x is from 0.1 to 2.5 and y can be in the range from 0.1 to 2.5. Such carbon-containing coatings have, in addition to gazoballonnym properties, good barrier properties against water vapor.
Another preferred coating is a coating of silicon oxide with the formula SiOxCyNzwhere the carbon atoms and the nitrogen atoms are connected by covalent bonds, and x is from 0.1 to 2.5, y is from 0.1 to 2.5, and z is from 0.1 to 2.5.
Preferably, the thickness of a single coating of SiOxCyNzranged from 5 to 100 nm and that it was caused by a PECVD method using a process gas mixture comprising kremniyorganika is some connection and nitrogen as the carrier gas.
The thickness of the thin-containing inorganic oxide layers according to the invention is deposited from the gas phase, is in the nanometer range, i.e. their thickness is most conveniently expressed in nanometers, which is, for example, from 5 to 500 nm, preferably from 5 to 200 nm, and more desirable from 5 to 100 nm.
Another preferred coating is a coating of aluminum oxide with the formula AlOxwhere x is from 1.0 to 1.5, preferably of Al2O3. Preferably, the thickness of such coatings ranged from 5 to 100 nm, preferably from 5 to 30 nm.
Thanks to the benefits in terms of cost indicators cost, and also get to cover effective against the barrier properties and softness, the coating method of plasma-chemical vapor deposition (PECVD) is preferred to obtain a coating of inorganic oxides, however, other methods of deposition from the gas phase, i.e. any way reactive sputtering or the way the reaction of the coating when exposed to a beam of electrons or any method of thermal spraying are also valid in the implementation of the present invention. Usually these methods are periodic processes which require reaction chamber with a reduced pressure or vacuum for the job, associated with reactive sputtering. In more detail the PECVD method described in US patent No. 5,224,441.
On the other hand, a coating method, which uses atmospheric plasma is also acceptable and desirable, as is a method for continuous formation of the coating, allowing easier control and optimization of manufacturing having a coating film. Other similar continuous and highly desirable way to create coatings by deposition from the gas phase at atmospheric pressure is the so-called method of flame coating or chemical deposition from the gas phase oxidation (CCVD).
The main polymer film includes a layer required to receive the damage done by deposition from the gas phase of a substance, and this layer consists of the right to receive functional substance layer with good adhesion and good quality coating. Accordingly, such a substance is a thermoplastic polymer substance with Tg(glass transition temperature)greater than or equal to -10°C. As a rule, these polymeric substances are more suitable for substrates in the case of exothermic processes in the formation of coatings, because they are at the same time have the other characteristics of melting behaviour than, for example, poly is tilen. Examples of such polymeric compounds with high values of Tgselected from the group consisting of polyamide (PA), polyamide copolymer, a complex of the polyester and copolymer complex of the polyester. Examples are polyethylene terephthalate (PET) and its copolymers (PET's), such as, for example, modified picolinate parts of polyethylene terephthalate (PET-G), polybutylene terephthalate (RHT) and polyethylenterephthalat (PEN). All these polymers have values of Tgabove room temperature. Polypropylene is also a polymer with the desired value of Tgthen there is a Tgabout component -10°C. Preferably, the main film or layer consisted of(a) polyethylene terephthalate (PET) or polyamide (PA), and most preferably from polyamide, since the polyamide provides a smooth surface for receiving applied by deposition from the gas phase coating, which improves the quality and properties of the coating. Practical requirements with respect to the thickness of the primary film can set the lower limit of the film thickness of about 10 μm, while the upper limit of the thickness of about 30 μm, it is reasonable for reasons of cost. Examples of suitable, but not limiting the invention polyamides are PA-6, PA-6,6 and PA-6,6,6. However, all polyamides, under adamie for the manufacture of films, are also suitable substrates for the film of the present invention.
Has been out with the coating layer is thus made of the reaction product formed in the composition comprising essentially unsaturated silanes with three silanolate groups. To obtain the results in the application of this invention it is important that the composition consisted essentially only of the unsaturated silanes and may contain only minor amounts of the corresponding saturated silane compounds. Such an insignificant amount should be less than 5 wt.% from the total mass Milanovich compounds such compositions, preferably less than 3 wt.%. Similarly, the composition may include minor amounts of unsaturated silanes possessing only two silanolate groups, but it should be less than 5 wt.%, preferably less than 3 wt.% of the total weight of the composition. In conclusion, it should be noted that the content different from the unsaturated silanes with three silanolate groups of silane should be less than 10 wt.% from the total mass selectarray compositions for coating.
Unsaturated reactive silane with three silanolate groups, as a rule, can be represented by the formula R-Si-X3, R is radical, which contains a functional group capable of polymerization by free radical mechanism, and X represents capable of hydrolysis of the radical. Typical substituents R may include gamma methacryloxypropyl, gamma Acrylonitrile, vinyl or allyl. Typical silanolate the substituents X may include acetoxy and alkoxy with 1 to 8 carbon atoms, such as methoxy, ethoxy, isobutoxy, methoxyethoxy, ethoxyethoxy, ethoxyphenoxy. It is preferable to use reactive silanes selected from the group consisting of VINYLTRIMETHOXYSILANE, vinyltriethoxysilane, allyltriethoxysilane, allyltriethoxysilane, butyltrichlorosilane, butyltrichlorosilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-acrylonitrilebutadiene, gamma-acrylonitrilebutadiene, vinyltriethoxysilane and mixtures thereof. These reactive silanes are most suitable for use in materials related to food packaging. The most preferred reactive silane selected from the group consisting of vinyl, VINYLTRIMETHOXYSILANE and vinyltriethoxysilane.
The thickness of the coating applied, but not sewn organosiloxane oligomer is from 1 to 50 nm, preference is sustained fashion from 1 to 40 nm, it is advisable from 1 to 30 nm, most preferably from 10 to 30 nm. After stitching thickness organopolysiloxane coating will naturally be less than before stitching.
According to the second aspect of the present invention described above, the barrier film is suitable in the manufacture of laminated soft materials for food packaging, as well as hard laminated materials or semi-rigid laminated material for packaging food products comprising the inner layer of cardboard and the outer hermetically sealed by heating, impermeable to liquids layers of thermoplastic polymeric substance.
According to a third aspect of the present invention thus obtained laminated packaging materials are suitable for use in the manufacture of packing containers for long term storage and sterile packaging of food or drink.
According to an additional aspect of this invention, the barrier film according to the invention is manufactured by the method including the process of getting the main polymer films, drawing on the basic film deposition from the gas phase barrier layer containing an inorganic oxide, and applying an additional coating to the specified precipitated from the gas phase inorganic layer, where the adiya applying additional coverage includes the stage of preparation of the composition, consisting essentially of a solute in a solvent reactive unsaturated silane compounds with three silanolate groups, applying this composition on deposited from the gas phase inorganic layer, the applied composition reactions of hydrolysis and condensation to obtain ethyleneamines organosiloxane oligomer, which is connected by covalent bonds with the inorganic layer, and finally curing the applied organosiloxane oligomer to create a crosslinked polysiloxane layer. As the solvent evaporates by itself in the course of chemical reactions, usually a separate stage of drying is not necessary.
Containing reactive silane composition to obtain a coating is applied as a solution of a reactive silane in a solvent, preferably ethanol, the concentration of which ranges from 1 to 10 wt.%, preferably from 2 to 6 wt.%, it is advisable from 3 to 6 wt.%, in the form of a liquid film over the inorganic layer using any suitable method for applying representing a liquid film coatings. It is desirable that the solution for coating was applied by the transfer roller which is immersed in the solution and roll on the inorganic film layer. In the coating applied composition penetrates down into the cracks of the small holes in the micrometer and nanometer size of the inorganic layer, then this composition hydrolyzing and then carry out the condensation reaction so that part silanolate groups reacts condensation in the layer organosilane composition, forming organosiloxane oligomer, and some silanolate groups reacts condensation with hydroxyl groups formed on the surface of the substrate of the inorganic oxide. Therefore, organosiloxane oligomer is crosslinked in areas containing unsaturated carbon-carbon, thus forming a crosslinked organopolysiloxane layer which is tightly connected with the substrate of inorganic oxide covalent bonds.
Measured before condensation and curing thickness is thus the solution of the reactive silane may be in the range of 1 to 50 nm, preferably from 10 to 30 nm.
The reaction product, formed at the phase boundary between the layer of inorganic oxide and a layer of polyorganosiloxane, can be called a hybrid substance, and not be seen as two separate layers. Two substances react with each other, forming a tightly spaced throughout the surface of the barrier film in a covalent bond, and clear boundaries between the layers no longer exist. Therefore, these layers are inseparable and will not delaminate or separate from each other on the ACOM a section of the barrier hybrid layer. Moreover, due to the more organic nature of organopolysiloxane get the best adhesion to then formed by lamination by extrusion or other method of laminating a polymer layer than in the case of pure applied by deposition from the gas phase layer of metal oxide, such as SiOx.
It is desirable that the stage of curing was carried out, carrying out crosslinking by irradiation, and according to a preferred variant implementation of the use of UV irradiation in combination with the introduction of photoinitiator in the composition for forming the layer has been out of coverage. A suitable concentration of photoinitiator introduced into the composition for forming the layer has been out of coverage, which ranges from 1 to 10 wt.%, preferably from 2 to 5 wt.%, it is advisable from 3 to 5 wt.%, most preferably 3 to 4 wt.%. It is desirable to apply photoinitiator with functional groups, represents an amino group, as for the applied barrier layer get more good results.
According to another aspect of the present invention provides a rigid packing container, made from laminated packaging material according to the invention with properties such as low penetration rate of oxygen, the integrity of the packaging and internal adhesion between layers glossy is consistent material, moreover, these properties correspond to properties containing aluminum foil packaging containers of the prior art, commercially available at present for packaging liquid food products.
Preferred variants of the invention are described below with reference to the drawings, of which:
Figa-1c schematically show in cross section the context of the stage of creation of the barrier layer in the barrier film according to the invention,
Figa and 2b schematically show different options for obtaining the laminated packaging material according to the invention,
Figure 3 - example of the packaging container manufactured from the laminated packaging material according to the invention,
Figure 4 shows the principle of producing such a packaging container of laminated packaging material during a continuous process of forming, filling and hermetic sealing,
Figure 5 shows a device for applying to the main film coatings SiOxand SiOxCythe PECVD method,
6 to 9 represent dependencies that shows the relationship between the transmission of oxygen and conditional deformation in accordance with the relevant tests of hybrid layers described in the examples.
Thus, Figure 1 illustrates the receive hybrid barrier layer according to the invention. On Figa shows the defects 14, 15 micrometres is about and nanometer size for the layer 11 of inorganic oxide, preferably silicon oxide), and Fig.1b such defects filled organosilane monomer/oligomer. For optimum barrier properties of the inorganic layer, it is preferable that the main film 12, which is a polymer film had a very smooth surface. After hydrolysis, as shown in Figs, organosilane monomers/oligomers react condensation with each other and with hydroxyl/silanol groups on the surface of the oxide, and then polymerized under the influence of an external source of UV radiation with the formation of crosslinked organopolysiloxane layer 13 on the surface, representing the oxide substrate. Accordingly, the penetration of gases and vapors associated with defects in the layer of inorganic oxide is reduced and, thus, improve the barrier properties of the hybrid material. In parallel, the strength of forested and contains healed defects of the layer of inorganic oxide is improved, so that the corresponding crack deformation strain (COS) is shifted towards higher values. The COS value represents the degree of deformation, in which the permeability to oxygen is still standing before it begins to increase rapidly because of the increasing number of emerging barrier layer cracks.
On Figa shown in the context of the first variant is NT getting soft laminated packaging material 20A, manufactured according to the invention.
The laminated material includes a base layer 21 of the PET, the external is not permeable to liquid and sealed by heating layers 22, 23 on the basis of polyolefin and hybrid barrier layer 24, which is applied to the primary layer of the PET, and contains the first, caused by deposition from the gas phase method PECVD layer of silicon oxide 24-1 and the second covalently attached layer stitched organopolysiloxane 24-2. External is not permeable to liquids and sealed by heating layers 22, 23 include a polyolefin, such as, preferably polyethylene, more desirable, low-density polyethylene (LDPE), traditional quality in relation to sealing by heat. Most preferably also, when one or both of the printed when heated layers use linear low density polyethylene (LLDPE)obtained by polymerization of ethylene monomer with a C4-C8 alpha-olefin alkilinity monomer in the presence of a metallocene catalyst, i.e. the so-called metallocene-LLDPE (m-LLDPE).
Fig.2b shows in section a second option for obtaining hard laminated packaging material or semi-rigid laminated packaging material 20b, manufactured according to the invention. The stiffness of the laminated packaging material due to the presence inside the it layer 25 cardboard, and the laminated material further comprises an external sealed by heating and impermeable to liquid layers 22, 23 of thermoplastic polymer, preferably low density polyethylene or m-LLDPE described above. The barrier layer 24, as described above in connection with the description of Figa, applied on the base layer 21 and it consists of the first applied by deposition from the gas phase method PECVD layer of silicon oxide 24-1 and the second layer covalently attached stitched organopolysiloxane 24-2. Such film is covered with a barrier layer, the main layer, can be rotated in any direction when laminating with a layer 26 laminated to obtain containing cardboard laminated packaging material. Preferably, this part of the laminated material layer consisted obtained by extrusion of a layer of polyolefin, and more desirable layer of low density polyethylene.
Figure 3 shows the filled packaging container 30 of the Tetra Brik®, hermetically sealed along the longitudinal axis of the spike 31 and cross the spikes 32, around which the packing container cut off from the previous packaging container (46 figure 4), and continuous fillable tube (41 4), respectively. Packaging container according to the invention can additionally be provided with a device for revelation is of 33 for easier pouring filling his product and opportunity again to close the packaging container, if it is not empty.
Figure 4 shows the principle of which is described in the introduction to this practical application, that is, the roll of material for packaging containers forms a pipe 41 connecting the longitudinal edges 42, 42' roll one with another lap 43. The fill tube 44 in the desired liquid food product and is divided into individual packaging containers recurring cross the spikes 45 this tube located from each other at a distance below the level of the filling tube content. Packaging containers 46 are separated by cutting transverse commissures, and set the desired geometrical configuration, bending along the harvested material excesses.
Figure 5 schematically shows a preferred device 50 and the method of obtaining the primary coating film of SiOx. On the main film 51 create floor SiOxwhere x = 1.7 to 2.2, causing organosilicon compound, such as hexamethyldisiloxane (HMDSO) or tetramethyldisiloxane (TMDSO), from continuous plasma plasma-chemical deposition from the gas phase, PECVD, and asking such a coating thickness in the range from 5 to 500 nm, preferably from 5 to 200 nm, more desirable from 5 to 100 nm, so that the formed barrier film 1C.
This invention is not limited to the implementation shown and described above, p is because it can be modified within the claims. For example, the barrier film according to the invention can be combined with additional layers that provide functionality such as additional barrier, strength or similar property.
In addition, you can use the traditional methods of surface treatment to make it adhesive properties, as well as traditional adhesives and primers to further improve the properties of integrity, that is, the adhesion between the layers, laminated packaging materials and packaging containers, and they can be matched to meet the specific structure of the laminated material.
1. Used chemicals and materials
|Sample number||Connection name||Manufacturer||Properties|
|1||SiOx/PET-1||PET - DuPont Mylar, SiOxdeposited by PECVD method on the Tetra Pak||SiOx- 10 nm / PET 12 μm|
|2||SiOx/PET-2||PET - DuPont Mylar, SiOxdeposited by PECVD method on the company etra Pak||SiOx- 50 nm / PET 12 μm|
Testing has been out of the coating layer was carried out for PET films with a thickness of 12 μm, coated with silicon oxide with the General formula SiOxwhere x ranges from 1.7 to 2.2, applied plasma-chemical deposition from the gas phase PECVD. Conducted testing of coatings SiOxwith a thickness of 50 and 10 nm, respectively (see table 1.1).
Investigated unsaturated organosilane monomers represented MAPS and VS, as can be seen from table 1.2. Organosilane was dissolved in ethanol in an amount necessary for solution preparation with a concentration of from 3 to 6 wt.%, and additionally in the composition representing a solution of the composition included photoinitiator in number from 2 to 5 wt.%, as indicated in Table 1.2. Representing a solution of organosilane composition was applied in the form of a liquid film over a layer of SiOxusing the transfer roller, which is dipped in representing the solution composition, and then carried out his contact with the surface of SiOx. The thickness of the applied thus organosilane coating was about 25 nm.
Silanes and photoinitiator
|Purity 99%, available from GE speciality materials, Switzerland||Molecular weight 274, does not contain amine, density (g/cm3): 1,045||Curable under the action of UV-irradiation silane|
|Purity 99%, available from GE speciality materials, Switzerland||The molecular mass of 219,|
does not contain amine, density (g/cm3): 1,12, stitched double bond
|Curable under the action of UV-irradiation silane|
|Purity >99%, available from the company Ciba speciality chemicals, Switzerland||Melting point 127 depression -133°C light yellow powder||UV photoinitiator|
|Purity >99%, available from the company Ciba speciality chemicals, Switzerland||Molecular weight 366,5|
Melting point 115°C
|Photoinitiator, splits generalities|
2. The rate of introduction of oxygen under tensile strain for raw films SiOx/PET
Produced samples of films from a number of PET films coated with a way PEVCD coatings SiOxfor measurements on the rate of penetration of oxygen (OTR) when exposed to these samples uniaxial tensile strength. Device for the measurement consists of a device for stretching mounted on the diffuser for oxygen Mocon®. The location allows you to determine the dependence of the OTR and the coordinates corresponding to the cracking strain (COS) from the value attached to the samples uniaxial tensile strength. When the strain exceeds a critical value of COS, diffusion of gaseous oxygen through the sample increases by an order of magnitude due to the fragmentation of the layers of SiOxor organosilane/SiOx. The value OTR was determined by the La for each nominal strain, increase in increments of 1.0%.
Measurement of OTR for untreated samples were held for layers of SiOxthickness of 10 and 50 nm, deposited by PECVD method on PET film thickness of 12 μm. In Tables 2.1 and 2.2 lists the corresponding measurement results for flat films of SiOx/PET, not containing caused recuperating from his organosilane floor.
The results of determining the permeation rate of oxygen measured for untreated organosilane layers of SiOxthickness of 10 nm
|Conditional deformation (%)||SiOx10 nm|
|The standard deviation|
The results of determining the permeation rate of oxygen measured for untreated organosilane layers of SiOxthickness of 50 nm
|Conditional deformation (%)||SiOx50 nm|
|The standard deviation|
3. The rate of introduction of oxygen under tensile strain for films containing layer has been out of organosilane
Samples of PET films with a thickness of 12 μm coated with a layer of SiOxthickness of 50 nm, received in the form of a roll on pilot line to obtain a coating liquid film through coating of organosilanols layer covered with SiOxand the subsequent curing by means of UV-irradiation to unwinding. MAPS-1 MAPS-2 was a formulation containing gamma methacryloxypropyltrimethoxysilane diluted ethanol is m to a concentration of 3 wt.%, with the addition of, respectively, photoinitiator PI-1 and PI-2 in the amount of from 2 to 5 wt.%. VS-1 and VS-2 was a formulation containing VINYLTRIMETHOXYSILANE diluted with ethanol to a concentration of 3 wt.%, with the addition of, respectively, photoinitiator PI-1 and PI-2 in the amount of from 2 to 5 wt.% (for information about connections PI-1 and PI-2 see Table 1.2). These four organosilane formulation was applied to achieve a thickness of about 25 nm to under the action of UV-irradiation stage curing and unwinding of the roll. Taken from the received rolls of samples of the films were placed in the device for the measurement of OTR deformed samples, as described above.
Table 3.1 contains the results of measurements of the OTR values for the samples, respectively, treated with formulations MAPS-1, MAPS-2, VS-1 and VS-2. Figure 6 in semi-logarithmic coordinates shows the dependence of the OTR values from conditional deformation. Figure 6 also shows the corresponding dependence OTR, taken from the Table 2.2 data for deformed raw organosilanes samples SiOx/PET. When comparing the COS values for different samples clearly shows the influence of the cured under the action of UV-irradiation of organosilane. Raw samples SiOx/PET have the COS value 2% of the conventional deformation, whereas processed formulations MAPS and VS education is s SiO x/PET show values of COS in 3, 4 and up to 5% depending on the type added to a solution of compounds of photoinitiators, PI-1 or PI-2. Photoinitiator No. 2, containing as functional groups of the amino photoinitiator allowed to get the best improvement for values of COS and OTR.
The results of determining the permeation rate of oxygen measured for layers of SiOxthickness of 50 nm, processed recuperating from his recipes MAPS-1, MAPS-2, VS-1 and VS-2
|Conditional deformation (%)||MAPS-1|
|3||to 2.06||1,76||for 6.81||1,22|
Figure 6 in semi-logarithmic coordinates shows the dependence of the OTR values from conditional deformation during tensile specimens with a barrier coating of SiOxthickness of 50 nm is deposited by the PECVD method on the PET film with thickness of 12 μm. Figure 6 shows the dependencies of the OTR values for untreated samples SiOx/PET samples and SiOx/PET treated organosilane formulations MAPS-1, MAPS-2, VS-1 and VS-2.
From the results given above clearly suggests that the best recipe is recuperating from his composition VS-2 (3% solution of vinylsilane in ethanol containing photoinitiator PI-2). Therefore, to evaluate the reproducibility of the results was performed eight consecutive tests for this particular recuperating from his compositions. In Table 3.2 lists the results of determining the amount OTR for samples with the deformation and processing of the formulation VS-2. 7 in semi-logarithmic coordinates are given according to eight obrabotan the x formulation VS-2 samples SiO x/PET. For easier comparison, figure 7 shows the dependence of the OTR values for untreated samples SiOx/PET, built according to Table 2.2.
The results of determining the permeation rate of oxygen through eight deformation tests for samples containing layers of SiOxthickness of 50 nm, treated organosilanols formulation VS-2
|Conditional deformation (%)||VS-2/|
7 in semi-logarithmic coordinates shows the dependence of the OTR values from conditional deformation during tensile specimens with a barrier coating of SiOxthickness of 50 nm is deposited by the PECVD method on the PET film with thickness of 12 μm. 7 shows the dependence of OTR for eight samples SiOx/PET treated organosilanols formulation VS-2. It also shows the dependence of the OTR from conventional strain curve for untreated samples SiOx/PET.
7 shows the typical behavior for containing layer has been out of samples for which the value of OTR is constant below the critical value of deformation (COS) and increases significantly above this value. Of the eight samples of seven had a value of COS in 5%, whereas the value of 6% showed only one sample. For raw layers of SiOxwhat thickness of 50 nm, the behavior is significantly different from which is characteristic for the modified organosilanes samples: the values of COS are near 2% conventional tensile strain and the magnitude of the OTR at 5% reaches 100 cm3/m2/day/bar.
Another important characteristic feature of the formation of polysiloxane is associated with improved barrier properties contains has been out of the coating layers of SiOxwith respect to oxygen. This improvement is clearly shown in Fig.7, in which all the treated samples show a much smaller values OTR compared to the untreated sample, for which this value is 1.6 cm3/m2/day/bar.
Averaging the results of determining the value of OTR for each experimental point provides a clear picture of the effectiveness of the curing of defects for organosilanols recipe VS-2 in comparison with the untreated sample SiOx/PET with a thickness of SiOx50 nm, for which the results are presented in Table 2.2. This is illustrated Fig on which the results of determining the amount OTR represented in linear coordinates.
On Fig shows the dependence of the OTR from conventional deformation during tensile specimens with a barrier coating of SiOxthickness of 50 nm is deposited by the PECVD method on the PET film with thickness of 12 μm. On Fig shows the dependencies OTR for eight samples SiOx/ET, processed organosilanols formulation VS-2, and according to OTR from conventional deformation for the three raw images SiOx/PET, for which the results are presented in Table 2.2.
In order to reduce the cost it would be interesting to cover the polymer films are so thin oxide layer as possible. In this regard, this study was carried out for the barrier layer of SiOxcaused by the PECVD method on a 12 μm PET film. After further processing by organosilanes VS-2 and cured under UV-irradiation samples of the films were tested to determine the OTR under tensile strain. The results are shown in Table 3.3 and plotted in Fig.9. It also graphically presents the results of determining the OTR values specified in Table 2.1 raw samples.
The results of determining the permeation rate of oxygen through three deformation tests for layers of SiOxthickness of 10 nm, treated organosilanols formulation VS-2
|Conditional deformation (%)||VS-2/SiOx|
Figure 9 shows the dependence of the OTR from conventional deformation during tensile specimens with a barrier coating of SiOxthickness of 10 nm is deposited by a PECVD method on the PET film with thickness of 12 μm. Figure 9 shows the dependence of OTR for the three samples with SiOx/PET, for which the results are presented in Table 3.3, processed what's organosilanols formulation VS-2, and the dependence of OTR from conventional deformation for raw images SiOx/PET, for which the results are presented in Table 2.1.
For treated samples barrier properties against oxygen increase in the formation of polysiloxane hybrid and the corresponding value of COS is 5 to 6% nominal strain. This improvement significantly less than for thicker layers of SiOx. Another characteristic feature of the barrier layers of oxide SiOxis the dependence of the values of COS on the thickness of the SiOx. This dependence is clearly visible when considering the values COS untreated specimens 10 and 50 nm, respectively. The values of COS layers of SiOxthickness of 10 nm is 4%, whereas they make up only 2% for layers of SiOxthickness of 50 nm (6-8 and 9, respectively). This difference may explain why the effect curing of defects for custom made of organosilane becomes weaker with decreasing thickness of the layer of SiOx.
Thus, on the basis of the above examples we can draw the following conclusions.
Values of COS not containing organosilane layer has been out samples of SiOx/PET layer thickness of SiOx50 and 10 nm are 2 and 4%, respectively.
Values COS, covered with 3% solution of vinylsilane treatment the samples SiO x/PET layer thickness of SiOx50 and 10 nm are 6 and 5.5%, respectively.
In the coating using a 3% solution VS-2 observed a very strong improvement in the values of COS for films of SiOx/PET layer thickness of SiOx50 nm, whereas for the same silane improvement values COS for films of SiOx/PET layer thickness of SiOx10 nm is expressed weaker.
In addition, in the coating using a 3% solution VS-2 observed a very strong decrease of the values of OTR as for samples SiOx/PET layer thickness of SiOx10 nm, and samples SiOx/PET layer thickness of SiOx50 nm.
1. Barrier film (1C) for packaging food or beverages, including the main film (12) of the polymer and applied to the main film barrier layer (11)containing precipitated from the gas phase inorganic oxide, wherein the deposited barrier layer is additionally coated recuperating from his layer (13), consisting of cross-linked organopolysiloxane, which is covalently connected to the inorganic barrier layer (11) and represents the reaction product of a composition consisting essentially of unsaturated organosiloxanes with three Selenastrum groups.
2. Barrier film according to claim 1, characterized in that the inorganic barrier layer (11) contains at least on the surface of xed metal.
3. Barrier film according to claim 1, characterized in that the inorganic barrier layer (11) comprises an oxide selected from the group consisting of silicon oxide and aluminum oxide.
4. Barrier film according to claim 3, characterized in that the inorganic barrier layer (11) includes a silicon oxide with the formula (SiOxCy), where x is from 0.1 to 2.5, y is from 0.1 to 2.5, optionally containing covalently attached carbon atoms.
5. Barrier film according to any one of claims 1 to 4, characterized in that the thickness specified applied inorganic barrier layer (11) is from 5 to 500 nm, preferably from 5 to 200 nm.
6. Barrier film according to any one of claims 1 to 4, characterized in that the main film (12) includes a polymer layer for receiving applied by deposition from the gas phase layer, and a polymer layer composed of a substance selected from the group consisting of polyethylene terephthalate (PET) and polyamide (PA).
7. Barrier film according to any one of claims 1 to 4, characterized in that the specified applied by deposition from the gas phase inorganic barrier layer (11) is applied plasma-chemical deposition from the gas phase (PECVD).
8. Barrier film according to any one of claims 1 to 4, characterized in that the specified applied by deposition from the gas phase inorganic barrier layer (11) is applied atmospheric plasma coating or chemical OS is being introduced from the gas phase oxidation (CCVD).
9. Barrier film according to any one of claims 1 to 4, characterized in that the applied organopolysiloxane layer (13) is a crosslinked reaction product of a composition consisting essentially of a reactive unsaturated of organosilane selected from the group consisting of VINYLTRIMETHOXYSILANE, vinyltriethoxysilane, allyltriethoxysilane,allyltriethoxysilane, butyltrichlorosilane, butyltrichlorosilane,gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane,gamma-acrylonitrilebutadiene,gamma-acrylonitrilebutadiene,vinyltriethoxysilane and mixtures thereof.
10. Barrier film according to any one of claims 1 to 4, characterized in that the applied organopolysiloxane layer (13) is a crosslinked reaction product of a composition consisting essentially of a reactive unsaturated of organosilane selected from the group including VINYLTRIMETHOXYSILANE, vinyltriethoxysilane and mixtures thereof.
11. Barrier film according to any one of claims 1 to 4, characterized in that the thickness specified applied organopolysiloxane layer (13) is from 1 to 50 nm, preferably from 1 to 40 nm, it is advisable from 1 to 30 nm, most preferably from 10 to 30 nm.
12. Multilayer laminated packaging material (20A, 20b) for packaging food etc the products or beverages, including a barrier film (1C) according to any one of claims 1 to 12.
13. The laminated packaging material (20b) for rigid or semi-rigid containers for food or beverage, comprising an inner layer (25) of the cardboard and the outer capable of hermetic sealing when heated, impervious to fluid layers (22, 23) of the polymer, based on the polyolefin, characterized in that it further comprises a barrier film (1C) according to any one of claims 1 to 11.
14. A method of manufacturing a barrier film (1C) for packaging food or beverage according to any one of claims 1 to 12, comprising the stage of:
obtain basic film (12) of the polymer;
drawing on the basic film barrier layer (11)containing inorganic oxide deposited from the gas phase;
additional coverage specified caused by deposition from the gas phase inorganic layer,
characterized in that
stage additional coverage involves the following stages:
obtain a composition consisting essentially of the reactive unsaturated silane compounds with three silanolate groups dissolved in the solvent;
application (1b) of the composition applied by deposition from the gas phase inorganic layer (11);
the reaction of hydrolysis and condensation for the applied composition to obtain ethyleneamines organosiloxane is legomena, which is connected by covalent bonds with the inorganic layer; and
curing the applied organosiloxane oligomer to obtain custom made organopolysiloxane layer (13).
15. The method according to 14, characterized in that the stage of curing is conducted by crosslinking with radiation.
16. The method according to item 15, wherein the composition for the coating layer has been out add photoinitiator and the curing is carried out by ultraviolet radiation.
17. The method according to item 16, characterized in that photoinitiator added in an amount of from 1 to 10 wt.%, preferably from 2 to 5 wt.%, it is advisable from 3 to 5 wt.%.
18. The method according to any of PP-17, characterized in that the solvent dissolve this amount of reactive unsaturated silane compound to its concentration ranged from 1 to 10 wt.%, preferably from 2 to 6 wt.%, it is advisable from 3 to 6 wt.%.
19. The method according to any of PP-17, characterized in that the unsaturated silane compound composition for coating is applied to measured before curing the coating thickness ranged from 1 to 50 nm, preferably from 1 to 40 nm, it is advisable from 1 to 30 nm, most preferably from 10 to 30 nm.
20. The method according to any of PP-17, characterized in that the solvent dissolve this amount of reactionsare what about the unsaturated silane compounds, to its concentration ranged from 3 to 6 wt.%, and apply the coating, measured before curing, the thickness of which ranges from 10 to 30 nm.
21. The method according to any of PP-17, characterized in that the reactive unsaturated silane compound selected from the group consisting of VINYLTRIMETHOXYSILANE, vinyltriethoxysilane, allyltriethoxysilane,allyltriethoxysilane, butyltrichlorosilane, butyltrichlorosilane,gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane,gamma-acrylonitrilebutadiene,gamma-acrylonitrilebutadiene, vinyltriethoxysilane and mixtures thereof.
22. The method according to any of PP-17, characterized in that the reactive unsaturated silane compound selected from the group consisting of VINYLTRIMETHOXYSILANE, vinyltriethoxysilane and mixtures thereof.
23. The packaging container (30) for packaging food or beverages made from barrier film or the laminated packaging material according to any one of claims 1 to 11.
FIELD: process engineering.
SUBSTANCE: invention relates to composite materials, method of producing multifunctional coat on microporous carrier to be used in many fields exploiting properties of both microporous carrier and coat material. Proposed composite material comprises microporous layer having pore walls and apparent porosity and multifunctional coat of two or more functions on at least a portion of microporous layer pore walls. Microporous layer preserves at least a definite portion of apparent porosity on a section of coated microporous structure. Proposed method comprises producing mix for water wetting, adding first additive to said mix and at least one additional functional additive. It comprises also applying said wetting solution on microporous structure and heating microporous material containing said wetting mix with two or more functions wherein microporous layer preserves at least a definite portion of apparent porosity on a section of coated microporous structure.
EFFECT: method of producing multifunctional coat on microporous carrier to be used in many fields exploiting properties of both microporous carrier and coat material.
46 cl, 3 ex, 3 dwg
SUBSTANCE: invention relates to the technology of obtaining elastomeric materials and particularly to processing surfaces of elastomer films in order to prevent creating in a roll. The method involves forming a film layer from an elastomeric polymer from a block-copolymer of vinyl arylene and conjugated diene monomers, which can be stretched by at least 150% of the initial size and then shrink to not more than 120% of the initial size. An anti-crease coating layer is applied on the first surface of the film. The coating consists of a solvent and an anti-crease coating component selected from lacquer and a surfactant. The film is rolled into a roll, the anti-crease coating component being in contact with the second surface of the film.
EFFECT: efficient method of processing surfaces of elastomer films to prevent creasing in a roll.
18 cl, 5 dwg, 2 ex
SUBSTANCE: disclosed is a method of producing a coated adhesive layer with improved optical characteristics, in which a curable composition containing curable organopolysiloxane is applied onto the surface of a substrate, and improved optical purity is achieved owing to that the composition contains a group of silicon dioxide particles having average size ranging from approximately 1 to approximately 7 micrometres. The invention also discloses a method of producing a multilayer article with improved inter-layer adhesion characteristics owing to reduction of the air space between layers, where the adhesive layer is obtained using the disclosed method, and the corresponding multilayer article.
EFFECT: higher optical purity of the coating adhesive layer and adhesion between layers in multilayer articles owing to virtually no air trapping when applying the adhesive layer.
20 cl, 6 tbl, 4 ex
FIELD: process engineering.
SUBSTANCE: invention relates to laminate used in glass panels, lenses etc. Proposed laminate comprises base made up of polycarbonate resin, first layer resulted from hardening acrylic resin hardening, second layer produced by thermal hardening of organosiloxane resin. Acrylic resin composition comprises (A) acrylic copolymer containing at least 70 mol % of repeating link of formula (A)
where X is hydrogen or methyl, Y is methyl, ethyl, cycloalkyl or hydroxyalkyl with the number of atoms of 2 to 5, or residue of UV radiation absorber based on triazine; blocked polyisocyanate compound; hardening catalyst; and (D) UV radiation absorber based on triazine. Note here that total content of UV radiation absorber based on triazine in formula (A) and as component (D) varies from 1 to 40 wt %. Composition of organosiloxane resin in proposed laminate comprises (E) colloidal silicon dioxide and (F) hydrolytic condensate of alkoxy silane. Invention covers also window glass made based on said laminate.
EFFECT: higher strength and longer life.
25 cl, 15 tbl, 50 ex
SUBSTANCE: composition contains at least one expandable microsphere and at least one ionic compound which is cationic. The composition also contains a certain set of cellulose fibres. The ionic compound is selected from a group comprising a polyamine, polyethyleneimine, colloid and sol. The colloid or sol contains at least one member from a group comprising silica, alumina, tin oxide, zirconium dioxide, antimony oxide, iron oxide and rare-earth metal oxides. The outer surface of the expandable microsphere, which is anionic, is not covalently bonded with an ionic compound. The composition has electrokinetic potential greater than or equal to 0 mV at pH of approximately 9.0 or less with ionic strength between 10-6 mol and 0.1 mol. The composition is prepared by bringing into contact at least one expandable microsphere and at least one ionic compound to form a mixture. The mixture is centrifuged to form a first phase containing at least one ionic compound and a second phase containing a particle. A solution containing a certain amount of cellulose fibre is also added. A low-density paper or cardboard base and article which is a cardboard container with good operational characteristics is obtained. The weight of the article is equal or less than 1 oz. The paper or cardboard base has Sheffield smoothness less than 250 units measured using a TARR1 T 538 om-1 technique, and colour speckling 2nd cyan not greater than 6. The base has Parker Print surface roughness from approximately 1.0 to 0.5, measured using a TARRI T 555 om-99 technique.
EFFECT: improved properties of the composition.
28 cl, 5 dwg, 4 tbl, 2 ex
SUBSTANCE: method of coating substrates comprises the following steps: a) preparing the substrate, b) depositing a composition onto at least one side of the substrate, the composition containing an inorganic compound which contains at least one metal and/or semimetal selected from a group comprising Sc, Y, Ti, Zr, Nb, V, Cr, Mo, W, Mn, Fe, Co, B, Al, In, Tl, Si, Ge, Sn, Zn, Pb, Sb, Bi or mixtures thereof, and at least one element selected from a group comprising Te, Se, S, O, Sb, As, P, N, C, Ga or mixtures thereof, c) drying the composition deposited at step b), d) applying at least one coating onto at least one side of the substrate onto which the composition was deposited at step b), wherein the coating contains silane of general formula (Z1)Si(OR)3, where Z1 is R, OR or Gly (Gly=3-glycidyloxypropyl), and R is an alkyl residue with 1-18 carbon atoms, and R can be identical or different, oxide particles selected from a group comprising oxides of Ti, Si, Zr, Al, Y, Sn, Zn, Ce or mixtures thereof, and an initiator, wherein the coating preferably contains 3-aminopropyl-trimethoxysilane and/or 3-aminopropyl-triethoxysilane and/or N-2-aminoethyl-3-aminopropyl-trimethoxysilane, and e) drying the coating applied at step d). The composition at step b) and/or the coating at step d) contain at least one pigment which reflects infrared radiation, and said pigment has a core coated by an electroconductive layer which contains tin oxides and/or titanium oxides. The invention also discloses use of the coated substrate obtained using the disclosed method as wall-paper.
EFFECT: method enables cheap production of a coated substrate capable of reflecting infrared radiation, and simplifies facing buildings.
FIELD: process engineering.
SUBSTANCE: invention relates to coat and method of coating outer surfaces. Proposed method of coating pipeline outer surfaces by polymer capable of forming cross-links under action of water comprises the following stages: a) pipeline outer surface is coated by, at least, one polymer that forms cross-links under action of water. Note here that said polymer represents HDPE grafted by alkoxy silane. b) Polymer is cross linked on subjecting it to water at increased temperature to produce cross-linked polymer layer unless cross linking degree makes ≥30% to ≤80%. c) Polymer is cross linked that can form cross links under action of water at ≥50°C to ≤350°C, preferably at ≥150°C to ≤300°C, more preferably at ≥200°C to ≤260°C. Note here that during these stages, pipeline is heated to ≥170°C to ≤230°C, preferably to ≥180°C to ≤220°C, more preferably to ≥190°C to ≤210°C. Powder ionic spraying method is used epoxy resin layer is applied with thickness of ≥0.08 to ≤0.16 mm, preferably of ≥0.10 to ≤0.13 mm, more preferably, 0.125 mm. Method of envelopment extrusion is used to apply a layer of glue with thickness of ≥0.15 mm to ≤0.30 mm, preferable of ≥0.22 mm to ≤0.27 mm, more preferably of 0.25 mm. By method of extrusion, applied is upper layer of HDPE with thickness of ≥2.8 mm to ≤3.2 mm, preferably of ≥2.9 mm to ≤3.1 mm, more preferably of 3 mm. Extrusion is used to apply layer of HDPE cross linked by silane with thickness of ≥0.8 mm to ≤1.2 mm, preferably of ≥0.9 mm to ≤1.1 mm, more preferably of 1 mm. Now, pipeline is treated by water with temperature of ≥10°C to ≤40°C, preferably of ≥20°C to ≤30°C, more preferably of 25°C. Coat is made as described above. Invention covers also coated pipeline.
EFFECT: improved operating performances and expanded applications.
11 cl, 2 tbl, 3 dwg, 2 ex
SUBSTANCE: invention describes a foamed vinylaromatic polymer containing a) a matrix obtained via polymerisation of 100 wt % vinylaromatic monomer; b) 1-10 wt % (per amount of polymer (a)) foaming agent incorporated in the polymer matrix; c) 0.01-25 wt % (per amount of polymer (a)) technical carbon, characterised by average diametre between 30 and 2000 nm, specific surface area between 5 and 40 m2/g, sulphur content between 0.1 and 1000 parts per million and ash content between 0.001 and 1%; d) 0-10 wt % (per amount of polymer (a)) graphite; e) 0-10 wt % (per amount of polymer (a)) aluminium; f) 0-10 wt % (per amount of polymer (a)) antimony trisulphide, provided that the total amount of components (a)-(f) equals 100, and that concentration of matrix (a) is not less than 80 wt % and at least one of (d)-(f) is present. The invention also describes a foamed article having density between 5 and 50 g/l, characterised by thermal conductivity between 25 and 50 mW/mK, obtained after foaming at temperature several times higher than the glass transition point of the polymer and granules of the vinylaromatic polymer given above. Described is a method of improving insulating capacity of the foamed vinylaromatic polymer given above.
EFFECT: improved insulating capacity of the foamed product.
13 cl, 6 ex
SUBSTANCE: present invention relates to a method of treating and modifying materials. Described is a method of preparing materials which protects said materials from UV radiation and ozone using a modifier, involving obtaining the modifier by reacting a stilbene derivative in form of 4,4'-bis(s-triazinyl-)diamine-2,2'-disulphostilbene at temperature of up to 55°C in the presence of water with diamine of carbonic acid in amount of 0.5-55 wt % with respect to weight of said stilbene derivative, and material such as foamed or foamable plastic, cement or concrete is then directly treated with the prepared modifier, and/or active radicals of said modifiers are introduced into the surface of said materials. Described also is a method of preparing materials for their protection from UV radiation and ozone using a modifier, involving obtaining the modifier by inoculating a stilbene derivative in form of 4,4'-bis(s-triazinyl-)diamine-2,2'-disulphostilbene with solid diamine of carbonic acid with crystal size less than 40 mcm at 55°C in the absence of water, by grinding the modifiers in a mill and homogenisation at ambient temperature for more than 4 hours, with amount of diamine of carbonic acid of 0.1-45 wt % with respect to the solid stilbene derivative, and material such as foamed or foamable plastic, cement or concrete is then directly treated with the prepared modifier, and/or active radicals of said modifiers are introduced into the surface of said materials.
EFFECT: elimination of negative effect of UV radiation and ozone on surface of materials.
2 cl, 4 ex
SUBSTANCE: invention relates to an article having at least one base (S) which has at least one polyolefin composition (C1) containing at least one non-functionalised polyolefin (PO1), wherein said base has a surface and at least one layer (Σ) covering at least one section of the surface of the said base, wherein said layer (Σ) is formed by at least one polyolefin composition (C2) which contains at least one functionalised polyolefin (POg) obtained by grafting acid and/or anhydride groups to at least one non-functionalised polyolefin (PO2), whereby said acid and/or anhydride groups are completely or partially neutralised with at least one neutralising gent, and at least one emulsifying agent.
EFFECT: article has improved surface properties, improved antistatic and electroconduction properties.
36 cl, 2 ex
SUBSTANCE: invention relates to polymer compositions for making fluorescent and selectively radiation-absorbing films, which transform the ultraviolet component of natural or artificial light into radiation in the red region, which can be used in agriculture to coat greenhouses and soil when growing plants. The light-correcting polymer film contains a photoluminescent phosphor and a light-stabiliser, where the photoluminescent phosphor is yttrium phosphate-vanadate-borate activated with europium and/or yttrium phosphate vanadate activated with europium, and the light stabiliser is Tinuvin 622. The composition for making a light-correcting polymer film contains yttrium phosphate-vanadate-borate activated with europium and/or yttrium phosphate-vanadate activated with europium - 1.0-5.0 wt %, Tinuvin 622 - 1.0-3.0 wt % and high-pressure polyethylene - the rest. Composition is in form of granules which are a concentrate of modifying additives in a polymer matrix.
EFFECT: longer service life of the film.
8 cl, 1 dwg, 5 tbl, 4 ex
SUBSTANCE: film contains a polyolefin base resin and a polyolefin carrier resin which contains 5-35 wt % CaCO3. The base and carrier resins are distinguished by molecular weight, density, flow melt index and/or polydispersity. The film can be multilayered, where the first layer contains one or more compounds such as ethylene vinyl acetate, ethylene ethyl acetate and ethylene acrylic acid, and the second layer is made from polyolefin containing calcium carbonate. The calcium carbonate can be surface-treated with one or more fatty acids having 8-24 carbon atoms. The films have low rate of vapour and moisture penetration.
EFFECT: packaging materials made from said films are moisture sensitive.
33 cl, 5 tbl, 34 ex
SUBSTANCE: method involves: (A) putting a product in a packing article, containing a multilayer wrapping film welded onto itself, (B) heat sealing the closed product so that the product is surrounded by the multilayer wrapping film; (C) heating the packed product to temperature of at least 212°F for at least approximately 0.5 hours, where heating takes place in the presence of vapour under pressure. The multilayer wrapping film contains: (1) a cross-linked first outer layer which serves as an insulating layer and the in contact with the product, and (2) a cross-linked O2-impermeable layer containing a mixture of: (i) 50-95 wt % in terms of the weight of the mixture of amorphous polyamide, which contains at least one polyamide selected from a group comprising PA-6I/6T; PA-MXD,I/6,I; PA-6/6,T; PA-6/6I; PA-6,6/6,I; PA-6,6/6,T; and (ii) polycrystalline polyamide which contains at least one polyamide selected from a group consisting of (a) 5-50% of the weight of the PA-MXD,6/MXD,I mixture and (b) 5-15% of the weight of the mixture, polyamide with or without a nucleating agent, having reduced viscosity measured in accordance with the ISO 307 test method from 150 ml/g to 245 ml/g.
EFFECT: obtaining a packed food product sterilised in an autoclave and having a long shelf life.
11 cl, 2 ex, 2 tbl, 2 dwg
SUBSTANCE: film is obtained from a polymer composition. The composition contains 90-99.95 wt % transparent thermoplastic - polycarbonate and 0.01-10 wt % transparent polymer particles on an acrylate base with a "core-cladding" structure with average diameter from 1 to 100 mcm. The film contains more than 500 mln-1 transparent polymer particles on the acrylate base with average diameter from 80 to 200 nm.
EFFECT: invention enables to obtain films with high light transmission and light scattering.
5 cl, 4 tbl, 7 ex
SUBSTANCE: sheet includes, in standard version, a permeable fibre-reinforced thermoplastic middle layer, having the first surface and the second surface. The middle layer includes structures with open cells, formed by accidental weaving of multiple reinforcing fibres, having the average length approximately from 5 to 50 mm and attached to each other by thermoplastic resin, having density approximately from 0.1 g/cm3 to 1.8 g/cm3, content of cavities is approximately between 1 and 95%, and approximately 20-80 wt % of fully or mostly noncompacted fibres or particles of thermoplastic materials. The multilayer sheet also includes at least one first reinforcement shell on the first surface of the middle layer, and at least one second reinforcement shell on the second surface of the middle layer. Each first and each second reinforcement shell includes a matrix of reinforcement fibres and thermoplastic resin, where reinforcement fibres of the matrix on the first surface, and reinforcement fibres of the matrix on the second surface are aligned in two directions. The structural component of a vehicle interior includes a seat back of the specified multilayer fibre-reinforced material.
EFFECT: increased operational reliability.
20 cl, 3 dwg
SUBSTANCE: invention relates to use of terpolymers of propylene/butylene/ethylene with a nucleating agent to form sterilising films obtained via extrusion blowing. A film is obtained from a polymer composition containing (i) and (ii) 0.001-1.0 wt % of one or more phosphorus-containing and/or polymeric α-nucleating agents. The terpolymer of propylene, ethylene and butylene consists of 86.0-98.0 wt % propylene, 2.0-12.0 wt % butylene and 0.1 to less than 1.0 wt % ethylene. The obtained films have a) turbidity according to ASTM D 1003-92 for a 50 mcm film less than 8% before and after steam sterilisation at 121°C for 30 minutes and b) lustre at 20° according to DIN 67530 for a 50 mcm film of at least 55% before steam sterilisation at 121°C for 30 minutes and at least 60% after steam sterilisation at 121°C for 30 minutes. The films are sterilisable and have excellent optical and mechanical properties.
EFFECT: improved method of obtaining films.
16 cl, 4 tbl, 3 ex
SUBSTANCE: silicon layer is extruded. The silicon layer can be extruded onto a carrier layer or the silicon layer and the carrier layer are extruded together from an extruder bore.
EFFECT: method enables to obtain thin silicon layers in a single step.
40 cl, 3 dwg, 3 ex
FIELD: process engineering.
SUBSTANCE: inventions relate to production of polyimide film used as heatproof electric insulation or as metalised film substrates for electronic hardware. Proposed device comprises two containers with solutions of polyamine acid with catalysts and dehydrating agent 1, two gear pumps 2, two-slit spinneret 3, drum 4 or endless tape 6, and high-temperature rolls. Primary element of proposed device is said two-slit spinneret with two separate slit heads to feed solutions and constrictors, 5-10 mm-wide and 10-20 mm-long, arranged on faces of each slit on spinneret edges. Said spinneret consists of two cheeks 7, two half-dies 12 and 14, spacer 13, differential screw 11, threaded coupling 10, lock screw 5, assembly screw 15 and four limiters 8. Produced method comprises feeding two solutions of polyamine acid with ring formation catalysts and dehydrating agent on drum or endless tape moulding surface via one spinneret at 0.8-1.0 MPa with solutions dynamic viscosity of 200-500 p, and performing imidine formation at stepped temperature increase from 150°C to 350°C.
EFFECT: high-quality, uniform-thickness polyiminide film.
4 cl, 4 dwg, 1 tbl
SUBSTANCE: composition contains polyethylene and traditional additives, has density of 0.915-0.955 g/cm3, melt index MI from more than 0 to 3.5 g/10 min, flow-rate rating HLMI/MI of 5-50 and polydispersity Mw/Mn of 5-20. Z-average molecular weight Mz of the mouldable composition is less than 1 million g/mol. The mouldable composition is obtained in one reactor in the presence of a mixed catalyst which contains a pre-polymerised chromium compound and metallocene.
EFFECT: films containing disclosed mouldable compositions have very good mechanical properties, high impact resistance and high breaking strength coupled with very good optical properties, the films do not easily stick together and they can be transported in a car without adding lubricants and anti-adhesives or only in their small amount.
9 cl, 3 tbl, 6 ex
SUBSTANCE: composition contains a mixture of polyamide, where the ratio of terminal amino groups in the terminal carboxyl groups of the polyamide polymer is less than 0.2, polyester which is capable of crystallising and an interfacial tension reducing agent.
EFFECT: composition enables to obtain dispersed particles with average size of less than 200 nm when stretched, good colour composition which will not exhibit high increase in turbidity with increase in the amount of dispersed material, or has acceptable turbidity during production, and has good colour, especially in the absence of cobalt.
7 cl, 3 tbl, 18 ex, 8 dwg
SUBSTANCE: coating composition contains a polyvinyl chloride polymer, an acrylic resin which is preferably a polymer obtained from monomer acrylates or methacrylates, such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate resins, copolymer resins of said components or mixtures thereof, a cross-linking agent which is obtained from phenol, para-tert-butylphenol, xylenol or mixture thereof, and formaldehyde, an additive, a dye and a solvent component, and the composition essentially does not contain bisphenol A diglycidyl ether (BADGE) and bisphenol A resin. The coatings are suitable for containers made from three parts, as well as for metal cans made through deep-drawing. The coatings are particularly useful for covers which are torn in order to open due to their unusual flexibility and resistance to sterilisation.
EFFECT: composition provides coatings for metal cans which have suitable flexibility, resistance to scratching, adhesion and sterilisation during processing while in contact with food.