Multi-product, multi-layered workpiece, a method of manufacturing articles made of polyester with plastic barrier coating (options), method for the production of multilayer plastic container (options) and the method of manufacture of polyethylene terephthalate plastic with a barrier layer of a copolymer of terephthalic acid, isophthalic acid and diol

 

(57) Abstract:

The invention relates to products made of polyester plastic, preferably polyethylene terephthalate (PET) having one or more layers of thermoplastic material with good barrier characteristics for gas applied directly to at least one of its surfaces, and new methods of making such products. Preferably products with barrier coating have the shape of a workpiece covered at least one layer of barrier material, and containers, formed out of them blowing. Such containers with barrier coating preferably are of the type for storing beverages such as soft drinks, beer or juice. Preferred barrier materials have a lower permeability to oxygen and carbon dioxide than PET, and their key physical properties are the same with PAT. Materials and methods ensure that the barrier layers have good adhesion to PET even during blow molding and thereafter for forming containers from blanks. Preferred materials barrier coatings include poly(hydroxylaminopurine). In one preferred method saunasauna procurement, a method of manufacturing articles made of polyester with plastic barrier coating (options), method for the production of multilayer plastic container (options) and the method of manufacture of polyethylene terephthalate plastic with a barrier layer of a copolymer of terephthalic acid, isophthalic acid and diol. Describes a multilayer product, the murine portion of which contains the inner and outer layers. The inner layer has at least two discrete sublayers: one of the sublayers contains polyethylene terephthalate, other barrier material made of thermoplastic proxytype or copolymer of terephthalic acid, isophthalic acid and at least one diol, and the outer layer contains recycled polyethylene terephthalate. 6 C. and 31 C.p. f-crystals, 17 ill.

The invention relates to polyester plastic with barrier coating, preferably the polyethylene terephthalate (PET) with a barrier coating and the products made from it. Preferably PET barrier coating takes the form of workpieces with at least one layer of barrier material, and bottles made of them blow molding. The invention further relates to methods of manufacturing products formed Yemeni glass or metal containers for packaging of beverages has become extremely popular. Advantages of plastic packaging include lighter weight, reduced brittleness compared with glass and potentially lower cost. The most common plastic used in the manufacture of beverage containers, is currently the PET. Clean PET was approved by the FDA for use in contact with food products. Containers made from PET, transparent, thin wall, light weight and have the ability to maintain its shape by the resistance force applied to the vessel wall compressed content, such as carbonated beverages. PET polymers are also very inexpensive and easy to handle.

Despite these advantages and widespread use, there is a serious downside in the use of PET in thin-walled containers for beverages - permeability to gases such as carbon dioxide and oxygen. These problems are particularly important when the bottle is small. In a small bottle of the ratio of surface area to volume is large, allowing a large surface for penetration of the gas contained inside through the walls of the bottle. The permeability of PET bottles is reflected on soft drinks, which become "burned out" from spat unsuitable for all applications, required in industry, and for many of the existing uses, and the expiration date of liquids, Packed in PET bottles, shorter than desired.

Although the industry of plastic bottles for beverages is large and competitive, and the problem of permeability of PET bottles is known from the beginning of their use, there is still no good working problem solution permeability. Attempts to produce containers with barrier coatings until now, most have been unsuccessful.

Most of the problems with the production of tanks coated stems from the difficulty in finding suitable barrier materials. When most materials are deposited on the PET, they are not concatenated or concatenated so weak that they will peel off from the PET through a short period of time or at the minimum pressure. Examples of such materials are polyvinyl chloride (PVC) and grades (PVDC). The pieces that interlock with PET, often do not have good barrier properties or have other characteristics that make them suitable for use in cheap commercial vessels with barrier coating.

U.S. patent 5464106 issued Slat et A1., opisyvaemye materials: polyethylenterephthalat, Saran, ethylenevinylacetate alcohol or copolymers of Acrylonitrile. In technology Slat barrier material and the material for forming the inner wall of the workpiece pressed together in the shape of a tube. This pipe is cut to lengths corresponding to the length of the workpiece, and is then placed inside the shape, where the outer layer of the preform is injected through the tube to form the final preform. The workpiece can then be formed by blowing to form the bottle. The disadvantages of this method lie in the fact that most of the considered barrier materials not linked to PET, and the process itself is quite bulky.

A set of materials with good barrier characteristics discussed in U.S. patent 4578295 issued Jabarin. Such barrier materials include copolymers of terephthalic acid and isophthalic acid with ethylene glycol and at least one diol. This type of materials commercially available as In-010 from the firm Mitsui Petrochemical Ind. Ltd (Japan). These barrier materials are mixed with polyethylene terephthalate to form the compositions of 80-90% PET and 10-20% of the copolymer, from which the formed containers with barrier coatings. Containers made from such compositions have barriers from prohozhdenie, only considered harvesting or packing containers are manufactured from the compositions of these materials. There is no evidence that anyone by now really made a layered workpiece or the capacity to use these materials to substantiate this assertion.

Another group of materials, polyaminoacid, was proposed for use as barrier coatings on gas. These materials can be used to form the barrier coating on the polypropylene surface treated PET, as described in U.S. patent 5489455 issued by Nugent et al. These materials are normally supplied as a solution or liquid termotorgmash mixture and is typically applied by spraying on the tank and then are heat-cured for forming a complete barrier coatings. As termootdelenija, these materials are unsuitable for use as coatings, castings, as when the floor once hardened, it can no longer be softened by heating, and thereby can be formed by blowing in contrast to thermoplastic materials which can be softened at any time after application.

Another t the ditch to effect the bonding between the PET and the barrier material. Farha describes two types of layered materials, sandwich and DL. In a three-layer laminated material of the amorphous thermoplastic copolymer is placed between the barrier layer of thermoplastic phenoxy-type and a layer of PET, to serve as a mediating layer for bonding the inner and outer layers. In the two-layer laminated material thermoplastic, phenoxy-type first mixed with an amorphous thermoplastic polyester, and then this composition is applied on a PET for the formation of the barrier. These laminates manufactured by extrusion or by blower molding, where each layer is allowed to cool before blown another layer of material.

Thus, it remains an inexhaustible need for blanks and containers made of PET with a barrier coating, which are cost-effective, visually appealing, easy to manufacture and has good barrier and physical characteristics.

This invention relates to products made of PET having one or more thin layers of thermoplastic material with good barrier characteristics from the gas deposited on surfaces of products. Products of the present invention are preferably in the form is phenoxy-type containing poly(hydroxyamino).

In one aspect of the present invention proposed a multilayer article containing murine portion containing an internal multi-component layer and the outer layer. Internal multi-component layer has at least two discrete sub-layer with the surface of the coupling between the sublayers and stretches along the length of the product, and one of the sublayers contains polyethylene terephthalate, and the other of the sublayers contains a barrier material containing (i) thermoplastic phenoxy-type or (ii) a copolymer of terephthalic acid, isophthalic acid and at least one diol, and the material has a permeability for carbon dioxide, equal to not more than one-third of the permeability of carbon dioxide poly (ethylene terephthalate). The outer layer contains recycled polyethylene terephthalate and internal multi-component layer and the outer layer contain materials with absolute refractive index of 1.55 and 1.75.

In another aspect of the present invention proposed a multilayer billet containing the murine portion of the inner layer and outer layer. The inner layer contains polyethylene terephthalate, stretched along the length of the workpiece, ending at the end of the threaded throat Castelbajac the throat part and has a thickness of at least 2 mm and an absolute refractive index 1,55-1,65. The outer layer together with the inner layer acts to end below the support ring and contains (i) a copolymer of terephthalic acid, isophthalic acid and at least one diol or (ii) thermoplastic phenoxy-type selected from the group consisting of poly(hydroxyether), poly(hydroxy complex and simple ether) and poly(hydroxylaminopurine), and the outer layer has a permeability to oxygen is less than the inner layer, and a thickness of not more than a quarter of the thickness of the inner layer. Next, the outer layer has an absolute refractive index of such value to ensure that the ratio of the refractive indices in the range of 1.0 to 1.2.

In another aspect of the present invention, a method for manufacturing articles made of polyethylene terephthalate with a barrier coating. Polyester product, at least with the inner surface and the outer surface is formed by injection box molten poly (ethylene terephthalate) through the first valve into the space defined by the first half of the form and the Central half of the form, where the first half of the form and the Central half of the form is cooled by circulating liquid and the first half of the forms in contact with the external surface is of interelate. Following this, the molten polyethylene terephthalate left in contact with the halves of the form until, until you form a shell on the outer and inner surfaces of polyethylene terephthalate, which surround a core of molten polyethylene terephthalate. The first half of the form is then removed from the articles of polyethylene terephthalate and the sheath on the outer surface of the polyethylene terephthalate is softened by heat transfer from the molten core of polyethylene terephthalate, while the inner polyester surface is cooled with continued contact with the Central half of the form. In the operation of applying a barrier layer comprising a barrier material, is placed on the outer surface of polyethylene terephthalate by injection of molten barrier material through the second valve into the space defined by the second half of the form, and on the external surface of the polyethylene terephthalate to form the products of polyethylene terephthalate with a barrier coating. Barrier materials used in the method preferably contain a thermoplastic, phenoxy-type or a copolymer of terephthalic acid, isophthalic acid and at least one diol.

In another aspect nastojasih is, aderrasi several operations. Provided first polymer containing polyethylene terephthalate and a second polymer containing a copolymer of terephthalic acid, isophthalic acid and at least one diol that injections through thin-layer injection system to provide a composite stream from many thin layers having at least one discrete thin layer of polyethylene terephthalate and at least another discrete thin layer of the copolymer. The composite stream is then fed into a form for shaping a starting material with the inner and outer sublayers containing polyethylene terephthalate and a copolymer, where the sublayer containing copolymer has a permeability to air is less than the permeability to air of the sublayer containing polyethylene terephthalate. Recycled polyethylene terephthalate is then fed through the initial blank for forming the outer layer to form the final preform. End billet is then subjected to a blow molding operation for forming a multilayer plastic container.

In another aspect of the present invention, a method of "TYPHOID fever after injection box" for the production of multilayer plastic container is ethyleneterephthalate. Provided by the first body of thermoplastic polymer containing recycled polyethylene terephthalate, and a second body of thermoplastic barrier polymer containing (i) a copolymer of terephthalic acid, isophthalic acid and at least one diol or (ii) thermoplastic phenoxy-type, and these bodies injections through thin-layer injection system with block joint extrusion to provide a composite stream from many thin layers having at least one discrete thin layer of recycled polyethylene terephthalate and at least one discrete thin layer of thermoplastic barrier polymer. The composite stream is then fed through the initial workpiece to form the final preform and composite thread has sublayers of recycled polyethylene terephthalate and a thermoplastic barrier material covers the initial preparation of poly (ethylene terephthalate) and the target workpiece is subjected to the blow molding operation for forming a multilayer plastic container.

The following aspect of the present invention, a method for manufacturing and coating of workpieces. The method begins by closing the form that contains the fixed mounia billets and at least one cavity for coating workpieces, and a movable half of the form contains a swivel pad installed a number of bars equal to the amount of cavities forming blanks and cavities of the coating of workpieces. Other operations include: injection box of the first material in the space defined by the mandrel and into the cavity of the molding blanks for forming a workpiece with an internal surface and an external surface; opening the mold; rotating the rotating platform; closing the mold; the injection box of the second material in the space defined by the outer surface of the workpiece, and the cavity of the cover blanks for forming a coated workpiece; opening the mold; removing the coated workpiece.

In further aspects of the above invention, the barrier materials of the present invention may further contain nanoparticles. The layer of barrier material in the products of the present invention may consist of many lamellae containing barrier material.

Brief description of drawings

Fig.1 is uncovered by the workpiece, is used as the starting material for the present invention.

Fig. 2 is a cross with the s in accordance with the present invention.

Fig. 3 is a cross-section of one preferred implementation of the workpiece with the barrier coating of the present invention.

Fig. 4 is a cross-section of another preferred implementation of the workpiece with the barrier coating of the present invention.

Fig. 4A is an enlargement of part of the wall of the workpiece, such as is manufactured by a process of injection with TYPHOID. Not all blanks of the type shown in Fig 4, made in accordance with the present invention, will have this type of layout layers.

Fig. 5 is a cross-section of another preferred implementation of the workpiece with the barrier coating of the present invention.

Fig. 6 is a cross-section of the preferred preform in a cavity of a blow molding device of the type which may be used for the manufacture of the preferred containers with barrier coating of the present invention.

Fig. 7 is one preferred implementation of the capacity with the barrier coating of the present invention.

Fig. 8 is a cross-section of one preferred implementation capacity barrier coating according to the present izobreteniya for manufacturing the preferred preform with a barrier coating of the present invention.

Fig. 10 and 11 are the two halves of the molding machine for the manufacture of workpieces with a barrier coating.

Fig. 12 is a schematic representation of the system thin-layer injection molding (TYPHOID).

Fig. 13 and 14 are the two halves of the molding machine for the manufacture of forty-eight two-layer blanks.

Fig.15 is a view in perspective schematic form image with the mandrel, partially located inside the cavities forming.

Fig. 16 is a view in perspective of the form with the mandrel, completely taken out of the molding cavities to the rotation.

Fig.17 is a two-layer implementation of the workpiece.

This invention relates to plastic articles having coatings containing one or more layers of thermoplastic material with good barrier characteristics from the gas, and to methods for producing such products. As currently anticipated, one of the executions of the products with the barrier coating is a bottle of the type used for beverages. Alternative products with the barrier coating of the present invention may take the form of cans, tubes, trays or bottles for storage of the LM is the context of bottles for beverages and preparations, from which they are manufactured by blow molding.

In addition, the invention described herein specifically in connection with polyethylene terephthalate (PET), but applicable to many other thermoplastics polyester type. Examples of such other materials include 2,6 - and 1,5-naphtalate (PAN), polytetramethylene 1,2-deoxybenzoin and copolymers of ethyleneterephthalate and ethyleneterephthalate, but does not include copolymers of terephthalic acid, isophthalic acid and at least one diol, which are described elsewhere in the text as a barrier material.

Preferably procurement and capacity have a barrier placed on their outer surfaces or within the vessel wall. In contrast technology Slat, which produces a multi-layer preform, in which the layers are separated immediately, in the present invention thermoplastic barrier material bonded directly and firmly with the surface of the PET and can not be easily separated from it. The adhesion between layers occurs without the use of any additional materials, such as adhesive material or bonding layer. The coated workpiece is processed preferably by stretching blow molding for forming bottles with the bones in the solid, resistant to infiltration and attractive in appearance and have good barrier properties against gas.

As explained in more detail below, to perform the present invention uses one or more layers of barrier material. As used here, the term "barrier material", "barrier resin" and similar are materials that, when used for the formation of the items are of key physical properties similar to PET, well linked to PET and have a lower than PET permeability to oxygen and carbon dioxide.

A number of materials having the desired low permeability to gases such as oxygen and carbon dioxide, are suitable in the present invention, the choice of barrier material partially depends on the mode or application, as described below. Preferred barrier materials for use in the barrier coatings of the present invention fall into two main categories: (1) copolymers of terephthalic acid, isophthalic acid and at least one diol, which is described in the previously mentioned patent granted Jabarin, and which are commercially available as In-010 from the firm Mitsui Petrochemical Ind. Ltd (Japan), and (2) hydro is as described in U.S. patent 5134218, polyesters, such as described in U.S. patent 5115075 and 5218075, hydroxyquinoline polyesters, such as described in U.S. patent 5164472, hydroxyquinoline poly(eversonpaladini), such as described in U.S. patent 5149768, poly(hydroxy complex ethers), such as described in U.S. patent 5171820, polymers of hydroxytamoxifen, such as described in U.S. patent 5814373, and poly(hydroxyamino ethers) ("PHAE"), such as described in U.S. patent 5275853. Barrier materials described above in (1), here called by the term "Barrier material from copolymers". The mixture described above in the patents (2), are classified together, and they are called here in the text the term "Thermoplastic, phenoxy-type" All patents referenced in this paragraph, included in its entirety in this description by reference.

The preferred copolymer barrier materials have the imprimatur of the FDA. Sanction FDA allows these materials to be used in tanks where they are in contact with drinks, etc. that are intended for human consumption. As far as known to the inventor, none of thermoplastics, phenoxy type is not sanctioned by the FDA as of the date of this description. Thus, these materials predpochtiteljno edible.

For the implementation of the preferred methods of the present invention in the formation of preforms and bottles with barrier coating initial billet is prepared or obtained, and then coated with at least one additional layer of material containing barrier material, polyesters, such as PET, used or recycled PET (jointly recycled PET) and/or other compatible thermoplastic materials. The coating layer can contain a single material, a mixture or composition materials (heterogeneous or homogeneous), interwoven matrix of two or more materials, or many of the lamellae (thin layer) containing at least two different materials. In one implementation, the initial workpiece contains many of the lamellae, which can be prepared using the process of injection molding plates. A starting material include polyester, and particularly preferably, a starting material contained pure materials, which authorized the FDA to stay in contact with food.

Thus, the billet and the container of the present invention can exist in multiple executions, such as: net roloi barrier material and recycled PET; clean PET coated with a barrier layer, which is in turn coated with recycled PET; microlayers clean PET and barrier material coated with a layer of recycled PET; or a clean PET, coated with recycled PET, which is then covered with a barrier material. In any case, at least one layer must have at least one barrier material.

Different executions of blanks and bottles according to the present invention all have advantages in that they allow the use of a starting material, which may be made of a structurally strong unit. Thus, with commercial operations starting material can be prepared using the technologies of mass production, stored during the time periods from hours to months, and then be subjected to the imposition of one or more barrier layers and/or poly (ethylene terephthalate) to form the final preform, which can be immediately subjected to the blow molding operation or, as the initial procurement, stored for long periods of time to conduct the final blow molding operation.

In one preferred implementation of this izobrazevanje.

As described above, the preferred barrier materials for use in accordance with the present invention are copolymer barrier materials and thermoplastics, phenoxy-type. Other barrier materials having similar properties may be used instead of these barrier materials. For example, the barrier material may take the form of other thermoplastic polymers such as acrylic resins, including polymers of polyacrylonitrile and copolymers of Acrylonitrile. Preferred barrier materials of the present invention have a permeability to oxygen and carbon dioxide, which is less than one third of the permeability of polyethylene terephthalate. For example, a copolymer barrier materials of the type disclosed in the aforementioned patent issued Jabarin will have a permeability to oxygen of about 11 [SS mil]/100 square inches per day and a permeability to carbon dioxide of about 2 [SS mil]/100 square inches per day. For certain PGAE permeability to oxygen of less than 1 [SS mil]/100 square inches per day. The corresponding permeability for CO2poly (ethylene terephthalate) or recycled, either in its pure form, is approximately equal 12-20 [SS mil]/100 square inches is later blown into the bottle. Such methods are preferred to place the coating on the bottles themselves. The workpiece is smaller in size and have a smoother shape than the container blown from them, which makes it easier to obtain a smooth and continuous coating. In addition, bottles and containers of various shapes and sizes can be manufactured from blanks of the same size and shape. Thus, the same equipment and processing can be used for the production of blanks in the formation of several different kinds of containers. Blow molding can take place immediately after molding, or the workpiece can be produced and stored for subsequent blow molding. If blanks are stored before blow molding, their smaller size allows them to occupy less space when stored.

Even if you prefer to build the capacity of the coated blanks, they are typically not used because of the difficulties existing with the manufacture of containers made of coated or laminated blanks. One operation, where the greatest difficulties in the blow molding process for forming containers from blanks. During this process can occur defects such as peeling layers, removal to be overcome by the use of suitable barrier materials and coating workpieces thus, which provides good adhesion between the layers.

Thus, one key to the present invention is the selection of suitable barrier materials. When using a suitable barrier material, coating bonded directly to the workpiece without any significant exfoliation and will remain glued, when the workpiece after it is molded by blowing into the bottle. The use of a suitable barrier material also helps to reduce the chance of external and structural defects which can be formed from the blowing of the containers as described above.

It should be noted that although most of the discussion, drawings and examples of the manufacture of coated blanks are blanks of two layers, such discussion is not intended to limit the present invention the products of two layers. Barrier capacity and procurement of two layers according to the present invention are suitable for many uses and cost-effective due to savings in materials and operations. However, in some circumstances and for some applications it may be desirable to preform consisting of more than two layers. The use of three or more layers photosespecially barrier materials. Thus, as part of the invention it is assumed that all of these methods produce billets with a barrier coating of the present invention as disclosed herein and any other suitable methods of making such preparations can be used either singly or in combination for the manufacture of preforms and containers with barrier coating containing two or more layers.

In Fig.1 shows the preferred procurement 1 without a cover. The blank is preferably made of FDA sanctioned material, such as pure PET, and may be of any shape and size from the many shapes and sizes. The workpiece shown in Fig.1 refers to the type of workpieces, which forms the bottle for carbonated beverages to 16 ounces, which requires a barrier for oxygen and carbon dioxide, but, as will be clear to the specialist, other configurations of the workpieces can be used depending on the desired configuration, characteristics and use of the final product. Preferably billet blower manufactured by molding, as is known from the prior art.

In Fig.2 shows a cross-section of a preferred workpiece 1 without a cover according to Fig.1. The workpiece 1 otoki and elongated in the direction of the support ring 6 and includes it. Throat part 2 further characterized by the presence of the thread 8, which provides a means for securing the cap on the bottle, made from billet 1. Body part 4 is elongated and has a cylindrical form extending down from the throat part 2 and ending in a rounded end cap 10. The thickness of the workpiece 12 will depend on the total length of the workpiece, wall thickness and overall size of the final container.

In Fig. 3 disclosed a cross section of one type of workpiece 20 with the barrier coating of the present invention. The workpiece 20 with a barrier coating has a throat portion 2 and a body portion 4, as uncovered the workpiece 1 according to Fig.1 and 2. The layer 22 of the barrier coating deposited on the entire surface of the body part 4, ending on the bottom supporting ring 6. The layer 22 of barrier coverage is not extended by the throat part 2 and is not present on the internal surface of the workpiece 16, which preferably is made of FDA sanctioned material, such as PET. The layer 22 of the barrier coating can contain either a single material or multiple lamellae of at least two materials and manufactured using the process of TYPHOID, as described below. The thickness of the entire workpiece 26 rawney coating total capacity. For example, the bottom wall part may have a thickness of 3.2 mm; cross section of the wall of the throat end of about 3 mm; and imposed barrier material thickness of about 0.3 mm

In Fig. 4 in cross-section showing a preferred implementation of the coated workpiece 21. The first difference between the coated workpiece 21 and covered by the workpiece 20 in Fig.3 is the relative thickness of the two layers in the area of the end cap 10. Covered the workpiece 20 in Fig.3 the barrier layer is typically thinner than the thickness of the starting material throughout body part. Covered the workpiece 21, however, the layer 22 of the barrier coating is thicker at the point 29 about the end cap 10 than at the point 25 in the murine part 3 and, on the contrary, the thickness of the inner polyester layer is greater at the point 23 in murine part 3 than at point 27 in the area of the end cap 10. This construction procurement is particularly useful when the barrier coating is deposited on the starting material in the process of reorganization for the manufacture of covered procurement, as described below, where he represents certain advantages, including the fact that it is associated with the reduction of the cycle time of formation. Layer 22 and a barrier coating may be uniform or may contain many is providing the fabrication of the layers in the execution of the procurement process insufflation with TYPHOID. Layer 110 is an internal layer of the workpiece, and 112 is the outermost layer of the workpiece. The inner layer 112 contains many of the lamellae of the material, as will be done when the system will be used for TYPHOID. Not all blanks according to Fig.4 will be of this type.

In Fig. 5, another implementation of the coated workpiece 31 is shown in cross section. The primary difference between the coated workpiece 31 and covered with blanks 20 and 21 in Fig.3 and 4, respectively, is that the layer 22 of barrier coatings is located in the throat part 2, and also in the body part 4.

Procurement and capacity barriers of the present invention can have layers that have a wide range of relative thickness. For the present description, the thickness of a given layer and the entire workpiece or capacity at a given point or over the entire capacity can be selected to match the method of coating or specific end-use capacity. Moreover, as discussed above with respect to the layer with the barrier coating according to Fig.3, the layer of barrier coating in the execution of the billet and the container disclosed herein may contain a single material or several of the lamellae of the two or more materials.

After Kano in detail below, it undergoes a process of stretch blow molding. In Fig.6 in this process, the workpiece 20 with the barrier coating is placed in the form of 28 with a cavity corresponding to the desired shape of the container. Procurement barrier coating is then heated and expanded by stretching and using air pressure inside the workpiece 20 to fill the cavity inside the form 28, creating a container with a barrier coating. The blow molding operation is usually limited body part 4 of the workpiece with the throat part 2, includes a threaded thrust ring and the supporting ring, retaining original configuration, as in the workpiece.

In Fig. 7 discloses the implementation capacity of 40 with a barrier coating in accordance with the present invention, such as that which may be produced during blow molding, the preform 20 with a barrier coating according to Fig.3. The tank 40 has a neck portion 2 and a body portion 4 corresponding to the throat and body parts of the workpiece 20 with the barrier coating according to Fig.3. Throat part 2 further characterized by the presence of the thread 8, which provides a means of fastening the cover on the container.

When the container 40 with the barrier coating is viewed in transverse seinasti 4 containers 40, stopping directly under the supporting ring 6. The outer surface 50 of the container, which is made of a material, FDA sanctioned, preferably PET, remains uncovered, so that only the inner surface is in contact with drinks or food. In one preferred implementation, which is used as a container for carbonated beverages, the thickness of the barrier coating is preferably 0,020-to 0.060 inches, more preferably 0,030-0,040 inch, the thickness of the layer 46 PET is preferably 0,080-0,160 inches, more preferably 0,100-0,140 inches, and the total thickness 48 of the vessel wall 40 with the barrier coating is preferably 0,140-0,180 inches, more preferably 0,150-0,170 inches. Preferably, on average, to the total thickness 48 of the vessel wall 40 had a large part of its thickness from the inner layer of PET.

Fig. 9 shows a preferred form for use with methods that use performance. The form contains two halves, half of the cavity 52 and half 54 of the mandrel. Half 52 of the cavity includes a cavity which is uncovered procurement. The workpiece is held in place between half 54 of the mandrel, which transmits the pressure to the workpiece, thus, hermetically separated from the body part. Inside the workpiece 58 is the mandrel 96. When the workpiece is in the form body of the billet is completely surrounded by a hollow space 60. The workpiece is located, therefore, acts as an internal matrix of the mandrel in a subsequent injection procedure, in which the melt performimg material is injected through the valve 56 in the hollow space 60 for forming the coating. The melt, as uncovered by the workpiece is cooled by fluid circulating through the channels 55 and 57 in the two halves of the form. Preferably the circulation in the channels 55 are completely separated from the circulation in the channels 57.

Fig. 10 and 11 are schematic images of parts of the preferred type of device for the manufacture of coated workpieces in accordance with the present invention. The device is a system of injection molding for the manufacture of one or more uncoated blanks and subsequent covering newly manufactured wood beringela barrier material. Fig. 10 and 11 show two halves of the form of the device, which will be located opposite each other in the molding machine. The pins 94 of the alignment in Fig.11 IG.11, has a few pairs of cavities form, and each cavity is the same with the cavity of the form shown in Fig.8. Oral forms are of two types: the first injection cavity 98 molding blanks and second injection cavity 100 forming the coating. Two types of cavities equal in number and preferably set so that all cavities of the same type are on the same side of the injection unit 101 when divided into two parts by a line passing between the pins 96 of the alignment. Thus, each molding cavity 98 of the workpiece is 180ofrom the cavity 100 of the coating of the workpiece.

Half of the form shown in Fig.10, has several bars 96, one for each pan cavity (98 and 100). When the two halves are shown in Fig. 10 and 11 are fitted together, the locking pin 96 is included inside each cavity and serves as a form for the inner surface of the blank in forming the cavity 98 of the workpiece and as a centering device for uncoated blanks in the cavities 100 of cover blanks, filling that becomes the inner space of the workpiece after it is molded. Mandrel mounted on rotatable platform 102, which rotates 180oaround its center so that Oprah is STU 100 coating of workpieces and Vice versa. As described in greater detail below, this type of installation allows the blanks to be shaped and then covered in a two-stage process using the same equipment.

It should be noted that the drawings of Fig.10 and 11 are merely illustrations. For example, these drawings show a device with three cavities 98 molding and three cavities 100 of coverage (device 3/3 cavity). However, the device can have any number of cavities, as there are an equal number of cavities for molding and coating, for example, 12/12, 24/24, 48/48, etc. Cavities can be arranged in any suitable manner that may be determined by a specialist. These and other smaller changes are seen as part of the invention.

In Fig. 12 shows a schematic representation of a device that can be used for the manufacture of melt flow, consisting of many of the lamellae or thin layers in the process of thin-layer injection molding (ELISA), as will be described in detail below.

Two halves of the form shown in Fig.13 and 14 show the progress of the form of the device having 48/48 cavities, as discussed for Fig.10 and 11.

In Fig. 15 shows a perspective view Faure mandrel 96 is partially located inside the cavities 98 and 100. The arrows show the movement of the mobile half of the form, on which lie the mandrel 96, when the form is closed.

Fig. 16 shows a perspective view of the form of that kind, which is used in the process of performance, where the mandrel 96 is fully extended from the cavities 98 and 100. The arrows indicate that the rotatable platform 102 is rotated 180oto move the mandrel 96 from one cavity to another. Also shows diagrams depicting the cooling means for half of the form. On the stationary half of the cooling cavity 106 molding blanks separately from the cooling cavity 108 of the coating of the workpiece. Both of these process are separated from the cooling mandrel 104 in the mobile half.

In Fig.17 shows a preferred three-layer preform of the present invention. This implementation coated billet is preferably made by applying two coating layers 80 and 82 on such a workpiece, as shown in Fig.1.

Preferred barrier materials in accordance with the present invention showing certain physical characteristics, which give the bottles and products with a barrier coating of the present invention the ability to withstand processing and physical effort the same athelny and have excellent barrier properties.

The clutch is the Union or bonding together two surfaces. The actual mutual coupling is a phenomenon that manifests itself at the microscopic level. It is based on molecular interactions and depends on the chemical bonds, van der Waals forces and other intermolecular forces of attraction at the molecular level.

Good adhesion between the barrier layer and a layer of PET is particularly important when the product is a barrier bottle, manufactured by blow molding the preform. If the materials are concatenated good, they will act as one unit when they are subjected to blow molding process, and subjected to effort, when there are in the form of capacity. When the clutch is weak, peeling, it will either over time or under physical stress, such as compression capacity or tightness of the containers during transportation. Exfoliation not only unattractive from a commercial point of view, this may be an indication of the lack of structural integrity of the vessel. Moreover, good adhesion means that the layers will be in close contact when the capacity is expanded during the molding process, and will move as the opening, thereby allowing you to apply a thinner coating. The barrier materials of the present invention preferably sufficiently grappled with the PET to the barrier layer could not be easily separated from the layer PET at a temperature of 22oC.

Thus, in terms of direct adhesion of the barrier layer with PET present invention differs from that disclosed Farha in U.S. patent 5472753. The Farha not disclosed and made suggestions on what thermoplastic phenoxy-type can or should be attached directly to the PET without mixing with the copolymer or the use of a copolymer as fixing layer or the copolymer itself could be used as a barrier material.

The glass transition temperature (TC) is defined as the temperature at which recrystallizes polymer undergoes a transformation from a state of soft rubber in the state of solid elastic polymer glass. In the temperature range above its TC, the material will become soft enough to allow him immediately to flow when it is subjected to external force or pressure, but not so soft that its viscosity is so low that it will act more like a liquid than as a pliable solid material. The range of temperature as the material is quite soft, to flow under the force of the air blown into the preform, and to occupy the entire form, but not so soft that it breaks or becomes uneven in texture. Thus, when the materials have the same glass transition temperature, they will have the same temperature ranges blowing, allowing the materials to be processed together without having to sacrifice quality of any of the materials.

In the blow molding process for the production of bottles from the workpiece, as is known from the prior art, the workpiece is heated to a temperature which is slightly higher than the TC of the workpiece material, so that when the inside of the preform is blown in the air, she will be able to flow to take the shape in which it is placed. If the workpiece is not hot enough and used a temperature lower than TC, then the material will be very difficult to flow properly, and it probably will break, crack or will not stretch to take shape. On the contrary, if the workpiece is heated to a temperature that is too exceeds TC, the material will become so soft that it will not be able to retain its shape and will not be processed properly.

If the material of the barrier coating imli procurement of PET covered in the barrier material, the temperature of the blowing can be selected to allow both materials to be processed within their preferred temperature ranges blowing. If the barrier coating should have the TC is different from the PET, it will be difficult, if not impossible, to choose the temperature of the blow, suitable for both materials. When the materials of the barrier coatings have TC, same with PET covered procurement behaves during blow molding as if she was made of the same material, flattening smoothly and creating visually appealing capacity with even thickness and uniform coating of barrier material where it is applied.

The glass transition temperature of PET appears in the range of 75-85oWith depending on how the PET has been treated previously. TC preferred barrier materials of the present invention preferably 55-140oS, more preferably 90-110oC.

Another factor that has influence on the quality of the barrier blanks during blow moulding is the state of the material. Preferred barrier materials of the present invention rather amorphous than crystalline. This is due to the fact that material is the material in the crystalline state. PET can exist both in crystalline and in amorphous form. However, in the present invention is very preferably, the PET has existed in amorphous form in order inter alia to help in the process of blow molding. The product of PET, formed from a melt of PET, can be brought to an amorphous form by cooling the melt at a high speed, fast enough to stop the crystallization process and to leave the amorphous state.

Internal viscosity and melt index are two properties that relate to the molecular weight of the polymers. These properties show how the materials will act under different conditions of processing, such as processes blower molding and blow molding.

Barrier materials for use in products and methods of the present invention have intrinsic viscosity preferably 0.70 to about 0.90 DL/g, more preferably 0,74-of 0.87 DL/g, most preferably from 0.84-of 0.85 DL/g and a melt index preferably 5 to 30, more preferably 7 to 12, most preferably 10.

The barrier materials of the present invention preferably have a tensile strength and resistance better than just a barrier to gas. Barrier coating with physical properties similar to PET, acts as a structural component of the vessel that allows the barrier material to replace the part of the polyethylene terephthalate in the tank without having to sacrifice quality capacity. Replacement PET allows the final containers with barrier coating to have a physical quality and characteristics, the same with their bare parts without significant changes in weight and size. It also allows you to pay any additional costs from the addition of barrier material by reducing the value of all capacity related to PET.

The sameness of the internal viscosity of the PET and materials barrier coatings help capacity to have structural integrity. This is especially important if part of the PET is replaced with the barrier material. Bottles and containers with barrier coating of the present invention is able to withstand the physical forces that uncovered capacity that allows, for example, to carry the tank with a barrier coating and treat them, as is customary for uncoated PET bottles. If the material of the barrier coating had a tensile strength substantially lower than that of PET, encosta capacity.

Sameness in creep resistance between PET and materials barrier coating helps the vessel to maintain its shape. Creep resistance refers to the ability of a material to resist changes in response to the applied force. For example, a bottle that contains a carbonated liquid, must be able to resist the pressure of the dissolved gas, pushing outwards, and to maintain its initial shape. If the material of the barrier coating had significantly lower creep resistance than PET in capacity, total capacity, probably deformed over time, reducing the shelf life of the product.

For applications where it is important optical purity, the preferred barrier materials have a refractive index equal to the same value in the PET.

When the refractive indices of the PET and the barrier material coating the same, procurement and probably more importantly, blown them optically pure products and, therefore, attractive for use as beverage containers, where the purity of the bottles is often desirable. However, if two materials have substantially different refractive indices, when they SIP or opaque depending on the degree of difference in the refractive indices of the materials.

The polyethylene terephthalate has an index of refraction for visible light in the range from 1.40 to 1.75 depending on the physical configuration. In the case of manufacturing in the form of billets, the refractive index is preferably in the range of 1.55 to 1.75, more preferably in the range of 1,55-1,65. After the workpiece has been made bottle, the walls of the final product, which can be characterized as focused on the two axes of the film, because it is subject to both for the district and axial stresses in the operation of blow molding, the polyethylene terephthalate usually indicates the refractive index in the range of 1.40-1.75 is usually 1,55-1,75 depending on the stretch factor involved in the operation of blow molding. For a relatively low coefficient of expansion of about 6:1, the refractive index is close to the lower limit, whereas for high scaling factors, about 10:1, the refractive index will be close to the upper limit of the above range. It will be clear that the scaling factors, which here is referred to, are the biaxial stretch factors derived from the ratio of the district stretching and coefficient of gotowka increased 2.5 times in the axial direction and 3.5 times in diameter, the stretch factor is about 8,75 (2,5x3,5).

When using the notation nito denote the refractive index of PET and n0to denote the refractive index of the barrier material, the relationship between the values of niand n0preferably 0.8 to 1.3, more preferably from 1.0 to 1.2, most preferably from 1.0 to 1.1. As will be clear to experts, for a relationship of ni/n0=1 the distortion due to the refractive index will be minimal, since two identical factor.

If, however, this attitude is gradually differs from the unit, the distortion increases gradually.

Preferred materials barrier coatings for use in the products and methods of the present invention are thermoplastic materials phenoxy-type and copolymers of terephthalic acid and isophthalic acid and at least one diol (copolymer barrier materials). Preferably thermoplastic phenoxy-type used as barrier materials in the present invention, belong to one of the following types:

(1) hydroxyquinoline poly(amide esters) with repeating units represented by any predstavlenie independently any one of the formulas IIA, IIb or IIc

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or

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(3) amide - and hydroxyethylpyrrolidine polyesters with repeating units represented by formula III

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(4) hydroxyquinoline polyesters with repeating units represented by formula IV

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(5) hydroxyquinoline poly(ether sulfonamides) repeating units represented by the formula Va or Vb:

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(6)poly(hydrocyclone and ethers) with repeating units represented by formula VI

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(7) hydroxyphenylethylamine repeating units represented by formula VII

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and (8) poly(hydroxylaminopurine) repeating units represented by formula VIII

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where each AG separately represents a divalent aromatic half, substituted divalent aromatic fraction or heteroaromatic share or a combination of different divalent aromatic fractions, substituted aromatic fractions or heteroaromatic shares; R is a single oxygen or a monovalent hidrocarburos shares; each AG1is a divalent aromatic fractions, or a combination of divalent aromatic fractions, bearing amide or hydroxymethylene group is, substituted divalent aromatic fractions or heteroaromatic shares or a combination of different divalent aromatic fractions, substituted aromatic fractions or heteroaromatic share, R1is separately predominantly hidrocarbonetos shares, such as divalent aromatic fraction, substituted divalent aromatic fraction, divalent heteroaromatic share, divalent Allenova share, divalent substituted Allenova share or divalent heterouncinata share or a combination of such shares; R2is individually a monovalent hidrocarburos share; And is the amine of shares or a combination of different amine shares; X is an amine, arrangiarsi, irelandireland or arrangiarsi - shares or a combination of such shares; and AG3is "carding" the shares represented by one of formulas

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where Y is nil, the covalent bond or a linking group, and suitable linking groups include, for example, an oxygen atom, a sulfur atom, the atom of the carbonyl group of sulfonyl or a methylene group or a similar binding; n=10-1000, an integer, x=0.01 to 1.0 and y=0-0,5.

The term "predominantly hydrocarbide" means the number of direct shares, such as oxygen, sulfur, imino, sulfonyl etc.

Hydroxyquinoline poly(amide ethers) represented by formula I, preferably prepared by contact N,N'-bis (hydroxyphenylazo)alkane or arene with diglycidylether, as described in U.S. patent 5089588 and 5143998.

Poly(hydroxyamide), represented by formula II, prepared by contact N,N'-bis (3-hydroxyphenyl) adipamide or N,N'-bis (3-hydroxyphenyl) glutarimide with epichlohydrin, as described in U.S. patent 5134218.

Amido - and hydroxyethylpyrrolidine polyesters represented by formula III can be prepared, for example, by reaction of diglycidylether, such as diglycidylether bisphenol a, with dihydrofolate with hanging amido, N-substituted amido and/or hydroxyalkylated share, such as 2,2-bis(4-hydroxyphenyl)ndimethylacetamide and 3.5-dihydroxybenzamide. These polymers and their preparation are described in U.S. patents 5115075 and 5218075.

Hydroxyquinoline polyesters represented by formula IV, can be prepared, for example, by allowing each diglycidylether or their combination to react with digitalanalog or a combination of dehydrolinalool using the method described in the patent itaniu of dehydrolinalool to react with epichlohydrin using the method described in Reinking, Barnabeo and Hale in the Journal of Applied Polymer Science, Vol. 7, p. 2135 (1963).

Hydroxyquinoline poly(eversonpaladini), represented by formula V are prepared, for example, by polymerization of N,N'-diacyl or N,N'-giurisdizione with diglycidylether, as described in U.S. patent 5149768.

Poly(hydroxy complex and ethers) represented by formula VI are prepared by reaction of diglycidylether aliphatic or aromatic diazide, such as diglycidylether, or diglycidylether of dehydrolinalool with aliphatic diazide, such as adipicola acid and isophthalic acid. These polyesters are described in U.S. patent 5171820.

The polymers of hydroxytamoxifen represented by formula VII are prepared, for example, by contacting at least one dinucleotide monomer with at least one diglycidylether of cardaustral, such as 9,9-bis(4-hydroxyphenyl)Floren, phenolphthalein or substituted cargolifter, such as substituted bis(hydroxyphenyl)Floren, substituted phenolphthalein or substituted phenolphthalein under conditions sufficient to cause nucleophilicity dinucleotide monomer to react with epoxidase for flea essential communication. These hydroxytamoxifen polymers described in U.S. patent 5184373.

Poly(hydroxyamino)esters (PGE or polyetheramines), represented by formula VIII are prepared by contacting one or more diglycidylether of digitifera with an amine having two amine oxygen under conditions sufficient to cause the amine fraction to react with epoxidase for forming the main chain of the polymer containing amine communications, terrestrial communications and hanging gidroksidami. These components are described in U.S. patent 5275853.

Thermoplastics, phenoxy-type formulas I-VIII may be obtained from Dow Chemical Company (Midland, Michigan, USA).

Thermoplastics, phenoxy-type, commercially available from the company Phenoxi Associates, Inc., suitable for use in the present invention. These hydroxytamoxifen polymers are products of the condensation reaction dihydroprogesterone phenol, such as bisphenol a, and epichlohydrin, and have repeating units represented by the formula IV, where AG is isopropylindole share. Method of preparation of this are described in U.S. patent 3305528, fully incorporated here by reference.

The most preferred thermoplastic is emy company Dow Chemical Company XU 19040.00 L.

Examples of preferred copolymer barrier materials and the method of their preparation are described in U.S. patent 4578295 issued Jabarin. They are in General prepared by heating a mixture of at least one reagent selected from isophthalic acid, terephthalic acid and their1and C4alkylation with 1,3 bis(2-hydroxyethoxy)benzene and ethylene glycol. Selectively mixture may further contain one or more aperforming of dihydroxypentanoic and/or bis(4-hydroxyethoxyphenyl)sulfones.

The most preferred copolymer barrier materials are those that are made from mixtures containing terephthalic acid and isophthalic acid. Particularly preferred copolymer barrier material are available as In-010 from the firm Mitsui Petrochemical Ind. Ltd. (Japan).

Preparation of polyester

Polyesters and methods for their preparation (including special monomers used in their formation, their proportions, the temperature of polymerization, catalysts and other conditions well known in the prior art, and references to them are given here for the purposes of the present invention. For purposes of illustration, but not limitation, the reference is specifically made to S. 1-62 is ns).

Usually polyesters derived from the reaction of di - or polycarboxylic with di - or policereported. Suitable di - or polycarboxylic include polycarboxylate and the esters and anhydrides of such acids and their mixture. Representative carboxylate include falikova, isophthalic, atypicality, terephthalic, oksolinovuyu, Melnikova, succinylcoa, glutaminovuyu, sebaliknya, etc. Preferred dicarboxyl components. Terephthalic acid is the most widely used and preferred in the preparation of polyester films. ,-Unsaturated di - and polycarboxylic acid (including esters or anhydrides of such acids and mixtures thereof) can be used as a partial replacement of saturated carboxyl components. Representative unsaturated di - and polycarboxylic acid include Malikova, shmarikova, continuou, itaconic, Mechnikova, citraconic, monochloracetate etc.

Normal di - and policereport used to prepare the polyester are those alcohols which have at least two hydroxy-group, although can be used small amounts of alcohol, have more or less hydroxyl groups. Preferred dihydroxyphenylglycol; ethylene glycol; 1,2-propylene glycol; 1,4-butanediol; 1,4-pentanediol; 1,5-hexanediol; 1,4-cyclohexanedimethanol, etc., 1,2-propylene glycol as preferred. Mixtures of alcohols may also be used. Di - or policereported component of the polyester is usually stechiometric or slightly excessive in relation to the acid. Excess di - or policereport very rarely will exceed 20-25 mol.% and is normally in the range of 2-10 mol.%.

Polyester is usually prepared by heating a mixture of di - or policereport with di - or polycarboxylates in their proper molar relationship at elevated temperatures, usually between 100 and 250oWith over extended periods of time, usually in the range of 5-15 hours polymerization Inhibitors, such as t-butylcatechol, can be successfully used.

PAT, the preferred polyester can be purchased, among others, the Dow Chemical Company (Midland, Michigan) and company Allied Signal Inc. (Baton Rouge, Louisiana).

Materials to enhance the barrier properties of the resins barriers

Barrier materials disclosed above can be used in combination with other materials that enhance barrier properties. Speaking in the General case, one reason for the diff is through which may pass the gas molecules. The presence of intermolecular forces in the material, such as the relationship of oxygen, allows megamachine communication in the matrix, which closes this gap prevents the diffusion of gases. You can also increase the ability to be a barrier to good gas barrier materials by adding additional molecules or substances, which takes the advantages of such intermolecular bonds and acts as a bridge between the polymer chains in the matrix, thereby helping to close the openings in the matrix and reduce the diffusion of the gas.

Derivatives resorcinol (m-dihydroxybenzene) when entering into reaction with other monomers in the manufacture of PGAA, PET copolymer and barrier materials and other barrier materials will in General lead to a material, which has better barrier properties than the same material, if it contains no derivative resorcinol. For example, resorcinol diglycidylether can be used in PGAA, and hydroxyethylated resorcinol can be used in PET and other polyesters and copolymer barrier materials.

One measure of the effectiveness of the barrier is its effect on the shelf life of the material. The shelf life of carbonated soft drink in the pays, for which less than 85% of the initial carbon dioxide remains in the bottle. It was found that the bottles covered PGAE using method injection for injection, described below, have a shelf life of 2-3 times more than one PET. If, however, uses PGAA with resorcinol diglycidylether, the shelf life can be increased to 4-5 times compared with one PET.

Another way of enhancing the barrier properties of the material is the addition of a substance that "plug" the holes in the polymer matrix and thereby prevents the passage of gases through the matrix. Alternative substance can help to create a more complex path for gas molecules in their penetration through the material. One such substance, which here is referred to as the term "nanoparticles" or "nano-partial material is fine particles of materials that increase the barrier properties of the material by creating a more difficult path for moving oxygen and carbon dioxide. One preferred type of nano-particulate material is a micro-partially based on clay product available from the company Southern Clay Products.

Ways of making products with barrier coatings
which provides adhesion between the two materials. In the General case, the adhesion between the materials of the barrier coating and the PET increases as increases the surface temperature of the PET. Therefore, it is preferable to perform coating on the heated blanks, although the preferred barrier materials of the present invention will be coupled with PET at room temperature.

1. Coating by immersion

One preferred method of manufacturing a coated PET preform in accordance with the present invention is the coating of the workpiece from PET by immersion in a bath zolosoderzhashchikh solution. Immersing the workpiece in a bath zolosoderzhashchikh solution can be carried out manually by using support frames or so on, or can be performed fully automated process, which may include a process for blow molding in the end.

Bath contains a solution prepared from one or more solvents in which the resin barrier material dissolved and/or suspended. The term "solution", as used here, refers to the end result of mixing of solvent/her and resin regardless of whether the resulting combined solution, suspension or in any combination. the go into solution faster than larger ones. If the barrier material is not very soluble in this solvent, adding resin as powder will help to create a more homogeneous suspension. Can be used in many solvents, as well as solvents, constructed from a combination of solvents. Preferred solvents include dimethylformamide (DMF), ethanol, tetrahydrofuran (THF), methylene chloride, water, acetone, benzene, toluene, Dowanol DPM, Dowanol PPH and Dowanol RM and their mixtures with each other. Factors that affect the choice of solvent or solvent system include polarity, reactivity, solubility, boiling point, vapor pressure and Flammability. The solution for coating by immersion according to the present invention preferably contains 10 to 60% resin by weight, more preferably 20-50% resin by weight, most preferably 30-40% resin by weight. The temperature of the solution in the bath is preferably 0-100omore preferably 25-50oC.

The process of coating by immersion begins with receiving blanks from PET. Harvesting can be done by injectionem melt PET in the form of a billet. The form is cooled preferably at a speed that allows the molten PET rapidly the ssy to produce billets PET by injecting molding are generally well known in the prior art. The surface of the workpiece is preferably free of any oils, surfactants, agents, retention, or form, etc., so that the material of the barrier coating can be coupled directly with PET.

PET preform is then immersed in the solution in the bath. In Fig.2, the blank is preferably immersed up until at least all the body part 4 of the workpiece flooded in the bath to a depth directly on the supporting ring 6. The workpiece remains submerged in the bath preferably 1-30, more preferably 2-5 C. the Billet is then removed from the bath and dried up until the workpiece will not remain solvent. Drying can be performed by any of such methods, as the drying air or the location of workpieces in a vacuum and/or in a heated atmosphere, such as an oven. The choice of method may depend on the selected solution and the speed at which it is desirable to carry out the drying. Additional operations of immersion and drying can be performed to create additional layers, if desired. Preferably further processing, such as stretch blow molding is performed after the workpiece is dried.

Billets with a barrier coating, the floor is located on the body part 4 of the workpiece and does not cover the throat part 2. The inner surface is covered with the workpiece 16 is preferably not covered with a barrier material. The thickness of the barrier coating is preferably from 0.01 to 3 mm, more preferably 0.1 to 1.0 mm

EXAMPLE 1. A sample of the resin of thermoplastic phenoxy-type, more precisely, PGAA, available from Dow Chemical Company under the name of XU 19040.00 L, was obtained in the form of small tablets. These tablets were dissolved in dimethylformamide at a concentration of 40% by weight. Eight identical clean PET preforms according to 17.5 g of the type used for the manufacture of bottles for carbonated beverages to 16 ounces, were placed in the capture and immersed in a bath containing a solution of resin/DMF, which was at room temperature (approximately 21-23oC). After 5 blanks were removed from the bath and dried for 8 h in an oven set at the 75oC.

Before coating by immersion of the workpiece weigh, on average, 17.5, After coating by immersion of the workpiece weigh, on average, 18.0 g, with 0.5 g of the resin caused by the process on them.

2. The coating spray.

Another way to perform the covered products from PET in accordance with the present invention is a coating dispersion. In this method, the preform of PET raspletanie manually or through the use of the device, which provides atomization and spraying after spraying in a single device.

The solution, which is sprayed on the workpiece, contains one or more solvents in which the resin barrier material dissolved and/or suspended. Can be used in many solvents, as well as solvents, are made of combinations of solvents. Preferred solvents include dimethylformamide (DMF), ethanol, tetrahydrofuran (THF), methylene chloride, water, acetone, benzene, toluene, Dowanol DPM, Dowanol PPH and Dowanol RM and their mixtures with each other. The choice of what is used as the solvent or solvent system may depend on many factors, such as polarity, reactivity, solubility, boiling point, vapor pressure and Flammability, which can be determined by a specialist. The solutions preferably contain 5-50% resin by weight, more preferably 30-40% resin by weight.

One preferred method of coating workpieces PET spray is based on the use of the device, which is described in U.S. patent 4538542, issued in the name Kennon et al. (fully incorporated here by this reference) and sold by Nordson Corporation of Amherst, Ohio). This is between the two cameras. The device may further contain a system restore pereraspedeleniya.

The process of coating by spraying starts with obtaining the blanks, which is preferably made by way of injection molding, as discussed above. The throat of each workpiece is clamped by the fastening means and mounted on the conveyor. The workpiece evenly spaced from each other. The workpiece is thus delivered into the chamber coating spray, where they are very close with rows of spray nozzles, preferably airless spray nozzles. The solvent containing the resin barrier is sprayed through the nozzle so that the effect on the external surface of each workpiece when it passes through the chamber, leaving each workpiece is covered with a layer of wet coating. In order to promote adhesion of the barrier material and help to accelerate the evaporation of the solvent, the workpiece can be pre-heated by methods known to experts, before they will enter into the chamber of the coating spray.

The conveyor then moves the workpiece from the chamber coating by sputtering in the chamber drying. The drying chamber may contain an oven, a set of lamps or other source Teplova wet coating, but not so strong as to cause distortion in the shape of the workpiece. When the workpiece passes through the drying chamber, the solvent evaporated, leaving blanks barrier coating.

3. Spraying flame

Another preferred method of manufacturing a coated preform of PET in accordance with the present invention is a sputtering flame for the procurement of PET powdered resin material of the barrier coating.

For the process of flame spraying resin barrier material is used as a powder, which preferably has 60-150 mesh, more preferably 80-120 mesh. Can be used normal spray flame, familiar to specialists, such as Unispray Jet Gun from firms Thermal Polymer Systems (Angleton, Texas). The use of other such commercially available devices or other conventional or modified devices is considered part of the present invention.

The process of coating by flame spraying begins with receiving blanks from PET, which is preferably made by the process of injection molding, as described above. The surface of the workpiece is preferably free of any oils, surface-active the PET. Billet pre-heated preferably 50-100oS, more preferably 65-75oAnd then the powdered resin barrier is supplied using a spraying device of the flame. The amount of applied resin and, therefore, the thickness of the barrier coating is determined by the amount of time that the workpiece remains in the flame. When the desired amount of resin applied, the workpiece is removed from the flame. Covered the workpiece can then be molded by blowing to form the bottle.

Billets with a barrier coating obtained by spraying flame, preferably are of the type shown in Fig.3 and 5. The inner surface is covered with the workpiece 16 is not covered, so any food or drink placed in a container, out of this procurement will be in contact only with pure PET. The thickness of the barrier coating 24 preferably is 0.01-5.0 mm, more preferably 0.5 to 2.0 mm

EXAMPLE 2. A sample of the resin of thermoplastic phenoxy-type, more specifically poly(hydroxyamino), available from Dow Chemical Company under the name of XU 19040.00 L, was obtained in the form of small tablets. Tablets were pounded into powder and sieved using Lucania powder at 120-180 mesh. Three pure billet made of pure PET of the type used to manufacture bottles 68 ounces, weighs approximately 48 grams, were heated to 100oAnd then napisany flame using Unispray Jet Gun. Blanks were removed from the flame at different times in order to obtain the barrier coatings of different thickness. Billet remaining in the flame for 5 s, was covered with 4.5 g of the resin, the billet remaining in the flame 8, obtained 8.6 g, and the billet remaining in the flame for 10 seconds, was covered with 11.5 g of resin.

4. Dive into the liquefied bed

Another method of making blanks from PET barrier coating in accordance with the present invention is immersed in the liquefied bed. In this process, the procurement of PET is immersed in a bed of powdered resin material of the barrier coating, which is diluted by the flow of air through the powder resin. In this process, the resin barrier material is a powder. having preferably 60-150 mesh, more preferably 80-100 mesh. As is known to the expert, can be used conventional devices and technologies liquefied bed.

The coating process in the liquefied bed begins with receiving blanks from PET, which practicelink free of any oils, surface-active substances, agents, retention, or form, etc., so that the material of the barrier coating can be coupled directly with PET. The workpiece at a temperature preferably 50-125oS, more preferably 75-100oWith, immersed in the liquefied powder. The workpiece is preferably immersed only to the depth of the support ring 6, because usually the resin barrier is not desirable to coat the inner side of the workpiece.

The workpiece is removed after a period of time, preferably 2-10, more preferably 5-7 C. the Workpiece coated with the powder must be heated, for example, using a furnace, flame or lamp, to cause the powder to melt or leak, so that it forms a smooth, uniform coating. When the coating is smoothed by heating, the workpiece can then be molded by blowing to form the bottle.

EXAMPLE 3. A sample of the resin of thermoplastic phenoxy-type, more specifically, PGAA, available from Dow Chemical Company under the name of XU 19040.00 L, was obtained in the form of small tablets. These tablets were pounded into powder and sieved using a screen of 80 mesh in accordance with standard processes known in the prior art, for selectingaWith each and then immersed in the liquefied bed containing the powder PGAE. The powder in the bed is maintained at room temperature, and the flow rate of air through the bed is sufficient for the liquefaction of air. Blanks are removed after 8 and processed by the flame to melt the powder and create a pure homogeneous coating. The billet was applied an average of 0.7 g of resin.

5. Electrostatic spray powder

Another method of manufacturing a coated preform of PET in accordance with the present invention is an electrostatic spraying for the procurement of PET using powdered resin material of the barrier coating. In this process, the resin barrier material is used as a powder, preferably with a 80-200 mesh, more preferably 100-140 mesh. Use the electrostatic spray device known from the prior art.

The process of electrostatic powder deposition begins by obtaining the blanks of plastic, preferably injection molding, as described above. The surface of the workpiece is preferably free of any oils, surfactants, agents, retention, or form, etc., so that the barrier material 70-80 kV, is placed on the powder as it exits from the nozzle. A charge opposite to the charge of powder, may be placed on the workpiece, or the workpiece can be grounded.

The billet at a temperature preferably 10-40oS, more preferably 20-25oWith sprayed preferably 1-15, more preferably 3-5 C. powder Coated workpiece must then be heated, for example, the lamp, flame or oven, to cause the powder to melt or leak so that it formed a smooth, uniform coating. After the coating is smoothed by heating, the workpiece can then be molded by blowing to form the bottle.

Billets with a barrier coating, manufactured by electrostatic spraying, preferably are of the type shown in Fig.3 or 5. Barrier coating 22 applied to the external surface of the billet and the inner surface uncovered.

EXAMPLE 4. A sample of the resin of thermoplastic phenoxy-type, more specifically, XU 19040.00 L (from Dow Chemical Company), was obtained in the form of small tablets. These tablets were pounded into powder and sieved for the selective reception of a powder at 120-140 mesh. There were used three pure billet, which was homesales within each billet at room temperature. On the workpiece does not ring any tension. The workpiece is sprayed powder for 5 s, and then they are processed. The billet was applied an average of 1.6 g of resin.

6. Performanee

Especially preferred method of manufacture of coated workpieces from a PET referred to here generally as performanee, and sometimes as injection by injection (FDI). The name refers to a procedure that uses forming injectionem for injection box of one or more layers of barrier material on an existing workpiece, which itself is preferably made by molding injectionem. The terms "preinjection and performanee" are used here to describe the process of coating, where the material layer, preferably containing barrier material is injected on top of the existing procurement. In a particularly preferred implementation of the process preinjection runs up until the main harvest is not fully hardened. Preinjection can be used to place one or more layers of materials such as those containing barrier material, recycled PET, or other materials on top of the covered or uncovered zag is receiving using the same equipment, which was used to form the uncoated preform. The preferred form for perforovane uncovered the workpiece at the location shown in Fig.9. The form contains two halves, half of the cavity 52 and half 54 of the mandrel shown in Fig.9 in the close position before preinjection. Half 52 of the cavity includes a cavity which is uncovered procurement. Support ring 6 of the workpiece rests on the ledge 58 and is held in place by half 54 of the mandrel, which transmits the pressure on the supporting ring 6, thereby hermetically closing the neck portion from the body portion of the workpiece. Half of the cavity 52 has a set of pipes or channels 55, in which is kept liquid. Preferably, the liquid circulates in the channels along the path through which fluid passes inside the entrance half of the cavity 52 through the channels 55, out of the half of the cavity 52 through the outlet, through a cooler or other cooling means, and then back to the entrance. Circulating fluid used for cooling the forms, which in turn cools the molten plastic, which is injected into shape for the formation of the coated workpiece.

Half of the mandrel form contains a mandrel. The mandrel 96, sometimes nasienie to aid in the centering of the workpiece in the form of the mandrel 96 cools the inside of the workpiece. Cooling is provided by circulating a fluid through the channels 57 in the half 54 of the mandrel forms and, most importantly, the length of the mandrel 96. Channels 57 half 54 of the mandrel are similar to the channels 55 in the half 52 of the cavity in which they create a part of the path lying inside half of the form, which passes through the coolant.

When the workpiece in the mold cavity, the body portion of the workpiece is centered within the cavity and completely surrounded by a hollow space 60. The workpiece is located, therefore, acts as an internal matrix of the mandrel in a subsequent procedure, injection box. Melt performanace material, preferably containing barrier material is then fed into the mold cavity from the injector through the valve 56 and flows around the preform, preferably surrounding at least the body portion 4 of the workpiece. After preinjection performancy layer will have the approximate size and shape of the hollow space 60.

For the procedure of perforovane initial workpiece to be involved, preferably heated to a temperature above its TC. In the case of PET, the temperature is preferably 100-200ooWith, be careful with cooling PET in the workpiece. Cooling should be sufficient to allow the PET in the blank to make the preferred amorphous state, not the state of crystallization. An alternative used the initial workpiece can be that which has just been molded by injectionem and not yet fully cooled, i.e. has a high temperature, which is preferred for the process of perforovane.

The coating material is heated to form a melt of such viscosity that is comparable to the use of devices forming injectionem. The temperature for this purpose, i.e., the temperature of the injection box will vary according to the materials depending on what ranges of melting the polymer and the melt viscosity may vary due to the history, chemical nature, molecular weight, degree of branching, and other characteristics of the material. For the preferred barrier materials described above, the temperature of the injection box preferably is in the range 175-235oS, more preferably 200-275oC. for Example, a copolymer of barrier material-010 preferred temperature and uses recycled PET, the temperature of the injection box is preferably 250-300oC. the coating Material is then injected into the form in an amount sufficient to fill the empty space 60. If the coating material contains a barrier material, the covering layer has a barrier layer.

Covered procurement preferably cooled at least to the point where it can be extracted from a form or to resist without damage, and is removed from the mold, where it is further cooled. If you are using PET and the billet was heated to a temperature near or above the crystallization temperature of PET, cooling must be very fast and sufficient to ensure that the PET is initially in the amorphous state, when the workpiece is cooled down completely. The result of this process is a strong and effective link between the initial procurement and consistently imposed by the coating material.

Performanee can also be used to create a covered boards with three or more layers. In Fig.17 shows a three-layer implementation of the workpiece according to the present invention. Shows the workpiece has two coating layers, the middle layer 80 and the outer layer 82. Otnositelnoj or to ensure the manufacturing of bottles of various sizes. As will be clear to experts, the similar procedure disclosed above can be followed, except that the initial workpiece is already covered by one of the methods for the manufacture of coated preparations described above, including performanee.

A. The preferred device for perforovane

A preferred device for performing the process of perforovane based on the use of the device 330-330-200 Enge-La (Austria), some forms of which contains a fixed half and a movable half. Both halves are preferably made of hard metal. The stationary part comprises at least two parts, where each part of the form contains N (N>0) of the same cavity shape, the inlet and outlet for the coolant channels, allowing coolant to circulate inside of the form, the device of the injection and hot gutters, leading the molten material from the injection device to the valves of each mold cavity. Because each part of the shape forms a separate layer of the workpiece, and each layer of the workpiece is preferably made of different material, each part of the form is controlled separately to adapt to potentially different conditions, require erial at a temperature a suitable specific material through the hot chute and valves of this section of the form and into the cavities form. Own input and output of the form to allow coolant to control the temperature of this part of the form to fit the specific characteristics of the material produced in this part of the form. Therefore, each part of the form may have a different temperature of injection, the mold temperature, pressure, volume of injection, coolant temperature, etc. to adapt to the requirements of material and of a particular layer of the workpiece.

The movable part of the form contains a swivel pad 102 and a plurality of cores or mandrels 96. The pin alignment guide Playground with a slide for movement preferably in a horizontal direction to a fixed half or from it. Rotary platform can rotate either clockwise or counterclockwise and mounted on Board. Many of the mandrel is attached to the rotary platform. These mandrels are used as a molding form for the inner part of the workpiece, and also serve as support and cooling means for the workpiece during the operation of molding. The cooling means in the mandrel oteea by circulating fluid. Therefore, in shape, having two parts, a fixed half has a separate cooling for each of the two parts of the form, plus a separate cooling in the movable part of the form. Similar in form, having three parts of the form in the stationary half, there are four distinct sets of coolant: one for each part of the form, only three plus one for the movable half. Each set of the coolant works the same way. The liquid flows into a form that flows through the network of channels or pipes inside, as discussed above for Fig.9, and then exits through the exit. From the output of the fluid goes through the pump means, which supports the fluid in motion, and cooling means for maintaining the liquid within the desired temperature range before returning back to the form.

In the preferred implementation of the mandrel and cavity contain vysokoteploprovodnyh material, such as beryllium, which is covered by a solid metal, such as tin or chrome. Hard coating keeps beryllium from direct contact with the workpiece, and also acts as a release for retrieval and provides a hard surface for long service life. Vysokoteploprovodnyh cycles. Vysokoteploprovodnyh material may be located over the entire area of each of the mandrel and/or the cavity or may be only on their parts. Preferably, at least the ends of the mandrels had vysokoteploprovodnyh material.

The number of bars equal to the number of cavities, and the location of the pots on the movable half mirror reflects the location of the cavities on the stationary half. To open the form movable half moves away from the stationary half so that the mandrel out of the fixed half. After the mandrel is fully extracted from the parts of the form, the turning space of the movable half of the mandrel rotates to align with the other part of the form. Thus, the movable part is rotated 360/(number of parts forms the fixed part) degrees after each extraction of the mandrel from the stationary half. When the device is in operation in the operations of extraction and rotation will be stocking up on some or all of the mandrels.

The size of the cavities in this part of the form will be identical, but the size of the cavities will be different in parts of the form. Cavity in which the first molded uncovered the workpiece, i.e. the cavity of the molding blanks, Aleuts is, is more than the cavity of the molding material in order to adapt to uncovered the workpiece and provide space for the covering of the material to be injection inside for forming performanace coverage. The cavity in each subsequent section of the form, where the following additional operations perforovane will be much larger in size to fit the workpiece when she gets bigger with each coating operation.

After a set of pieces was formed and performan to completion, the number of ejectors eject the finished workpiece from the mandrel. Pullers for mandrel simultaneously, or at least one ejector for a set of pots, equal in number and configuration of one part of the form so that only popped the finished workpiece. Uncovered or

not fully covered by the workpiece remains on the mandrel, so that they can continue the cycle for the next part of the form. Pushing could cause the workpiece to be totally separated from the mandrel to fall into the bin or on the conveyor. Alternative procurement may remain on the mandrel after popping, after which the robot arm or other such device SS="ptx2">

Fig.10 and 11 are schematic images of the complete device, as described above. Fig.11 is stationary half of the mold. In this execution unit 101 has two parts of the form, it contains one set of three cavities 98 coating of the workpiece and the other contains a set of three cavities 100 of the coating of the workpiece. Each of the cavities 100 of the coating of the workpiece is preferably identical with the cavity, shown in Fig.8, discussed above. Each of the cavities 98 molding blanks preferably identical with the cavity, shown in Fig.9, in that the material is injected into the space defined by the mandrel (though without blanks on it) and a wall of the form, which is cooled by fluid circulating through channels within a block of the form. Therefore, one complete cycle of production of this device will give three dual-layer blanks. If you want more than three blanks per cycle, the stationary part may be reconfigured to accommodate a larger number of cavities in each section of the form. An example of this is seen in Fig.14, which shows the stationary half of the form contains two parts form, it contains 48 cavities 98 molding blanks, and the other contains 48 cavities 100 pokrytiya to fit more parts of the form, one part for each layer of the workpiece.

Fig. 10 shows the movable half of the mold. Movable half contains six identical mandrels 96 attached to the rotating platform 102. Each frame corresponds to a cavity in the stationary section of the form. Movable half also contains the pins 94 of the alignment that correspond to the receivers 95 on the stationary half. When the movable half of the form is moved to close the form, the pins 94 of the alignment coincide with their respective receivers 95, so that the cavity 98 of the molding and the cavity 100 of the cover are aligned with the mandrel 96. After alignment and closing half of the mandrel 96 zentrums inside the cavities 98 molding blanks, and the other half of the mandrel 96 zentrums inside the cavities 100 of cover blanks.

The configuration of the cavities, pots and pins align and receivers must have a sufficiently symmetric form, so that after the form is separated and rotated to the proper number of degrees, all of the frame line up with cavities and all the alignment pins line up with receivers. Moreover, each frame must be in the cavity in a different form than it was before rotation for a DOS device.

Two types of two halves together form shown in Fig.15 and 16. Two of the mandrel 96, attached to the rotating platform 102, begin to enter the cavity, one enters into the cavity 98 of the molding, and the other is included in the cavity 100 of the cover installed on the block 101. In Fig.16 of the mandrel 96 is completely removed from the cavities on the stationary half. In this drawing, the cooling placement is shown schematically, with the cavity 98 molding blanks has a cooling circulation 106, which is separated from the coolant circulation 108 for cavity 100 of the coating of workpieces, which is another part of the form. Two of the mandrel 96 is cooled only by the system 104, which connects all the pots together. The arrow in Fig.16 shows the rotation of the rotatable platform 102. Swivel the site can also rotate counterclockwise. Not shown is covered and coated preform, which can be on the mandrel, when the device is in operation. The alignment pins and receivers removed for purposes of clarity.

The device perforovane will be discussed below in terms of preferred devices of the two parts of the mold for manufacturing two-layer preform. The form is closed by moving the movable half by nab, the pout of the material in the first part of the form through the hot chute and into the cavity 98 molding blanks through their respective valves for the formation of uncoated blanks, each of which becomes the inner layer is covered with the workpiece. The first material fills the void between the cavities 98 forming billet and mandrel 96. Simultaneously, the second an injecting unit injects the molten second material into the second portion forms a stationary half through the hot chute and into each cavity 100 coating workpieces through their respective valves so that the second material fills the emptiness (60 in Fig.9) between the cavity wall 100 of the cover blanks and uncovered the workpiece mounted on the mandrel 96.

Throughout the process, the coolant circulates through three separate areas 106, 108 and 104, corresponding parts of the mold cavities of the molding blanks, of the form of the cavities of the coating of the workpieces and the movable half, respectively. Thus, melts and blanks are cooled in the centre of the circulation in the movable part, which passes through the interior of the mandrel, as well as outside by circulation in each cavity. The operating parameters of the coolant in the first part of the form containing the cavity 98 molding blanks, are managed separately from the operating parameters of the coolant in the second part of the form containing cavity cover with the fate of the form, which provides constant cooling for the inner part of the workpiece during the entire cycle, whether the form is open or closed.

Movable half then moved back to separate the two halves of the form and open the form up until all of the mandrel 96, having a workpiece is fully released from the cavities 98 molding blanks and cavities 100 coating of workpieces. The push pullers covered with a finished workpiece from the mandrel 96, which have just been removed from the cavities of the cover blanks. As was discussed above, the extrusion may cause the workpiece to be totally separated from the mandrel and to fall into the bin or on the conveyor, or if the workpiece remains on the mandrel after popping, robot arm or other such device can capture the workpiece or workpieces to delete to the recycle bin, on a conveyor or other desirable place. Swivel pad 102 is then rotated 180oso that each mandrel having on themselves uncovered the workpiece is positioned over the cavity 100 of the coating of the workpiece, and each mandrel, which covered the workpiece has just been popped, is located above the cavity 98 molding blanks. Rotating swivel the camping and closed and the first injector injects the first material into the cavity of the molding blanks, while the second injector injects the barrier material into the cavity of the coating of the workpiece.

The production cycle of closing the form, injection box melts, opening the mold, removing the completed barrier harvesting, rotation of the rotary platform and the closing form is repeated, so that the workpiece is continuously molded and performous.

When the device starts to work the first time, during the initial cycle in the cavities 100 of coverage billets yet. Therefore, the operator must either prevent the injection box of the second material of the second injector to the second part forms at the time of the first injection box, or allow to inject the second material, and then throw the single-layer preform consisting only of the second material. After this initial operation, the operator can either operate manually or programmed to the desired settings so that the process is controlled automatically.

b. A method of manufacturing a dual-layer blanks using the preferred device perforovane

Two-layer preform can be performed by execution of a two-layer billet contains the inner layer, containing the polyester and the outer layer comprising a barrier material. In a particularly preferred executions of the inner layer contains pure PET. The following description is directed to a particularly preferred implementation of a two-layer blanks, containing an inner layer of pure PET. This description focuses on the formation of one set of coated workpieces of the type shown in Fig.4, i.e., the passage of the set of sheets through the molding process, perforovane and retrieval, and not on the description of the operation of the device as a whole. The described process is directed at the workpiece, having a total thickness in the murine part 3 of about 3 mm, consisting of 2 mm pure PET and approximately 1 mm of the barrier material. The thickness of the two layers will vary in other parts of the workpiece, as shown in Fig.4.

The specialist will be clear that some of the parameters, described in detail below, will be different if you use other run of blanks. For example, the time during which the mold is closed, will vary depending on the wall thickness of the workpieces. However, giving the following description of this preferred, and reminders of the description, the specialist must be capable of definition is so, what injector feeding part of the form containing cavity 98 molding blanks, served pure PET, and to the injector, the supply portion of the form containing the cavity 100 of the coating of workpieces, served barrier material. Both halves of the form are cooled by circulating a liquid, preferably water, at a temperature preferably 0-50oS, more preferably 10-15oC.

The movable part of the form is moved so that the form is closed. Melt clean PET is blown through the back of the unit 101 and each cavity 98 forming blanks for forming the uncoated preform, which becomes the inner layer is covered with the workpiece. The temperature of injection of the molten PET is preferably 250-300oS, more preferably 265-280oC. the Form is kept closed, preferably from 3 to 10 seconds, more preferably 4-6 seconds until the PET is cooled by water circulating in the form. During this period of time the surface of the workpieces, which are in contact with the cavities 98 forming of billets or bars 96, begin to form the shell, whereas the cores of the workpieces remain molten and not hardened.

The movable part of the form then peremeshayt the I on the mandrel 98, free from immovable form. The inner part of the workpiece in contact with the mandrel 96 continues to cool. The cooling is preferably performed in a way that reduces the heat at a rate higher than the rate of crystallization of PET, so in the blanks PET will be in the amorphous state. Chilled water circulating through the form, as described above, should be enough to complete this task. However, while inside the billet is cooled, the temperature of the outer surface of the workpiece begins to grow, as it collects heat from the molten core of the workpiece. This heat begins to soften the shell on the outer surface novoportovskoi blanks.

Rotary Playground 102 then rotates 180oso that each mandrel 96, having on itself molded workpiece which is located above the cavity 100 of the coating of the workpiece. Situated thus, each of the mandrel 96, who do not have a formed workpiece, is placed over the cavity 98 molding blanks. Then the form is closed again. Preferably the period of time between removal from the cavity of the molding blanks for insertion into the cavity of the coating of the workpiece is 1-10 the closure of the workpiece, the outer surface of the workpiece is not in contact with the surface of the form. Thus, the outer shell is still soft and heated, as described above, since the cooling contact is only with the mandrel inside. The high temperature of the outer surface of the uncoated preform (which forms the inner layer is covered with blanks) helps to ensure adhesion between the PET and the barrier layers in the final workpiece with a barrier coating. It is alleged that the surface materials are more reactive at high temperatures and, thus, the chemical interaction between the barrier layer and clean PET will intensify high temperatures. The barrier material will cover and will engage with the workpiece with a cold surface, and thus, the operation can be performed using the cold start uncoated blanks, but the grip is clearly better when the process perforovane is performed at elevated temperature, as it occurs immediately after the formation of uncoated blanks.

Then, the operation of the second injection, in which the melt barrier material is injected into each cavity 100 of the coating of the workpiece for coating the workpiece. The temperature of the melt Barinov gornogo material depends on the specific characteristics of the barrier material, but in the abilities of a specialist to determine the appropriate range by using a simple experiment carried out in this description. For example, if the barrier material PGAE XU 19040.00 L, the temperature of the melt (temperature injection) preferably 160-240oS, more preferably 200-220oC. If you are using a copolymer barrier material-010, the temperature is preferably injection 160-240oS, more preferably 200-220oC. during the same period of time, when this set of blanks performeda with barrier material in the cavities 100 of the coating of the workpiece, a different set of uncoated blanks molded in the cavities of the molding blanks, as described above.

The two halves form again separated, preferably 3-10, more preferably 4-6, followed by the beginning of the operation of the injection box. Billet, which just got a barrier coating in the cavity 100 of the cover blanks are removed from the mandrel 96. Uncoated blanks that have just molded in the cavities 98 molding blanks remain on your mandrel 96. Rotary Playground then rotates 180oso that each mandrel having on themselves uncovered the workpiece is positioned over the cavity 100 p is olotu 98 molding.

The cycle closes the form, the injection of the material, opening the mold, removing the completed barrier harvesting, rotation of the rotary platform and the closing form is repeated, so that the workpiece is continuously molded and performous.

One of the many benefits of using the process disclosed here is that the cycle times for the process are the same as for standard production of uncoated blanks, shaping and coating of workpieces by this process is performed for a time period equal to that required for the manufacture of uncoated preforms of PET of the same size standard methods currently used in the production of blanks. Consequently, it is possible to produce blanks from PET barrier coating instead of uncoated preforms of PET without significant changes in output and capacity output.

If the molten PET is cooled slowly, the PET will take crystalline form. Because crystalline polymers are not formed by blowing as well as amorphous polymers, from semi-crystalline PET, you cannot expect the same run of the formation of containers in accordance with the present invention. However, if PET cools rfna form is ideal for blow molding. Therefore, sufficient cooling PET is necessary for the formation of blanks that will work as needed during processing.

The speed with which the layer of PET is cooled in the form as described above, is proportional to the thickness of a layer of PET, as well as the temperature of the cooling surfaces with which it is in contact. If the temperature factor of the form to keep a constant, a thick layer of PET is cooled more slowly than a thin layer. This is because heat is required over a long period of time to move from the inner part of a thick layer of PET to the outer surface of PET, which is in contact with the cooling surfaces of the form, more than a thin layer of PET, because of the larger distances that must pass more heat in a thick layer.

Thus, the workpiece having a thicker layer of PET, you need to be in contact with the cooling surfaces form longer than the workpiece, with more than a thin layer of PET. In other words, other things equal, more time is required for forming blanks with thick wall PET than on the shaping of the workpiece with a thin wall PET.

Outstanding piece on this from the thinner, than the usual PET raw material for tanks of this size. This is because in the manufacture of workpieces with a barrier coating of the present invention, the number of PET, which should be in regular PET raw material, can be replaced with the same amount of one of the preferred barrier materials. This can be done, because the preferred barrier materials have physical properties similar to PET, as described above. Thus, when the barrier materials replace an approximately equal number of PET in the walls of the preform or container, there is no significant difference in the physical characteristics of the vessel. Because the preferred uncoated blanks that form the inner layer of the workpiece with the barrier coating of the present invention are thin, they can be removed from the mold faster than their more conventional thick-walled counterparts. For example, uncoated workpiece according to the present invention can be removed from the mold preferably 4-6 with no crystallization compared to the 14-24 for conventional PET preform having a total wall thickness of approximately 3 mm At the end of the period of time for the manufacture of wood with a barrier coating according to the present sobri the same total thickness.

Additionally, because the preferred barrier materials are amorphous, they will not require the same type of treatment that PET. Thus, the cycle of the molding process/perforovane, as it is written below, usually dictated by the cooling time required for PET. In the above method of procurement with a barrier coating can be produced in about the same time, which is required for the manufacture of uncoated plain billet.

Compared to the advantage gained more than a thin workpiece, it is possible to make a step forward, if the workpiece is made in the process, will be of the same type as in Fig, 4. In this execution, the coated preform wall thickness PET at the point 27 of the field on the terminal cover 10 preferably decreases to 1/3 of the total wall thickness. When moving from the center of the end cap to the end of the radius end cap thickness gradually increases up to preferably about 2/3 of the total wall thickness, as in position 23 in murine part 2. The wall thickness may remain constant or may, as shown in Fig.4, to move into a smaller thickness to the support ring 6. The thickness of the various parts of the workpiece can vary, but in all cases the wall thickness of the PET and the barrier layer>/P>The use of blanks of the same design as in Fig.4, provides even faster cycles of time than used for the production of workpieces of the same type as in Fig.3. As mentioned above, one of the biggest barriers to reducing cycle time is the length of the period of time that is required PET for cooling in the form of subsequent injectionem. If the workpiece containing the PET was not cooled enough before pushing out from the mandrel, it will become crystallized and potentially cause difficulties in the process blow moulding. In addition, if the layer PET was not sufficiently cooled before you begin the process of perforovane, the strength of the barrier material included in the form, will wash away the part of the PET from the area of the valve. The design of the workpiece according to Fig.4 takes into account both problems by making the layer PET the thinnest in the center area of the end cap, which is the place where the form has a valve. The thin part of the valve allows the area of the valve to cool faster, so the uncovered layer of the PET may be removed from the mold in a relatively short period of time, still avoiding crystallization of the valve and the flushing of the PET during the second injection box aoademy invention help to make this type of design procurement working. Because of the similarity in physical properties of the vessel with murine parts, which are the primary barrier material can be made without having to sacrifice performance capacity. If the barrier material is not the same with PET, the capacity of the variable composition of the walls, as in Fig. 4, will have weak spots or other defects that may affect the characteristics of the vessel.

7. Thin-layer injection molding

The barrier layer or barrier procurement can also be made by a process called thin-layer injection molding (ELISA). The essence of the process TYPHOID is to create a flow of the melt, which consists of many thin layers. In this application it is preferable that the melt flow TYPHOID contained alternating thin layers of PET and barrier material. One way thin-layer injection molding is carried out using a system similar to that disclosed in several patents issued Schrenk - U.S. patents 5202074, 5540878, 5628950, descriptions of which are fully incorporated here by reference, although the use of this method as well as other ways of receiving similar thin-layer flows melts, rassmatrivaetsia, but it should be understood that the system for three or more materials may be used similarly. Two materials that must shape layers, at least one of which is preferably a resin barrier, placed in separate bins 84 and 85, which are fed by two separate cylinder 86 and 87, respectively. The materials are squeezed together at speeds designed to provide the desired relative amounts of each material for forming the thin layer of melt flow from each cylinder.

The output of the thin-layer flow of melt from the United cylinders are then fed to the system 88 generation layers. In this system, the production of layers of the melt flow of the two layers is multiplied by a multilayer melt flow by repeating sequences of actions that are very similar to the steps for the production of cakes with multiple layers. First, part of the melt flow is divided into two parts perpendicular to the place of coupling of the two layers. Then these two parts are flattened so that each of the two parts is about as long as the original part before it was divided into two parts: in the first operation, but has only half of the same thickness as the original by Choi, folded in the foot on top of one another, so that two sublayers materials are parallel to each other. These three operations division, flattening and connection of flow of the melt can be performed several times to create even more thin layers. The melt flow can be multiplied by performing division, flattening and connections several times to generate a single stream of a melt consisting of multiple sublayers of the component materials. In this execution with two materials, the composition of the layers will alternate between the two materials. The output of the generation system layers passes edition 89 and injected into a mold to form the preform or coating.

System, such as shown in Fig.12, for the production of thin-layer melt flow can be used instead of one or more injectors in the process of perforovane and the device described above. Alternative barrier billet may be formed using a single injection of melt flow TYPHOID, if the melt flow contains a barrier material. If the workpiece is made of the melt flow TYPHOID or made with an inner layer that is made of melt flow TYPHOID, and capacity, made from it, prednisne the imprimatur of the FDA.

In one preferred implementation of the workpiece of the type shown in Fig. 4, is fabricated using the process of injection box after injection box, in which the melt flow of the workpiece is injected into the cavity 100 barrier coatings (Fig. 11). This process, in which the workpiece performeda with thin-layer flow of the melt, can be called TYPHOID fever after the injection box. In the process of TYPHOID fever after injection box for creating a billet bottle of drink is created by injection molding, the first or middle layer are preferably pure PET, and the flow TYPHOID melt preferably is a barrier material such as PGAA, and recycled PET. Recycled PET is used only for the outer layer, since it will not be in contact with food products, and for the manufacture of bulk containers is cheaper to use it, but not clean PET or most barrier materials.

Fig. 4A shows an enlarged view of the murine part 3 procurement of the type shown in Fig. 4 produced by the process of TYPHOID fever after the injection box. The inner layer 110 is the only material, but the outer layer 112 consists of many of the lamellae formed by the process of TYPHOID fever.

Is fed through the feed hopper 84 to the first cylinder 86, while at the same time the barrier material is fed through the second feed hopper 85 to the second cylinder 87. These two materials together can be removed at such speeds, to provide a two-layer thin-layer flow of a melt containing preferably 60-95% by weight recycled polyethylene terephthalate, and preferably 5-40% by weight of the barrier material. Thin-layer flow of the melt is fed into the system 88 generation layer in which a thin-layer flow of a melt containing two materials, is formed by splitting, flattening and merging flow of the melt, preferably at least twice. This thin stream of the melt enters at point 89 and then insectorama in shape, as shown in Fig.9. Preferably the thin-layer flow of the melt is injected into the cavity 100 of the coating of workpieces device perforovane, such as in Fig.11 and 12, on top of the workpiece to form the workpiece is covered with a FEVER on top of the injection box containing barrier layer consisting of alternating microlayers of barrier material and recycled PET.

In another exemplary process, a clean PET is fed through the feed hopper 84 to the first cylinder 86, while at the same time In-010 is the velocity, to provide a thin-layer flow of a melt containing preferably 60-95% by weight of pure polyethylene terephthalate and preferably 5-40% by weight of B-010. Two-layer thin-layer flow of the melt is fed into the system 88 generation layer in which a thin-layer flow of a melt containing two materials, is formed by splitting, flattening and merging flow of the melt, preferably at least twice. This thin stream of the melt enters at point 89 and then injected into the cavity 98 molding blanks preferred device perforovane described above. This initial procurement TYPHOID preinjected recycled PET in the cavity 100 of the coating of the workpieces to produce a workpiece with an inner layer consisting of alternating microlayers of barrier material and clean PET, and an outer layer of recycled PET. This process may be referred to as the injection box after TYPHOID.

In the multilayer billet perform the injection box after TYPHUS or TYPHOID fever after injection box thin-layer injection system can be used for the benefit of providing multiple alternating or repeating layers, preferably containing PET and barrier material. Majesties side walls of the beverage containers or containers for other food products.

The formation of the preferred tanks blow molding

Containers with barrier coating of the present invention is preferably made by blow molding of preforms with a barrier coating, which are disclosed above. Billets with a barrier coating of the present invention can be molded by blowing using methods and conditions, which are very similar, if not identical, to those for which of the uncovered pieces of PET-blown capacity. Such methods and conditions for molding by blowing from a single billet of PET bottles are well known in the art and may be used or adapted as necessary.

Usually in this process, the workpiece is heated to a temperature preferably 90-120oS, more preferably 100-105oWith, and it is given a short period of time on balancing. After equilibration she stretched in length approximately the length of the finite capacity. After stretching inside the workpiece enters the compressed air, which expands the wall of the workpiece to fill in the form in which it is located, thereby creating capacity.

Although the present invention has been described in terms of the Oia, this is not limited. On the contrary, the applicant believes that the invention is limited only by reference to the appended claims, and that changes in the methods and materials disclosed here that are obvious to the expert, fall within the scope of applicant's invention.

1. A multilayer product, containing the murine portion containing an internal multi-component layer and the outer layer, in which (a) mentioned multicomponent layer has at least two discrete sub-layer with the surface of the coupling between the sublayers and stretches along the length of the product, and one of the sublayers contains polyethylene terephthalate, and the other of the sublayers contains a barrier material containing (i) thermoplastic phenoxy-type or (ii) a copolymer of terephthalic acid, isophthalic acid and at least one diol, and the material has a permeability for carbon dioxide, equal to not more than one-third of the permeability of carbon dioxide of polyethylene terephthalate; b) the said outer layer contains recycled polyethylene terephthalate and (C) referred to internal multi-component layer and said outer layer contain materials with absolute refractive index of 1.55 and 1.75.

2. The product under item 1, in which the mentioned internal mnogokriterial and barrier material.

3. The product under item 2, which referred to the inner multi-component layer contains at least two sublayers of polyethylene terephthalate in a stripe configuration at least two sublayers mentioned barrier material.

4. The product under item 1 in the form of billets.

5. The product under item 1 in the form of a vessel.

6. The product under item 1, in which the said sublayer terephthalate forms the inner layer of the aforementioned multi-component layer.

7. The product under item 1, in which the mentioned internal multi-component layer is not thicker than said outer layer.

8. Multilayer billet containing the murine portion having an inner layer and an outer layer, in which (a) mentioned inner layer contains polyethylene terephthalate, stretched along the length of the said workpiece, ending at the end of the threaded throat portion with protruding outward threaded to receive cap element has a supporting ring at the bottom of the mentioned end of the threaded throat portion and has a thickness of at least 2 mm and an absolute refractive index 1,55-1,65; (b) the said outer layer together with the aforementioned inner layer acts to end the below mentioned underwater diol or (ii) thermoplastic phenoxy-type selected from the group consisting of poly(hydroxyether), poly(hydroxy complex and simple ether) and poly(hydroxylaminopurine), and the aforementioned outer layer has a permeability to oxygen is less than said inner layer, and a thickness of not more than a quarter of the thickness mentioned inner layer; and (C) of the said outer layer has an absolute refractive index of such value to provide the above-mentioned refractive indices in the range of 1.0 to 1.2.

9. Procurement under item 8, in which said workpiece contains a cylindrical throat portion immediately under the said supporting ring and a transitional portion below mentioned cylindrical throat portion, which tapers down to the body part with a reduced diameter of the said workpiece and in which the mentioned outer layer mentioned murine portion stretched over the said body part, referred to the transition portion and said cylindrical throat portion, to end with the bottom of said support ring.

10. A method of manufacturing articles made of polyester with plastic barrier coating containing the following: (a) the injection box molten first material, Soderini forms the core for the formation of products of polyester plastics, containing an internal surface and an external surface, in which is mentioned the first half of the form and the above-mentioned half forms the core are cooled by circulation of liquid, referred to the first half of the forms in contact with the outer surface of the polyethylene terephthalate and the above-mentioned half of the core form is in contact with the inner surface of the polyethylene terephthalate; (b) the resolution referred to molten polyethylene terephthalate to stay in contact with the said halves of the form before the form a shell on said external and internal surfaces of polyethylene terephthalate, and said shell surrounds a core of molten polyethylene terephthalate in the above-mentioned product of polyester plastics; (C) removing the first mentioned half of the forms from the mentioned products of polyester plastics; (d) resolution shell on said outer surface of polyethylene terephthalate to soften by heat transfer from the molten core of polyethylene terephthalate, while the aforementioned inner surface of the polyethylene terephthalate is cooled ongoing contact with the said half of the core form; (e) the location of the mentioned articles of palatia fluid; f) the injection of the molten second material containing barrier material, through the second valve into the space defined mentioned the second half of the form and the above-mentioned outer surface of the polyethylene terephthalate to form the products of polyester plastic with barrier coating containing barrier layer comprising a barrier material on said outer surface of polyethylene terephthalate; (g) the resolution referred to the molten second material containing barrier material to stay in contact at least with said second half of the form; (h) deleting mentioned the second half of the forms from the mentioned products of polyester plastic with barrier coating and (i) remove the mentioned products of polyester plastic with barrier coating from the mentioned half of the core form.

11. The method according to p. 10, in which the mentioned barrier material contains (i) thermoplastic phenoxy-type or (ii) a copolymer of terephthalic acid, isophthalic acid and at least one diol.

12. The method according to p. 10, in which the mentioned barrier material includes poly(hydroxyamino).

13. The method according to p. 10, in which the said layer of barrier MaterialName product of polyester plastic is in the form of billets.

15. The method according to p. 14, further containing an operation of blow molding the above-mentioned preform to form the container.

16. The method according to p. 10, in which the said product of polyester plastics has the smallest thickness in the region nearest to the first mentioned valve, and the barrier layer has a maximum thickness around the area nearest to the said second valve.

17. The method according to p. 10, in which the operation (b) is carried out for 5-15 C.

18. The method according to p. 10, in which the operation (g) is performed at 5-15 C.

19. The method according to p. 10, wherein the operation (C), (d) and (e) are carried out in General at 1-10 C.

20. The method according to p. 10, wherein the operation (C) - (e) are performed in General for 1-3 C.

21. The method according to p. 10, wherein the operation (a) - (i) are generally 20-30 C.

22. The method according to p. 10, in which said half of the core form is attached on the rotary platform, in which the mentioned rotation of the rotary platform moves mentioned half forms the core from a position opposite to the first mentioned half of the form, in the position opposite referred to the second half of the form.

23. The method according to p. 10, in which the aforementioned first and second half of formania and conditions for each of these halves of the form.

24. Method of manufacturing a multilayer plastic container that contains the following operations: a) providing a first polymer containing polyethylene terephthalate and a second polymer containing a copolymer of terephthalic acid, isophthalic acid and at least one diol; (b) the injection box mentioned first and second polymers through thin-layer injection system to provide a composite multi-layer flow having at least one discrete layer of polyethylene terephthalate and at least another discrete layer of the above-mentioned copolymer; (C) submission-mentioned composite stream into a form for molding a starting material, having inner and outer sublayers containing polyethylene terephthalate and the above-mentioned copolymer, moreover, the above-mentioned underlayer containing the above copolymer has an air permeability that is less than the permeability to air of the mentioned sub-layer containing polyethylene terephthalate; (d) supply of recycled polyethylene terephthalate mentioned on the initial blank for forming the outer layer around the mentioned starting material to form the final preform and (e) the exposure mentioned end of the preform blow molding operation f the th recycled polyethylene terephthalate is fed over the said workpiece in such numbers, to provide an outer layer which is thicker than at least one of the inner and outer sublayers provided in the operation (C).

26. The method according to p. 24, in which the aforementioned first and second polymers injections through the mentioned thin-layer injection system in relative amounts to provide the thickness of the aforementioned discrete layer of the above-mentioned copolymer, which is less than the thickness of the discrete layer of polyethylene terephthalate.

27. The method according to p. 24, in which at least one diol includes ethylene glycol.

28. The method according to p. 24, in which the mentioned composite stream is fed to the form so that the polyethylene terephthalate formed an internal sublayer mentioned starting material, and the aforementioned copolymer formed outer sublayer mentioned starting material, and the aforementioned outer sublayer covers mentioned internal sublayer.

29. The method according to p. 28, in which the aforementioned first and second polymers together injections through the mentioned thin-layer injection system in relative amounts to provide thickness mentioned outer layer of the above-mentioned copolymer, which is less than the thickness of the above-mentioned inside the together injections through the mentioned thin-layer injection system, having at least one multiplication operation layers to provide a composite multi-layer flow with multiple discrete layers of polyethylene terephthalate and many discrete layers of the above copolymer, and the above-mentioned multi-layer composite stream is served on the form for the formation of a starting material having multiple sublayers of polyethylene terephthalate and many sublayers of the above-mentioned copolymer, alternating multilayer configuration.

31. Method of manufacturing a multilayer plastic container, containing the following: a) submission of polyethylene terephthalate in the form for shaping a starting material containing polyethylene terephthalate with a thickness sufficient for forming a self-sustaining structure with the removal of these forms; (b) providing a first body of thermoplastic polymer containing recycled polyethylene terephthalate, and the second body of thermoplastic barrier polymer containing (i) a copolymer of terephthalic acid, isophthalic acid and at least one diol or (ii) thermoplastic phenoxy-type; (C) the injection box thermoplastic polymer and said thermoplastic barrier polymer h is lologo thread having at least one discrete layer of recycled polyethylene terephthalate and at least one discrete layer mentioned thermoplastic barrier polymer; (d) submission-mentioned composite stream to the mentioned initial workpiece to form the final preform, which mentions a composite stream containing sublayers of recycled polyethylene terephthalate and the above-mentioned thermoplastic barrier material covers the mentioned initial preparation of the polyester; (e) the exposure referred to the final harvesting of the blow molding operation for forming a multilayer plastic container.

32. The method according to p. 31, in which the mentioned initial workpiece includes a throat portion at its upper end and body portion at its lower end, and referred to the throat portion includes a supporting ring at the lower edge mentioned a throat portion and said throat portion is threaded, and said composite stream is served on the said body part mentioned starting material and bottom ends of said support ring.

33. The method according to p. 31, in which the aforementioned thermoplastic barrier polymer is pool.

35. The method of manufacture and coating of polyethylene terephthalate plastic with a barrier layer of a copolymer of terephthalic acid, isophthalic acid and diol containing the following operations: closing the form that contains the fixed and movable halves, with the mentioned stationary half of the form contains at least one cavity for forming workpieces and at least one cavity for coating workpieces, and the movable half of the form contains a rotary platform having attached to it a number of bars equal to the amount of cavities forming blanks and cavities of the coating of the workpieces; the injection box of the first material in the space defined by the mandrel, and in the cavity of the molding blanks for forming a billet having an inner and outer surface; the opening of the mentioned forms; the mentioned rotation of the rotary platform; closing the said form; the injection box of the second material in the space defined by the aforementioned outer surface of the said workpiece, and mentioned in the cavity of the cover blanks for forming a coated workpiece; opening mentioned forms; the destruction referred to covered procurement.

36. The method according to p. 35, kotoruyu mentioned stationary half of the form.

37. The method according to p. 35, in which said workpiece is not solid or finished before injectionem mentioned second material.

Priority points:

19.03.1998 - PP. 1-9, 24-34;

17.10.1997 - PP. 10-23, 35-37.

 

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