MXPA99002205A - Zero oxygen permeation plastic bottle for beer and other applications - Google Patents

Abstract

Multilayered plastic bottles are disclosed having oxygen scavenging capacity sufficient to maintain substantially zero or near zero (depending on product requirements) presence of oxygen in the bottle cavity for the planned shelf life of the bottled product under specified storage conditions. The bottles feature a layer comprised of oxygen scavenger copolyester and may be used for bottling beer and other products requiring nearly total absence of oxygen for the duration of the target product shelf life.

Description

PLASTIC BOTTLE OF NULA PERMEATION TO THE OXYGEN FOR BEER AND OTHER APPLICATIONS FIELD OF THE INVENTION The invention relates to multi-layer plastic containers having improved resistance to oxygen permeation, and to compositions and processes for the production of multi-layer plastic bottles.

BACKGROUND OF THE INVENTION In order to be technically acceptable beer containers or containers (glass, metal, or plastic) they must keep the beer contained in them in an almost oxygen-free environment. A generally accepted industry standard is considered to be a maximum of 1 ppm of oxygen entering the bottle during the planned storage time of bottled beer. In addition, not only should oxygen be excluded from bottled beer, but the carbon dioxide discharge of the beer from outside through the walls of the bottle must also be eliminated or at least contained by defined standards. * " REF .: 29406 Oxygen may be present in the bottled beer from at least three separate sources. In some cases, undesirable (air) oxygen is not completely removed from the top space of the liquid in the beer bottle during the bottle filling process. The oxygen that rises from this source is known as oxygen from the upper space. Even the packaging of beer in cans is susceptible to the presence of oxygen from the upper space. In glass beer bottles conventionally covered or capped, oxygen can enter the bottle during storage by permeation through the medium used as the package in the crown of the bottle, bent or corrugated. A third source of oxygen in bottled beer is specific for the use of plastic bottles. Oxygen, from the air, has the ability to infiltrate many conventional bottling polyesters and end up inside the bottle cavity. Also, for plastic bottles, oxygen can be dissolved or adsorbed on the plastic. The oxygen dissolved in or adsorbed on the walls of the plastic bottle can be desorbed and end up in the cavity of the bottle. Such oxygen desorbed is imperceptible from the oxygen of the upper space once inside the cavity of the bottle, except that it should be seen as a possible source of oxygen that continues, the which must be consumed or emptied. For the purposes of this, oxygen desorbed should be considered to be a factor which contributes to the oxygen of the upper space. The oxygen dissolved in the plastic wall is imperceptible from the oxygen that tries to permeate through the walls of the plastic bottle. For the purposes of this, the oxygen dissolved in the walls of the plastic bottle will be considered as oxygen that tries to permeate the walls of the bottle. In summary, therefore, the packaging of beer in cans or metal containers is generally at risk only from the oxygen in the upper space. Beer in glass bottles is generally at risk of oxygen from the headspace and also oxygen permeation through the bottle closure means, especially corrugated crown packings. Beer in plastic bottles is at risk of oxygen from the two sources indicated above and also oxygen permeation through the bottle wall in the bottle cavity. These considerations also applied to other products packaged in cans and bottles for the effects of oxygen, can vary considerably depending on the oxygen sensitivity of the product. While the "bottling of beer in plastic bottles is still in its infancy, the Previous disclosure as methods for undesirable oxygen to be present in a plastic bottle cavity is well documented in the art, not only for packaging applications that have such stringent oxygen requirements as those for beer, but also for applications less rigorous than those for bottling beer. Attempts to overcome these problems for plastic bottles have often involved the use of multi-layer bottles where at least one of the layers comprises a polymer (such as ethylene vinyl alcohol copolymer, EVOH) having superior passive resistance to permeation of oxygen that is compared with the polyester packaging or bottle making which is usually polyethylene terephthalate (PET). There are disadvantages to such proposals including the following: (1) the bottles are no longer suitable for recycling with other polyester (PET) bottles because of the presence of a secondary and incompatible polymer (EVOH), (2) the bottles tend to delaminate at the PET / EVOH interfaces, although such delamination can be slightly decreased (at additional costs) by the use of adhesive tape layers, (3) differences in melting points and other physical properties between PET and EVOH they cause numerous problems in the bottle manufacturing process, and (4) the use of a passive oxygen barrier, such as an EVOH layer, it tends to keep oxygen in the upper space trapped inside the bottle cavity instead of eliminating it. This invention addresses these and other problems related to prior art efforts to manufacture plastic bottles with zero and almost no oxygen permeation.

DESCRIPTION OF THE INVENTION Accordingly, in a broad sense, this invention relates to new bottles and a process for the production of plastic bottles of substantially nil, multilayer oxygen permeation. The oxygen permeation substantially zero means that the oxygen which finds its way to the bottled product is an amount which is only measured sparingly with instruments that measure such permeation. In the absence of a specific amount of oxygen, the substantially zero oxygen permeation will be considered to be 1 ppm of oxygen, in terms of the weight of the bottled product, for the target storage time of the bottled product. The multi-layer plastic bottles of this invention are suitable for recycling or recirculating with other polyester bottles, They have excellent rigidity, have good clarity when such clarity is desired, resistant delamination, do not need layers of tape, and also have the ability to not only maintain oxygen (of air) from the inlet of the bottle cavity but also have the ability to consume or empty the presence of undesirable oxygen in the cavity of the bottle. The new bottles of this invention involve the use of processes and equipment that make modern multi-layer bottles, in conjunction with the deployment of at least one layer (of the multi-layer plastic bottle) comprising a copolyester oxygen cleaning formulation, the which is an active oxygen cleaner. Active oxygen scavengers consume (or otherwise empty) oxygen from a given environment. As noted in the copending application, a multi-layered bottle of zero oxygen permeation will have sufficient oxygen scavenging or expulsion capacity to consume any undesirable oxygen (from the headspace) in a bottle cavity and still have sufficient spare capacity to consume oxygen at the speed or range at which it reaches the cleaning or expelling layer from the outside air to the container, by the necessary storage time of the filled bottle.

The Applicants' oxygen scavenging or stripping systems are copolymerized from blocks comprising predominantly polycondensate segments and an oxygen scavenging amount of polyolefin oligomer segments. Predominantly means that at least 50% by weight of the copolycondensate can be attributed to polycondensate segments. Preferred polycondensate segments, especially for use in packaging or packaging production, are polyester segments. For layers in multi-layer bottles in which some of the layers are PET, or modified polyesters such as PETI, PETN, APET, PETB and / or PEN, segments of the block copolyester comprising these same polyesters are especially preferred. A major reason is that the copolyesters more closely emulate the polyester from which their polyester segments are derived. The aforementioned polyesters and various modified polyesters for packaging, considered except for use with foods as listed in 21 CFR § 177.1630, are the polyesters of choice for bottles because of their clarity, rigidity, and their great history of use for storing Drinks and food. It will be understood that many references to PET made in this specification will cover (unless "otherwise specified") not only PET, but will also include PET as is commonly used. in various modified forms for bottling including, but not limited to, the list of modified polyesters, cited above and later defined in greater detail in this specification. The polyolefin oligomer segments are prepared by copolycondensation by first functionalizing the polyolefin oligomer segments with end groups capable of forming part in the polycondensation reactions. This is an important feature because the polyolefin oligomers are, in effect, addition polymers. The functionalization of the polyolefin oligomers with end or end groups provides a convenient method for the incorporation of polymeric addition segments in a copolycondensate. A preferred polyolefin oligomer is polybutadiene (PBD) because it has good oxygen scavenging or oxygen scavenging capacity and reacts rapidly with oxygen especially in the presence of a transition metal catalyst, such as cobalt, and in the presence of benzophenone, or both cobalt and benzophenone. One of the salient features of the oxygen scavenger or expeller copolyesters of this invention is its ability to clean or draw oxygen in the presence or absence of water or even moisture. While much of the discussion of this description focuses on No oxygen permeation beer bottles, many other materials are suitable to be bottled and / or packaged in packaging or packaging environments with zero or near zero oxygen permeation, provided and included by this invention. Examples, in addition to beer, beverages and perishable foods for which a jar, bottle or specialized container of zero oxygen permeation, could be desirable, are well known and include wines, fruit juices, beverage concentrates, flavored teas , isotonic, tomato-based products such as tomato sauce, sauces, and seasonings for roasting, vinegar, mayonnaise, baby food, nuts and dry foods of all varieties. Non-food items that require zero-permeation packaging to oxygen may include electronic parts sensitive to oxygen. One reason that the success of this invention is thus appropriate has been the recent tilt in the beverage and food industries to provide information to the consumer as to the freshness of the product. If it is legislated or voluntary, it has become a standard practice in the beverage and food industries to provide information "sold by," "used by," or "bottled in," uncoded, easily understood, clearly printed on the bottle or packing. This great need for felting to satisfy consumer awareness or awareness of product freshness has recently been well exemplified by a warning campaign from leading US breweries that characterize their so-called "made in" data for beer. bottled up. This consumer information data on packaging and bottles helps consumers in their determination of convenience and freshness of the product. These data are also of value in the application of this invention, since the knowledge of the target storage time for a given product, allows the easy calculation of the capacity of cleaning or of expulsion of the oxygen required to maintain the zero permeation (or almost zero) to oxygen for the maximum planned storage time. The adjustment of the oxygen cleaning or expulsion capacity of the bottles of this invention ensures the zero oxygen permeation that varies not only by the product but also within a given product line. In a document titled REQUIREMENTS FOR PLASTIC BEER PACKAGES presented at the conference "Future-Pak? 96" by Dr. Nick J. Huige of the Miller Bre ing Company, it is described that for "home-brewed" beers US, it is generally recognized as the industry standard a maximum income of 1000 ppb (1 ppm) during 120 days of shelf storage when stored at 24CC (75 ° F). It is a common practice to throw away any 120-day old beer (that is, 120 days since the bottling) from the retail shelf, and destroy it. This is true for any US beer not only because of the possible presence of oxygen, but also because of other changes which occur once the beer is bottled, especially the appearance of a moldy or stinky character. Huige also estimates that approximately 95% of beer from major US breweries reaches consumers within 60 days of bottling. But according to the industry standard, a planned shelf life of zero oxygen permeation for 120 days at 24 ° C (75 ° F) is a realistic target for bottling beer from the major breweries in the US. For producers of microbreweries in the US and European beers, the requirements can be totally different. For US microbreweries, it is unlikely that 95% of the product will be delivered to consumers within 60 days of bottling. Also, producers of European beers (and for US microbreweries of smaller scope), consider it desirable for bottled beer, assume that they are characterized by beer flavors as a "paper-like / coal-like" flavor. mineral, "a characteristic associated with at least the partial oxidation of beer in the bottle.This is strictly an undesirable attribute for American beers balanced or balanced in a more delicate, lighter-bodied form. It should be obvious that adjusting the range of permeation to acceptable oxygen, including storage duration requirements of zero oxygen permeation, is not always a simple issue, but it can be predicted and calculated in many cases and empirically derived in other cases. Known, methods of adjusting oxygen scavenging or expulsion capacity and / or storage duration of zero oxygen permeation required by the bottle, can be achieved by one or a combination of several of the methods of this invention as described subsequently in detail The PCT Application Published (WO 96/18686 published on June 20, 1996) describes the use of materials of aliphatic polyketone as oxygen scavengers or expellers. This reference has no examples of zero oxygen permeation bottles manufactured. There are non-experimental data in the reference other than the primary aliphatic polyketone permeability coefficients, and it is not clear if these data were experimental or provided by the resin manufacturer The function of cleaning or expulsion of oxygen, described in the reference, is insufficient by several orders of magnitude to maintain zero oxygen permeation, that is, the cleaning or expulsion capacity is insufficient to consume the oxygen in the range at which the reaches the cleaning or expulsion layer by permeation through the outer PET layer. Japanese patent document 3-275327 left open on 06/12/1991, describes a blown bottle having walls which include an "oxygen impermeable" layer of a "methoxyarylenediamine". The data in this reference shows a reduction in oxygen permeation that decreases to 28% of the amount that passes using PET bottle walls only. This amount is inconsistent with the goal of this invention which is zero oxygen permeation. A cleaning or expelling single-layer oxygen bottle wall (homogeneous and monolithic) is described in European Patent Application EP 380,830 published on August 8, 1990. This reference describes OXBAR bottle walls (suitable for manufacturing bottles of beer according to the teaching). OXBAR is a mixture of approximately 96% by weight of pure PET, approximately 4% by weight "of MXD6, and a solution of cobalt carboxylates of 8 to 10 carbon atoms which they have about 10 wt.% cobalt as expanded metal to provide approximately 50 ppm cobalt in terms of the weight of the mixture. MXD6 is a polyamide prepared from equimolar amounts of adipic acid and metaxylene diamine. According to the reference, the presence of the MXD6 not only serves as an oxygen scavenger or expeller but also improves the ability of the PET to retard the discharge of C02 from the cavity of the bottle outside through the walls of the bottle. Any bottles made in accordance with this reference could have some serious deficiencies including, among others, (1) loss of recirculation or recycling possibilities, (2) higher cost since the entire bottle consists of oxygen scavenging or depleting material, ( 3) without opportunity to use recirculated or recycled PET since the homogeneous walls are in contact with the bottled product, (4) leaching of potential excess of cobalt in the bottled product, (5) without means to efficiently and effectively adapt the cost of the ability to clean or expel oxygen from the bottle, to the required storage time, and (6) rapid loss of the capacity to clean or expel oxygen (even in the preformed state) due to the obvious oxygen attack of the air directly on the cleaning or ejection portion of oxygen. While not described in this reference, applicants have speculated on the effectiveness of a bottle comprising an outer layer of PET, an intermediate layer of OXBAR, and an inner layer of PET. The cost (very thick layer of OXBAR needed to supply the required oxygen ejection capacity) and the recirculation or recycling emitted could be present in one modality. The only significant disadvantage of using multi-layer bottle walls is that more complex bottle making machinery is required to form the multiple layers. The advantages resulting from the use of novel multi-layer bottle walls, consider the only simpler processing advantage associated with a single or single, homogeneous bottle wall. Typically, the bottle wall embodiments of this invention are three layer constructions of Layers A-B-C. Layer A is the outer layer that forms the outside of the bottle and is in contact with the outside air. Layer B is the layer that cleans or expels oxygen. Layer C is the innermost layer and defines the cavity of the bottle. Among the advantages of a multi-layer construction are (1) ability to use recirculated or recycled PET in Layer A, (2) ability to "dilute (within limits) the expelling or cleaning layer, Layer B, with the PET recirculated or pure to facilitate and effectively adjust the cost of the zero permeation capacity to the oxygen for the planned shelf life of the product, (3) isolation of the packaged product (bottling) from the oxygen cleaning or expulsion layer via Layer C (Layer C is normally virgin or pure PET), (4) isolation of the oxygen cleansing layer from oxygen in the air because of the presence of external Layer A, and (5) retention of the ability to recirculate or recycle when the multi-layer bottles of this embodiment of the invention are typically above 99.6% PET and PET segments. The use of a 5-layer bottle wall of type A / B / A '/ B / A where A is PET, B is (are) the cleaning or ejection layer (s) either pure or diluted and A 'is also PET, especially recirculated or recycled PET.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view of the wall construction of the multi-layered bottle, of zero oxygen permeation, preferred.

Figure 2 shows a graph of idealized oxygen permeation data for bottles of three different constructions. Figure 3 shows a graph similar to that of Figure 2, which refers to ranges of oxygen permeation for the duration in bottle storage. Figure 4 shows a graph with oxygen permeation data for the bottles of Examples 1-6. Figure 5 shows a graph with data confirming the ability of the copolyesters to consume oxygen from the headspace, even when they are used as Layer B in a wall construction of the A / B / A or A / B / C bottle. Figure 6 shows a graph with data similar to those in Figure 5 and further shows the ability of the copolyesters to clean or expel oxygen to empty oxygen from the headspace even when they are used as the Layer B in a wall construction. the bottle A / B / A or A / B / C. Figure 7 shows a graph that shows data confirming the increase in oxygen expulsion capacity of the oxygen-releasing copolyesters when diluent blended such as Layer B is used in a wall construction of the A / B / bottle. A or A / B / C.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES For the purposes of this invention, it is useful to define substantially zero or almost zero oxygen permeation bottles. Oxygen permeation bottles are substantially non-existent, which do not allow the reliably measurable entry of oxygen into the bottle cavity during the period of storage of the bottled product under specific storage conditions. In the absence of a specific amount of oxygen permeation, which can be tolerated by the product, the substantially zero oxygen permeation will be defined as not greater than 1 ppm (in terms of weight of the bottled product) of oxygen permeation in the product for the duration in white stock, of the product bottling. In the absence of a storage duration in white shelves, specific, shelf life as a target, for the purposes of this, an attempt will be made to define a period of time typically in the range of 30 to 365 days, more specifically in the range from 60 to 365 days, and more specifically in the range of 60 to 180 days. Also, in the absence of specifically defined storage conditions, specific storage conditions, for the purposes of this, are defined as temperatures environment (from 4 ° C to 25 ° C). The bottles of almost zero oxygen permeation, are bottles which delay the entry of oxygen into the cavity of the bottle to levels equal to or less than the amount specified for the given application and / or for the duration in white shelves of the bottled product , under specified storage conditions. For bottles with almost no oxygen permeation, the storage duration in target shelves will be in the range of approximately 30 days to 2 years and the storage conditions specified are the same as defined above for substantially zero oxygen permeation bottles. . In a general sense, this description involves the combination of several inventive elements in more modalities to achieve that the bottles have capacities and qualities of cleaning or expulsion of oxygen as defined above. It has been found that new copolyester compositions for cleaning or expelling oxygen can be easily adapted to manufacture bottles and containers of multiple layers of zero or almost zero oxygen permeation using commercially available processing equipment. As such one of the inventive elements involves the use of known apparatus, machinery and equipment, used in the processes of manufacture for multi-layer bottles in a process for manufacturing the oxygen permeation resistant bottles of this invention. Another inventive element relates to the use of the oxygen cleaning copolyester compositions, as a layer (or at least one layer) of the multi-layer bottle. Another inventive element involves the simple but eloquent techniques described to adjust the oxygen ejection capacity of the manufactured bottles to the planned application in the most cost effective manner. Combinations of these inventive elements serve to define the various modalities of the new, multi-layered, zero-permeation plastic bottles of this invention. The size (volume) of the substantially zero or almost zero oxygen permeation bottles of this invention will be in the range of 0.03 liters to 4 liters. The smaller volume bottles that have a capacity of approximately 0.03 liters could be used, for example, to bottle or pack individual snacks that are frequently used by airlines. Larger volume bottles with a capacity of approximately 4 liters could be used, for example, to bottle such wines "as in the double-liter bottle size." Double-sized bottles could be suitable for beer, V numerous oxygen sensitive products, different, as mentioned elsewhere in this specification. While the bottles or this invention are primarily intended for storing edible products, the bottles could also be suitable for use with non-corrosive products more sensitive to oxygen, capable of being stored at ambient temperatures and pressures. As an extreme case, for example, the bottles of this invention could be unsuitable for storing liquid oxygen, not only because they are outside the range of pressure and useful storage temperature, but also because the liquid oxygen could consume all the cleaning capacity or oxygen ejection from the bottles in a very short period of time. To be economically feasible, the amount of material used in the bottles of this invention must be in the order of magnitude of that used in conventional polyester bottles. The amount of material is directly related to the total wall thickness of the bottles and could typically be in the range of 0.1 - 2 millimeters (4 - 80 thousandths of an inch). Thus, this invention discloses a substantially zero volatile oxygen permeation container or container for storing an edible product having a volume in the range of 0.03-4. liters and a wall of multiple layers of total thickness in the range of 0.1 - 2 millimeters. The containers and bottles of this invention may additionally comprise a base which may be optionally of a monolithic construction and may also be optionally thicker than the walls as a means to provide oxygen barrier properties for the non-layered base. The containers and bottles of this invention may further comprise a segment suitable for securing a sealing means or bottle cap. This segment may optionally be of a monolithic construction and may also optionally be thicker than the walls as a means to provide oxygen barrier properties for the non-layered segment. In another preferred embodiment, this invention describes a thermoplastic bottle of zero oxygen permeation, having a storage cavity of the edible product, the bottle comprising a base which defines the lower part of the cavity of the bottle and a generally cylindrical side wall , multi-layered, fixed to the base and extending away from the base that forms the wall of the cavity of the bottle and provides the necessary volume to the cavity of the bottle, the side wall ending to end an opening in the bottle. The upper part of the bottle cavity is suitable for fixing a bottle cap wherein an inner layer of the side wall is comprised of a copolyester cleaning or oxygen expelling formulation comprising predominantly polyester segments and an oxygen scavenging amount of polyolefin oligomer segments, and wherein the bottle , after filling and capping, has sufficient oxygen cleaning capacity (a) to consume and drain oxygen from inside the bottle cavity, (b) consume and drain oxygen which can enter through the opening of the lid of the bottle, and (c) consume oxygen at a range approximately equal to the range at which the oxygen in the air reaches the internal cleaning layer, where the near-complete oxygen consumption (a), (b) and (c) ) is maintained at least at a level of oxygen deviation required for a shelf life of the bottled, target or target product, under a specified storage condition. In another preferred embodiment, this invention describes a process for manufacturing a multi-layer oxygen expelling bottle, comprising the steps of. (i) forming a first resin layer using multi-layer bottle manufacturing apparatuses, (ii) forming a second resin layer using multi-layer bottle manufacturing apparatuses, (iii) forming a third resin layer using multi-layer bottle manufacturing apparatuses, and (iv) transforming the first, second and third resin layers into a finished multilayered bottle, using multi-layer bottle making apparatuses.; wherein the apparatus has means (A) for separately processing at least two different resins and (B) forming a layered bottle having at least three layers, and wherein at least one of the layers of the bottle comprises a copolyester oxygen cleaning or expelling resin formulation, comprising predominantly polyester segments and an amount cleaning or oxygen expulsion of oligomeric polyolefin segments. Preferred embodiments are directed not only to packaging items, but also to processes for manufacturing the articles, compositions used to manufacture the articles, and methods that effectively adjust the cost of the oxygen expulsion capability of the articles. As such, it is more convenient, for the purposes of this specification, to sequentially describe inventive elements (I) the multi-layer bottle made by processes included in this invention, (II) cleaning or ejection of oxygen, of copolyester, included for use in at least one of the layers of the bottle, and (III) techniques and several modalities to adjust in a more economical way the ability to clean or expel oxygen from the bottles, followed by the planned application. 1. METHODS AND EQUIPMENT FOR MANUFACTURING MULTI-LAYERED BOTTLES In all cases, the layer comprising the compositions for cleaning or expelling oxygen, or copolyester, will be an inner layer of the bottle. For this description an inner layer is defined as being an inner layer of the bottle wall. An inner layer is not a layer which is directly in contact with air. Also, an inner layer is not a layer which defines the cavity of the bottle and, as such, is not a layer in contact with the contents of the bottle. In more embodiments of this invention, three layers will be preferred. The term "multi-layer blow molding by co-extrusion" refers to a technique for manufacturing a blow-molded product using two or more extruders and introducing the hot-melt resins into a die and joining them in a die or outside the die. In the simplest terms3, it is only necessary to fix auxiliary extruders and the multilayer die to a Conventional blow molding machine. The coextrusion of the same materials (resins) presents perhaps some problems. However, there are many difficulties involved in the molding of bottles by coextrusion of different resins. Some of these difficulties include (1) thermal decomposition of less stable resins, (2) reduced moldability, (3) insufficient adhesion strength between the layers, (4) reduced melting in the constriction sections due to the different melting temperature and different rheological characteristics of the molten resins, and (5) delamination due to the different contraction forces between the layers after molding and during cooling after hot filling the bottles. From this, the biggest problem is the poor adhesion between the layers. A typical formulation used as a layer in multi-layered bottles of oxygen delivery includes a copolyester comprising 96% by weight of PET segments and 4% by weight of polybutadiene oligomeric segments (PBD). This typical formulation is co-extruded, optionally with PET diluent, as an intermediate layer in a bottle wall typically interposed or interleaved between PET layers. PET resin and PET / PBD copolymer resin are virtually identical except for the smaller percentage of PBD segments. As such, they also have very similar properties and many of the problems noted above for the co-extrusion of dissimilar resins are not present when PET and the PET / PBD copolymer are co-extruded for the production of multi-layer bottles. Accordingly, processes and equipment that lack some or many of the special features described in the embodiments that follow are suitable for use in the production of multi-layer bottles when one of the layers comprises a cleaning or expulsion formulation. of oxygen, copolyester, of this invention. Of course, for on-the-go production, the manufacture of the multi-layer bottles of this invention can be carried out in the common multi-layer bottle manufacturing equipment, either in its place still through the process of manufacturing bottles having PET / copolyester / PET cleaner layers are subject to much less sophisticated bottle making equipment, particularly in terms of less need to control the separate temperature of these resins during the injection molding of bottles and preforms of bottles. The equipment that manufactures bottles, including the production of "bottle" preforms, which comprise means for the separate injection of two different resins for manufacturing layered or layered bottles, or bottle preforms, operates at approximately the same resin temperature for both resins, comprised in a general embodiment of this invention provided, one of the resins is a copolyester cleaning or expelling resin formulation. , of this invention.

Modality I-A Blown Molded Bottles (co-injected or sequentially injected resins) Co-extruded from Multiple Layers that include the use of Bottled Preforms. A process showing simultaneous injection is described in U.S. Patent 4,717,324 (Schad et al.). A first characteristic of the patent Schad et al. is to provide individual hot run systems for each resin from the resin source to the mold cavity, independently maintained and controlled at the temperature at which it is optimal to process selected resin. A further feature is to provide a nozzle structure thus constructed and arranged to provide individual channels for each resin, with individual heating means to maintain each channel at a temperature which is more satisfactory for processing the "resin through" the channel. the use of plural mold cavities is described which are filled simultaneously with each type of resin that produces a plurality of multiple layer articles simultaneously. This method is especially suitable for the production of three and five layer bottle preforms comprising internal EVOH layer (s) completely interposed between the PET layers. For this invention, applicants use layers of oxygen scavenger or copolyester, instead of or in addition to EVOH layers. A sequential or simultaneous injection process for multi-layer bottles is described in U.S. Patent 5,141,695 (Yoshinori Nakamura). The Nakamura patent describes the production of five and four layer bottom preforms using up to three different resins from a single nozzle having three flow passages. The preforms are subsequently made in containers or hollow containers by blow molding or orientation molding. Nakamura lists many resins which are suitable for forming the layers in the bottle by blowing, including PET with EVOH. For this invention, applicants use copolyester oxygen scavenger or expeller layers in place of or in addition to EVOH layers with PET. Another example of a sequential injection process for the formation of layer bottle preforms multiple is described in U.S. Patent 4,710,118 (Krishnakumar et al.). The Krishnakumar patent covers the production of five-layer bottles via the formation of five-layer bottle preforms having layers comprising resins A-B-C-B-A. Layers A and C may be the same and are usually PET. In some embodiments, Layer C can be recirculated or recycled polyester and / or reformed bottle-forming polyester. Normally B layers are EVOH and are usually much thinner than could be found in constructions that have only a single layer of EVOH. The two thin layers of EVOH have better barrier properties than a single thicker layer of EVOH. The Krishnakumar et al. Patent also describes new valve and manifold systems or manifolds that provide separate control for each injected layer and also separate control of the diverse temperature supply. For this invention, applicants use layers of copolyester oxygen scavenger or expeller in place of or in addition to EVOH layers with PET. Especially preferred are processes for multi-layer bottles comprising copolyester oxygen scavenger layers, wherein the expulsion copolyester layer is not centered in the wall of the bottle between two layers of PET of equal thickness. The walls of these bottles and bottle preforms can be designated as Al-B-A2 resin layers. The Al layer is PET or another polyester to make bottles and it is the layer which forms the skin or outer layer of the bottle. The polyester of the Al layer may be virgin or pure, recycled, claimed, or mixtures of the foregoing. The layer A2 is also PET or another polyester to make bottles and is the layer that defines the cavity of the bottle. Layer B is the copolyester cleaner or expeller. Usually, the thickness of the Al layer of PET, will be in the range of 2 to 10 times the thickness of the A2 layer of PET. This type of structure produces the cleaning or expulsion layer, of copolyester, a good opportunity to empty the undesirable oxygen in the cavity of the bottle since the oxygen has to go through only the layer A2 of very thin PET, to reach the cleaning layer or expulsion where he himself is consumed. Conversely, the oxygen of the air outside the bottle has to pass through the thicker Al layer of PET before it reaches the cleaning layer and is consumed. As such, the thicker or thicker PET layer with respect to the exit of the bottles helps to prevent the ingress of oxygen into the cleaning or expulsion layer so that the useful period of the cleaner or expeller is extended. Such construction of bottle and bottle preform, is described in the patent North American 4,990,301 (Krishnakumar et al.). The 301 patent of Krishnakumar describes the use of EVOH layers (centered and not centered) interposed between PET layers. Also disclosed in the '301 patent is the use of multi-step coaxial nozzles and supply means for administering resins other than the nozzle passages which allows the separate and simultaneous injection of different resins into the bottle preform mold. The use of external layers of PET and internal layers of EVOH are described. For this invention, applicants use expulsion copolyester layers in place of or in addition to EVOH layers with PET. An injection molding apparatus which includes similar coinjection modules, each provided with common supplies and provided with different resin materials at intermediate pressures by a plurality of extruders, is described in U.S. Patent 5,028,226 (De'ath et al. ). In the De'ath et al patent, each resin is injected by an injector directly into the associated nozzle and is controlled solely by the operation of the injector, and without the use of any control valve between the injector and the nozzle. This process can accommodate up to seven layers in the preform but typically there are five layers and only two or three resins. For this invention, applicants use a layer construction A-B-C-B-A wherein A and C are PET layers and at least one of the B layers is comprised of a copolyester oxygen ejection composition. An injection molding process wherein the multi-layer bottle preform is held in the upright position during manufacture, is described in U.S. Patent 4,957,682 (Kobayashi et al.). The Kobayashi patent describes the production of preforms and containers of three layers, ie a bottle wall having layers A-B-A. A key difference is that the injections are sequential and delays are described between the resin injections. In a typical process of the Kobayashi patent (1) the external resin layer A is injected, (2) after a delay of up to three seconds, the intermediate layer B is injected, and (3) after an additional delay of until a second, the second layer of A is injected. The sequential injection with delays provides improved uniformity of layer B. The resins described are PET (layers A) and EVOH (layer B). For this invention, applicants use layers of oxygen-cleaning copolyester as layer B instead of or in addition to EVOH layers with PET generally comprising layers A.

A process for manufacturing multi-layer bottle preforms by providing a hot guide mold by multilayer molding, including a plurality of nozzle bodies for injection of a plurality of different resins to form a multi-layer product, is described in U.S. Patent 5,232,710 (Miyazawa et al.). The hot guide rail mold comprises a plurality of hot guide rail blocks each having a guide rail for driving each resin to the corresponding resin body. The guide rail or hot slide blocks are stacked one on top of the other with thermal insulation layers located between the stacked slide guide blocks. Each hot sliding guide block has a separate temperature control to keep each resin at the optimum processing temperature. Typically, the three-layer bottles are made of PET-EVOH-PET resin layers. For this invention, applicants use copolyester oxygen-release layers in place of or in addition to EVOH layers with PET layers.

Modality I-B. Overmolding / Lamination Process for the Preparation of Multiple Layer Bottles and Bottle Preforms The published PCT application having International Publication Number WO 95/00325 and publication date of January 5, 1995, typically describes a PET-EVOH-PET three-layer bottle and bottle preform. The outer PET layer is comprised of post-consumer PET (recycled). The internal PET layer which defines the cavity of the bottle and is in contact with the contents of the bottle is pure PET. The EVOH layer can be omitted when there is no need for oxygen barrier properties to be imparted to the multi-layer container. An annular ridge in the pure PET layer is formed by the molding at the end of the preform which receives the closure device of the bottle (i.e., the open end of the preform). The projection extends far enough away so that the closure liner contacts only pure PET, while the closure threads are attached to threads formed from the recycled PET layer. Therefore, the virgin or purer, more internal PET layer is molded on the outer recycled PET layer. For this invention, applicants use layers of copolyester cleaner or oxygen scavenger instead of or in addition to EVOH layers of PET layers.

Japanese Patent Document JP 3,275,327 published on December 6, 1991 discloses a blow molded, extracted, hot beverage container comprising a PET laminate construction which also characterizes a PET base and heat resistant resin with a temperature of distortion in high heat. The extracted blow molded container is composed of a mouth, a projection, a body or main part, and a lower part. The body is made of PET. The lower part is composed of a PET laminate structure and a heat resistant resin that has a heat distortion temperature above 100 ° C. Preferably, the body and the base include an oxygen barrier resin layer, such as EVOH, in the laminated structure. The heat resistant resin is, for example, an aromatic polyester such as PEN. The beverage container is especially useful for hot fill applications when the heat distortion observed in the hot filling of conventional multi-layer bottles is eliminated. For this invention, applicants use layers of copolyester cleaner or oxygen scavenger instead of or in addition to EVOH layers with PET and / or PEN layers. A multi-layer plastic container with improved gas barrier properties, using a active oxygen scavenger or expeller (or vacuum tuning layer) of resins, is disclosed in U.S. Patent Number 4,107,362. (Emery I. Valyi). Some of the layers are formed by overmolding technology when they oppose co-or sequential injection to form the layers in the bottle or bottle preform. Instead, two layers of plastic are placed around a core contained within a mold which, therefore, expands in a blow molding container. Finally, a third layer is press molded around the two-layer sleeve. The result is a seamless multilayer plastic container or container. The container has three layers and the modalities are described which show the vacuum tuner in the innermost layer, as well as modalities which show the vacuum tuner in the intermediate layer. The material of the vacuum tuner, which is capable of combining with the undesirable permeation gas, is an additive for the plastic layer in which it resides. For this invention, applicants use copolyester oxygen-release layers as the intermediate layer in a three-layer mode in place of or in addition to the intermediate vacuum tuner based on a material other than the polyester containing the layer.

Modality I-C. Improved Processes for Bottles A method for manufacturing bottles having highly crystalline bottle walls with a sparingly crystalline bottle base is described in U.S. Patent 5,520,877 (Collette et al.). According to the description, Collette et al. Bottles are particularly useful as a refillable container or container which can withstand highly caustic washing temperatures and exhibit leftover reduced flavor. Also, in accordance with the description, Collette et al. Bottles are useful for hot filling applications. The bottle is formed of a single layer comprised of PET from a preform wherein a forming section of the side wall of the preform is initially expanded, heated to contract and crystallize, and then re-expanded. The forming portion of the base of the preform is protected from the heat treatment and expands either before or after the hot treatment step. For this invention, the ideal hot fill capacity characteristic is only exploited and the single layer of PET is replaced by a three-layer construction of PET / copolyester cleaner / PET. Another process for "the production of hot fill plastic bottles, is described in the Patent North American 5,474,735 (Krishnakumar et al.). Patent 735 of Krishnakumar et al., Discloses a method and apparatus for forming a plastic container having an enhanced level of crystallinity for improved thermal stability. A substantially amorphous and transparent preform in the molecular orientation temperature range is expanded by a pulse blowing process one or more times to form an intermediate article, prior to a final expansion step for the full container dimensions. The pulse blow step is conducted in a relatively high voltage range to maximize the formation of crystal nucleation sites, followed by deflation to relax the amorphous orientation, and the final expansion step is conducted to a lower voltage range for minimize amorphous orientation The resulting container has a higher thermal deformation temperature and reduces thermal breakage and is particularly adapted for use as a container for hot fill beverages. A fluid delivery and blow molding apparatus, including a metering chamber and piston, is provided to alternately supply the upper and lower voltage range inflations. For this invention, applicants use a 'three layer PET / copolyester construction cleaner / PET for the walls of the bottle instead of a single polyester bottle bottle wall. A method for the production of handling bottle articles is described in U.S. Patent 5,533,881 (Collette et al.). Patent 881 of Collette et al., Discloses a process and apparatus for manufacturing a blow molded container from a tension-curable polymer. The container has deep recesses to ensure the "post-molding" fixation of a handle or handle. The container is formed in a modified blow mold having retractable blades. The blades or vanes are partially extended for partial blow molding recesses, and then further extended to mechanically form the handle recesses or deep handles. The mechanical forming operation exceeds the elongation limits imposed by the stress hardening of the plastic material during blow molding, and the "post-molding" fixation of the handle or handle provides a reduced cycle time and lower level of defects compared to the operations of forming the handle or handle "in molding" known. For this invention, applicants use a three-layer PET / copolyester / PET cleaner construction for the walls of the bottle on the wall of the single polyester layer bottle.

A process of forming a three and / or five layer bottle preform is described in U.S. Patent 5,032,341 (Krishnakumar et al.). The patent? 341 of Krishnakumar et al., Describes a plastic preform from which a plastic container is blow molded. The preform replaces a three-layer preform by providing a preform which is of a five-layer construction, in the portion forming the base thereof and in which a secondary material which forms the core layer of the preform construction of three layers is divided into an inner intermediate layer and an outer intermediate layer by a third injection of material. The third injected material is preferably the same material as the primary material which is injected first. This results in the reduction of the cost of the preform and also provides, remaining in the injection nozzle, a quantity of the material injected to the latter which is the same as the first material injected for the next preform in the same injection molded cavity. the preform. The preform of the bottle is an ABA three-layer preform where the last part of layer B is filled with less expensive material C such that the base exceeds five layers (ABCBA) while the walls are three layers ( ABA). This serves to reduce the amount of layer B material at the base of the bottle and thus reduce the total cost of the container. For this invention, A is a packaging polyester such as PET, B is a copolyester resin formulation for oxygen expelling and C is a less expensive substance than the B layer, for example, packaging or packaging manufacturing polyester or recycled / reinforced packaging polyester.

Modality I-D. Techniques Which Minimize Delamination A multi-layer barrier vessel provided with openings is described in US Patent 4,979,631 (Collette et al.). The x631 patent of Collette et al. Discloses blow molded plastic containers wherein at least the container body is of a laminated construction including, for example, a barrier layer which in the case of the container receiving products carbonados could be a gas barrier layer. It has been found that the delamination of such bottles occurs and this is now solved by the selective provision of the container body with very small opening that opens, which does not extend completely through the container body, but in that area where delamination occurs where there is likely to be an accumulation of a permeate, such as C02 of carbonated beverages contained in the cavity of the bottle. Smaller openings can be formed in the outer wall of the container either by means of pins or drilling pins or by using a laser. In the case of the pins or piercing pins, the pins or pins are incorporated in the blow mold to blow-mold the container from a preform and are generally positioned along the lines of the blow mold and also in the central parts of the wall. The construction and operation of the pins or drilling pins can be provided in several ways. Delamination is not a problem in bottles having three-layer walls comprising PET / copolyester of cleaning or ejection / PET using typical polyester formulations because of the similarity of properties of the two resins. However, the use of oxygen-releasing copolyester which is heavily loaded with segments of polyolefin oligomers (eg, above 12% by weight of the copolyester derived from the polyolefin oligomer segments) represent examples in which applicants they could make use of special delamination minimization techniques, such as very small openings that open as described in this modality.

Other techniques for minimizing delamination, such as the use of adhesives, are well known in the art. Another method of manufacturing multi-layer preforms which resist delamination involves cooling the preform while still in the core. In this mode, the cores and preforms are removed from the cavities of the mold as soon as possible to produce it thus without physical deformation of the preform, significant. The preforms are then cooled in the cores for an advantageous period of time which prevents delamination of the layers of the preform. The cooling of the preforms out of the mold cavities is also faster and allows faster cycle times when the media is available, such as ur. rotating slide or turret, for the use of multiple cores. The use of adhesives or cold preforms is contemplated by the applicants in cases where the bottles produced could benefit from such additional treatment.

II. COPOLYTHER FORMULATIONS OF OXYGEN EXPULSION As previously indicated, the oxygen removal or cleaning compositions are block polycondensates containing polycondensate segments predominantly and a quantity of oxygen scavenger or expeller of oligomeric segments of polyolefins. Predominantly means that at least 50% by weight of the copolycondensate can be attributed to polycondensate segments. The preferred polycondensate segments, especially for use in packaging, are polyester segments. For layers in multi-layer bottles in which some of the layers are PET and / or PEN, segments of the block copolyester comprising PET and / or PEN are especially preferred. A main reason is that the oxygen-releasing copolyesters emulate or rival more closely the polyester from which their polyester segments are derived. PET and PEN are the polyesters of choice for bottles because of their clarity, rigidity, and duration or long history of use to store food and beverages. The use of polyesters other than PET and / or PEN for layers A in a layered or multilayer A / B / C bottle construction (A is the outer layer) could ensure the use of polyester segments derived from the polyester. layer A in the copolyester formulation of layer B of the bottle. Frequently, the layers A and C of a multilayer bottle construction A / B / C are the same, except that the "layer A can be recycled or recirculated polyester since it is isolated from the contents of the bottle cavity. The oligomeric polyolefin segments of the copolyester are the portions responsible for the oxygen expulsion capacity. As long as they do not intend to be bound by any theory, the applicants are subscribers to the school of appreciation or conception that believes that the mechanism of oxygen absorption in hydrocarbon materials, such as polyolefin oligomers, is by fixation of oxygen to the hydrocarbon material. via formation of either hydroxy groups or hydroxyperoxy groups. Additionally, it is believed that these groups are formed via a free radical process that involves a peroxy intermediary portion. In a hydrocarbon substance, carbon atoms that have only one fixed or bound hydrogen (a so-called tertiary hydrogen) are more susceptible to the formation of free radicals than carbon atoms that have two hydrogens bound or bound (so-called hydrogens) secondary), which are in turn more susceptible to the formation of free radicals than carbon atoms with three hydrogen atoms attached or bound together. Applicants also believe that allylic hydrogen atoms (hydrogen atoms attached to a carbon atom adjacent to a double bond) are also subject to the formation of free radicals. Applicants recognize that hydrocarbons such as polyolefins, especially polydienes, provide a potentially good source of secondary and tertiary hydrogens as well as chemically activated hydrogen atoms. The applicants therefore plan methods for the incorporation of these portions of oxygen hydrocarbon in the packaging polyesters via the formation of copolyesters using terminally functionalized polyolefin oligomers. Oxygen copolyester expelling compositions and systems are fully described in co-pending US Application No. 08 / 717,370 filed September 23, 1996. The polyolefin oligomer segments (of the block copolyesters which comprise the formulation used in the layers of the bottle), they are prepared by copolycondensation first by functionalizing the segments of polyolefin oligomers with final groups capable of participating in polycondensation reactions. This is an important and novel feature of these formulations because the polyolefin oligomers are, in effect, addition polymer segments incorporated into a polycondensate. The functionalization of polyolefin oligomers with end or end groups produces a convenient method for incorporation of polymeric addition segments to a copolycondensate. There are many extreme or final groups which can enter or participate in polycondensation reactions but the preferred end groups are hydroxy (-0H) and carboxy (-COOH) because the use of such end or end groups leads to a copolyester having all the polyester bonds between polyester segments and polyolefin oligomer segments. For example, the extreme or final amino groups (-NH2) are very acceptable but lead to the formation of some polyamide-type bonds in the vicinity of the polyolefin oligomer segments of the copolyester. Those skilled in the art will recognize that some or all of the hydrogens in the end groups can be substituted with other portions and still be conducted to the same copolyester structure. A preferred polyolefin oligomer is polybutadiene (PBD) because it has good oxygen expulsion capacity and reacts rapidly with oxygen especially in the presence of a transition metal catalyst, such as a cobalt. A polybutadiene oligomer functionally terminated in dihydroxy is especially preferred, in the molecular weight ranging from 1000 to 3000 'because it itself produces high clarity copolyester. when it is made in a block copolycondensate having predominantly PET, PEN, or other packaging polyester segments and also because it is commercially available in the required form and purity. The copolymers made with polyolefin oligomers of molecular weight in the range of 1000 to 3000 have a clarity in excess of 70% the clarity of the unmodified polyester, from which their polyester segments are derived. The polyolefin oligomer segments are responsible for the oxygen expelling capacity of the copolyester cleaning or expelling systems and are present only to the extent necessary to provide the desired oxygen expulsion capacity. The oligomeric polyolefin segments could normally represent less than 50% by weight of the copolycondensate with a preferred weight% range for the oligomeric polyolefin segments in the range of 2 to 12% by weight of the copolycondensate. Copolyesters comprising 2 to 12% by weight of polybutadiene segments with the remainder of the weight comprising PET, PEN, and / or other packaging polyester segments, including PETB, PETG and APET, are especially preferred to "cause of the high clarity of these copolyesters, because they are oriented biaxially without difficulty, and because they have glass transition temperatures higher than ambient temperatures (storage or environmental). PETG is modified to PET wherein up to about 40 mol% of the polyethylene glycol (as monomer) is replaced with a% mol equivalent of cyclohexane substituted with hydroxymethyl groups in the 1,4- or 1 / 3- positions in the cyclohexane ring. APET is amorphous PET available from Eastman. PETB is modified to PET where up to 40 mol% terephthalic acid is replaced with 4,4' -dicarboxibiphenyl. It will be understood by those skilled in the art that additional oxygen expellers, catalysts (such as cobalt), and other additives can be used in conjunction with the oxygen cleaner or copolyester expeller, to optimize the expulsion of oxygen and / or other properties. The ejection copolyesters can be prepared by direct polycondensation processes, including the desired amount of hydroxy-terminated polyolefin oligomer and retaining an equivalent amount of the dihydroxy monomer (eg, ethylene glycol) from the direct polycondensation process. The applicants have determined that the preferred mode for carrying out this invention is to prepare the copolyester formulations by transesterification in a reactive extruder (instead of direct polycondensation) using as starting materials a packaging polyester (eg PET), and PBD terminated in dihydroxy. The embodiments wherein the copolyester cleaner or expeller is prepared in-situ, concurrently with the bottle manufacturing process, or otherwise as part of the bottle manufacturing process, are also within the scope of this invention. The cleaning or ejection copolymer compositions referred to as Modalities II-A through II-J as listed in Table 1 below, were all prepared on a pilot plant scale in the manner as described herein. A ZSK-30 extruder was equipped with a weight loss PET pellet feeder under a blanket of nitrogen. The hydroxy-terminated PBD was maintained in a viscous fluid container from which it was separately transported via a positive displacement pump to a vacuum suction port in the extruder or ejection line. PET (Shell Clear Tuf® 7207) was extruded at a feed rate of approximately 3.6 kg (8 pounds) per hour to produce a residence period of approximately 4 minutes "while maintaining the temperature in the range of 260 to 270 ° C The finished PBD in hydroxy (Elf Atochem RLM20 - pm of 1230 or RHT45 - pm of 2800) was pumped to the extruder at variable speeds to produce weight percentages in the range of 2% to 12% for the hydroxy-terminated polybutadiene in the mixing zone of the extruder The models or designs of fusion seals were used to affect a vacuum zone that follows the mixing zone prior to the opening of the die. The extruded products were dried and not smoked, and were easily converted into pellets followed by rapid cooling in a water bath. The non-surface film (oily hydrocarbon layer) of any kind could be seen in the water bath, indicative of the formation of copolymer by transesterification during reactive extrusion. The appearance of a film in the water bath could have indicated the presence of unreacted polyolefin oligomer. The cobalt octoate (Hulls Nuodex® DMR, 6% cobalt) was used at a sufficient treatment rate to produce 50 PPM of Co when the hydroxy-terminated PBD was used at 2% by weight and 200 PPM of Co when the PBD hydroxy-terminated was used at 8% by weight. All cleaning or expelling copolymers prepared by the method described above had 'single vitreous transition temperatures (Tv) in the range of 62.0 ° C to 72.9 ° C. The copolymers prepared by the method described above were suitable for melt processing and were able to process bottles and / or layers in multi-layer bottles, in accordance with the preferred three-layer bottle wall embodiment of this invention. In applications requiring copolyesters of higher intrinsic viscosity (V.I.), techniques that improve molecular weight can be used. For example, the preparation of the copolyester by direct polycondensation (instead of transesterification) leads to much higher molecular weights for the copolyester. Alternatively, fusion rheology modifiers can be added to copolyesters prepared by transesterification to achieve high molecular weight for the copolyester. The copolyester compositions referred to as Modalities II-K to II-N as listed in Table 1 below, were also prepared by reactive extrusion in a twin screw extruder ZSK-30. First, the PET pellets (Shell Tray Tuf® 1006) were dried in a desiccant above 125 ° C for a minimum of 8 hours. The balls were then TABLE 1 Copolyester Formulations Cleaner or Expeller introduced to the feed section of the extruder via a weight loss pellet feeder covered with a blanket of nitrogen gas. The viscous low molecular weight polybutadiene (R20LM from Elf Atochem) diol (about 1230 μm) was placed in a pressure vessel and pressurized with nitrogen gas. The liquid was then transported separately to the PET fused through an injection port in the extruder via a positive displacement pump. The PET feed rate was adjusted to approximately 6.48 kg / h (14.4 lb / hr) while the PBD diol was supplied at a rate of approximately 0.27 kg / h (0.6 lb / hr). The residence time used was approximately 4 minutes which allowed the copolymerization to be completed in the extruder. The temperature profile of the reaction was maintained in the range of 250-270 ° C. The volatile substances generated from the reaction were removed through an open port of the extruder via a vacuum pump. The copolyester extrudate was rapidly cooled and transformed into pellets. The finished pellet was packed in a lobulated pouch or sheet of gas-resistant, wet aluminum sheet. To protect the product from oxygen contamination, the entire processing extrusion line was blanketed with nitrogen (including the 'spray application' of the storage bags).

PMDA was added to Modality II-K as an agent that extends the chain which serves to raise the molecular weight of the copolyester and, thereby, raise the intrinsic viscosity (V.I.) of the copolyesters. For example, the V.I. of the copolyester PET at 4% by weight of PBD (1230 ppm) (Modality II-B) was 0.57 which was still suitable for use in the manufacture of bottles. The addition of 0. 2% by weight of PMDA increases the V.I. to 0.71 while the addition of 0.3% by weight of PMDA raises the V.I. to 0.74. Such materials are very tightly bound in viscosity to that of pure PET (for example, Shell 7207 PET has a nominal V.I of 0.72). For beer bottles, it is necessary to eliminate, or at least minimize, the loss of carbon dioxide (C02) through the walls of the bottles. The tests by the applicants have produced results showing that the modified PET where some of the terephthalic acid monomer has been replaced by isophthalic acid (or equivalent derivatives) and / or where some of the terephthalic acid was replaced by naphthalene dicarboxylic acid (or equivalent derivatives) produces a packaging polyester which has superior CO2 permeation barrier properties. PETI and PETN in Table I are representative of such formulations. As such, the suitably modified PET is normally used to Beer bottles to improve the C02 barrier properties of the bottle. The combinations and / or mixtures of PETI and PETN are especially preferred. For the barrier effect for C02. At the maximum, similarly modified PET can also be used as the source of polyester segments in the oxygen cleaning or expulsion copolyester and can also be used as the diluent in the oxygen layer for cleaning or expelling the oxygen from the bottle.

III. OPTIMIZATION OF THE NON-PERMEATION TO OXYGEN Another inventive element in this complete invention has to be produced with the various means described to adjust the cleaning or ejection capacity to permeation levels substantially zero or almost zero to oxygen, depending on the application. The described means are not only varied but can also be implemented with greater security and ease, in some cases, with fine tuning of the ejection capacity directed to the manufacture of bottles and in other cases until the bottles are filled. Of course, it may be possible to use more oxygen cleaners or expellers and / or thicker layers of cleaner or expeller. But it is an objective to achieve the required degree of oxygen cleaning or expulsion capacity, necessary in the most cost effective way to manufacture bottles of viability commercial. Once the degree of cleaning or expulsion of oxygen, required, has been determined, the methods of adjusting the capacity of expulsion or cleaning of oxygen and / or the. shelf life of substantially zero / almost zero oxygen permeation, required from the bottle, can be achieved by one or a combination of several modalities described below.

Modality III-A Molecular Weight of the Segments of PBD in the Copolyester of Expulsion or cleaned. The variation of the molecular weight of the PBD segments used in the manufacture of the copolyester cleaner or oxygen expeller is a technique for adjusting the oxygen expulsion capacity of the copolyester, as described in the copending main application, presented on September 23. of 1996 and that has the Application Number 08 / 717,370. In this application, Examples 12 and 14 were copolyester formulations comprising segments of 4% by weight PBD and 96% by weight PET segments. Example 12 (having PBD of MW 2800) was a much more efficient oxygen scavenger or expeller than Example 14 (having PBD of MW 1230) at ambient temperatures and in the absence of cobalt catalyst. The variation of cleaning capacity or expulsion of oxygen or shelf life by this technique is probably the most retrospective method of all the described because the decision must be made prior to the manufacture of the system of expulsion of oxygen, copolyester.

Modality III-B The Weight% of Segments of PBD in the Copolyester of Expulsion or Cleaning The variation of% by weight of PBD segments in copolyester formulations is another technique, which was also described in the co-pending main application, filed on September 23, 1996, and that has the Application Number 08 / 717,370. This series of referred applications encompass and contemplate copolyesters comprising up to 50% by weight of PBD segments with the remainder comprising polyester segments. Table 1 above describes formulations of cleaning or expelling copolyester compositions having 2, 4, 6, 8, 10 and 12% by weight of PBD segments. Table 2, below, has data confirming that those compositions that have a higher percentage of PBD segments also have a higher oxygen expulsion capacity. The data of Table 2 were taken by the method of Examples 12 to 15 in the Application Number 08 / 717,370, main, co-pending.

Table 2 Cleaning Capacity or Oxygen Expulsion of Various Copolyester Formulations (data recorded at 22 ° C - 150 ppm of cobalt catalyst used) The variation of the capacity of cleaning or expulsion of oxygen or storage time by this technique is also a relatively retrospective method of what is described here, because the decision must be made at the time of the manufacture of the copolyester cleaner or expeller.

Modality III-C Concurrent Use of Other Oxygen Cleaners or Expellers with Expellers or Copolyester Cleaners Within the Walls of the Bottles In Figure 1, the layer 30 represents the intermediate oxygen expelling layer of the layer bottle wall construction preferred manifolds of this invention. While this expulsion layer may comprise, in some embodiments, about 100% copolyester expeller, applicants have found advantages to the deployment of diluted copolyester. For some it is easier to allow a uniform distribution of the cleaning or ejection system outside the bottle wall. Typically, the diluent is the outer layer polyester 26 of the bottle wall or inner layer 28 of the bottle wall in Figure 1. In some cases, the polyester of layers 26 and 28 are the same except that the polyester layer 26 can be totally or partially recycled material. Any diluent used in the layer 30 can also be totally or partially recycled material. Another advantage of the dilution of the layer 30 is that the technique itself leads to the anticipated preparation of the formulation to be used as a layer 30 and also to the anticipated preparation of single and / or plural concentrates, which will comprise the layer 30. when the bottle is manufactured. The anticipated formulation of layer 30 or concentrates therefor allowed for the simplicity of inclusion of additional oxygen scavengers or expellers in the layer, which will be available for oxygen scavengers or expellers concurrently with the oxygen scavenger or expeller copolyester in the 30 layer. Photoactive materials are preferred which remain inert towards "oxygen uptake during storage of the bottle until they are irradiated with enough UV light to activate them for such a purpose and therefore improves the range of oxygen absorption. A particularly preferred photoactive expeller is benzophenone. When used, the benzophenone is deployed in the range of 50-500 ppm with respect to the weight of the oxygen ejection copolymer layer. Generally the activation irradiation could be administered until before the shipment or shipment, or use (storage) of the manufactured bottles.

Mode III-D Extension of Co-Polyester Dilution in the Oxygen Expelling Layer As noted in III-C above, more modalities involve the addition of diluent to the copolyester oxygen expelling layer of the multi-layer bottles. The extension or prolongation of the dilution of the copolyester in the cleaning or expelling layer serves as another effective method for adjusting the oxygen expulsion capacity of the bottle. Typically, the diluent comprises from zero to about 95% by weight of the cleaning layer. In several extreme embodiments, the diluent has been deployed in excess of 99% by weight. The diluent is typically PET, pure or recirculated, but it could be any compatible low cost material. As such, the dilution of the copolyester drops to only level required for the given application, can substantially reduce the cost of the bottle.

Modality III-E Expanded Displacement of the Oxygen Expelling Layer Multilayer bottles comprising copolyester expulsion layers are especially preferred embodiments wherein the expelling layer of the bottle is not centered on the wall of the bottle between two PET layers of the same thickness. This can be additionally understood by reference to Figure 1. Layer 26, the outer PET layer of the bottle forming the exterior 24 of the bottle, is substantially thicker or thicker than layer 28, the innermost PET layer of the bottle forming the inside of the bottle 22. In practice, the thickness of the outer PET layer 26 would normally be in the range of about the same thickness at approximately 10 times the thickness of the internal PET layer 28. For any given total thickness (ie, the sum of layer 26 and 28 is constant), the degree of decentralization plays a decisive role in the capacity of Oxygen expulsion and storage of the bottles. When the outer layer of PET is thick or thick, there will be less oxygen entering the expiratory layer and therefore the shelf life is prolonged by the oxygen consumption from this source. When the inner layer of PET is thin, more oxygen from inside the bottle, (oxygen from the upper space or from other sources such as entry through the closure means) can infiltrate the ejection layer through the thin internal PET layer. Thus a thin inner PET layer provided for the fastest and most complete depletion or depletion of oxygen is present within the cavity of the bottle. In typical embodiments, the ejection layer (30 in Figure 1), including diluent if any, typically comprises approximately 10% by weight of the total weight of the bottle and the copolyester expeller because the layer will comprise about 0.5 a. Approximately 10% by weight of the bottle depending on the degree of dilution. Typically, the copolyester expeller is deployed with about 4% by weight of PBD segments in the copolyester. As such, the bottles of this invention are in the range of 99.6 to 99.98% by weight of polyester and polyester segments, and more typically about 99.92% by weight of polyester and polyester segments. It is understood by those skilled in the art that the ability to expel oxygen and / or shelf life from a bottle could also be adjusted by varying the thickness of only the PET layer. internal (28 in Figure 1) or just the outer PET layer (26 in Figure 1). These layers of internal and external PET can be varied individually and independently. There is no need for either to retain a constant sum for the thickness of the two aggregate layers together with another than for comparison purposes in accordance with a given amount of PET per bottle and / or to determine the optimal placement of the intermediate layer. While the thick or thick outer layer of PET may appear to be favorable, economic considerations will generally serve to establish a limit on the thickness of the outer PET layer, and in a manner related to the amount of PET used in the bottle.

Mode III-F Use of Oxygen Ejection Catalysts Examples 23 to 26 in the co-pending Application No. 08 / 717,370 clearly indicate that the oxygen expulsion or cleaning efficiency of the copolyesters can be significantly improved in the presence of a transition metal catalyst such as cobalt. According to the deployment (or lack of deployment) of a catalyst as well as the extension of deployment represents another method or modality to control the oxygen expulsion capacity and the shelf life of the bottles of this invention. The preferred transition metal catalyst is cobalt, because its effect on the efficacy of the expulsion copolyester is more pronounced. Cobalt is typically displayed in the form of a cobalt carboxylate. Cobalt octoate is preferred because it is effective at lower levels of deployment and is also commercially available in a suitable solvent and state of purity. Typically, cobalt is displayed in the range of 50 to 300 ppm in terms of the weight of the copolyester or (as further explained below) 50 to 300 ppm in terms of the combined weight of the most dilute copolyester used in the copolyester ejection layer of the bottle. The bottles of this invention are typically three layers and only PET (not the oxygen-expelling layer) is in direct contact with the bottled product. More glass used to make glass bottles contains some cobalt which can find its status in bottled beer. Cobalt is also found in PET as a trace of abandoned catalyst from cobalt-catalyzed PET polymerization. Several decades ago, it was common practice to add small amounts of cobalt to beer to improve - and maintain pressure retention or the top. Typically, cobalt is present in bottled beer to the extent of 0. 1 mg / l which was approximately the detection limit of several decades ago. The beer to which cobalt was added for the retention of pressure, had approximately 1.0 mg / l of cobalt. More recently, during the mid-1980s, evidence began to emerge indicating that the presence of cobalt could induce cardiomyopathies in some beer drinkers. Only very heavy beer drinkers, who were also exposed to the massive amounts of cobalt in their occupations were at any health risk. However, the international addition of cobalt for beer was discontinued at about this time. The previously described single layer PET / MXD6 bottle places the bottled beer in direct contact with the PET / MXD6 mixture which also comprises 50 ppm cobalt and creates the possibility of leaching the cobalt catalyst from the packaging material or from the formation of bottles, in beer. For multi-layer bottles, the beer is in direct contact only with the inner PET layer (as is the case for any beverage in a PET bottle) and is not in contact with the cobalt-catalyzed oxygen ejection layer. A control test was made and it was found that after 28 days of storage at an accelerated test temperature of 50 ° C (approximately 120 ° F) in a % by weight copolyester B-layer bottle (100 ppm Co in layer B), beer bottled therein was found to contain approximately 0.127 mg / l of Co which compared closely with the control beer of a bottle Glassware similarly stored, was found to contain approximately 0.086 mg / l cobalt. In tests to determine the optimum (minimum) load of cobalt catalyst for the oxygen expelled from the effective B layer, to obtain the required cleaning or expulsion requirements and shelf life during the dilution of the B layer with PET, Applicants make the surprising observation that dilution of the copolyester in layer B actually increases the efficiency of this as an oxygen scavenger on a weight basis per unit. Established otherwise, in the constant and sufficient presence of cobalt catalyst at% by weight, one gram of expulsion copolyester can be as much as 30% more efficient when used under dilution 4 times in films. A 4-fold dilution in the copolyester layer in the finished bottle compositions doubles the expulsion capacity above 84 days and gives an improvement of 50% in more than 168 days. While they do not intend to join or "be limited by theory, the applicants believe that the copolyester (present in the of expulsion) is acting as a collector for cobalt. As such the suitable cobalt (for catalytic purposes) ends where it is necessary (in the copolyester) despite the amount deployed, within the limits of the use of this invention. In addition, applicants believe that this property is due to the deployment of cobalt catalyst in the form of an aliphatic portion. Thus, the preferred catalysts are aliphatic cobalt carboxylates. Cobalt octoate is especially preferred because it exhibits these properties, it itself causes the copolyester to behave optimally towards oxygen uptake, and also because it is commercially available in the solvent, the concentration, and the state of purity required for the modes of this invention. Conducting the experiments leading to the discovery that the diluted copolyester has a higher ejection capacity, it was noticed by the applicants that the negative side of this effect is the introduction of a longer induction period before the copolyester reaches its potential of total expulsion.

Mode III-G Concurrent Use of Bottle Cap Coatings for Oxygen Expulsion As noted above, a possible source of oxygen intake in beer bottles is through the lining material of the bottle cap. The use of a bottle cap liner that has the ability to expel oxygen produces a good defense against this possible source of oxygen contamination. Also, a liner of the bottle cap, oxygen expeller, can be used to provide the additional expulsion capability for oxygen removal from the headspace since the liner of the cap is directly in contact with the top space of the cap. bottle. Such coatings of the bottle cap may also be comprised of the copolyester oxygen expellers of this invention, which have the ability to expel oxygen under both drying and humidity conditions. However, the environment of the cover coating allows the use of other ejectors which have the ability to eject only in the presence of moisture, for example, iron-based oxygen expellers. A bottle cap liner comprising an iron-based oxygen scavenger is disclosed in U.S. Patent No. 4,840,240. The optional use and the number of "oxygen" ejectors in the bottle cap liner represents another modality for controlling the oxygen expulsion capacity and / or the storage life of the multi-layer bottles of this invention. Preferred bottle cap liners for this invention contain the oxygen expeller between the outer layer (metal or plastic) of the bottle cap and an inner liner which is permeable to oxygen (and also vapor permeable). water for iron-based ejectors). The permeable inner liner serves to isolate the expeller from the bottled product while allowing oxygen from the upper space to reach the expeller and due to that be consumed. The caps of the bottle comprise a metallic or external plastic layer, an inner oxygen permeable layer / coating, and the oxygen expeller between these can be manufactured in advance and stored (in environments with reduced oxygen, if necessary) so that Be ready for immediate use during the bottle filling period. As such, the use of a bottle cap covering, for oxygen ejection, allows the final adjustment of the oxygen expulsion capacity and / or shelf life directed to the bottle filling process.

Modality III-H Use of Plural Oxygen Expulsion Covers While more of this description has been directed to bottles having only one layer of oxygen expelling, single or simple, in the wall of the bottle, the use of plural oxygen expelling layers is also considered. For example, a five-layer bottle wall of construction A / B1 / A '/ B2 / A (where A is PET, Bl is the external ejector layer, and A' is pure or recycled PET, and B2 is the ejector layer internal) provides a good opportunity for the use of recycled or recirculated PET. This modality also creates a construction in which Layer Bl can be optimized to expel the oxygen that infiltrates from outside the bottle and Layer B2 can be optimized for the expulsion of oxygen from inside the cavity of the bottle.

RELATION OF THE PERMEATION RANGE OF OXYGEN TO DURATION IN SHELLS It is intuitively obvious that a relationship exists between the speed or range of entry of oxygen into the cavity of the bottle under specific storage conditions and the shelf life of the bottled product. In the preceding section of this description, various means were described to conveniently and "effectively" adjust the cost of the oxygen permeation range to the required level, to ensure the required storage time of the bottled product. Referring to Figures 2 and 3 may help further understanding of the relationship of ranges or variations of permeation for oxygen at storage time. Figure 2 represents ideal data which could be developed by an oxygen permeation model for plastic bottles. Figure 2 is a graph showing oxygen permeation variations (in any convenient units of volume per unit area of the bottle wall) on the Y axis. The X axis denotes time. All data is for bottles that have a total (full) wall thickness provided. For a typical real bottle of the invention, the typical, total wall thickness could be in the range of about 0.25 to 0.625 mm (10 to 25 mils). The line or trajectory of permeation range for a bottle that has a PET wall is constant when PET has a fixed permeation range at 02, under a given set of conditions. The line or trajectory of the permeation range for a bottle that has a PET / EVOH / PET wall, is also constant but always lower than PET since the EVOH layer portion of the wall of the fixed-thickness bottle is a barrier to 02 more passive than PET. The "situation for a bottle that has a PET wall / copolyester ejector / PET is shown in several different diluent levels for the intermediate copolyester ejector layer as described in the previous section, (III-D). Because the copolyester is an excellent 02 expeller or cleanser, it itself can consume oxygen faster than permeating it through the outer PET layer of the bottle. This feature of the copolyester may still be present at high levels of diluent. For the reason of this discussion, only the complete oxygen depletion is shown, which does not exist any longer at diluent levels greater than moderate in Figure 2. In a similar way, the higher diluent levels are shown to be more permeable to oxygen. and are consistent with the description made in Section III-D above, when the amount of diluent is used to regulate the expulsion capacity of 02 (also the speed and storage time of the bottle). In Figure 2, the copolyester bottles are initially shown to have a permeation rate approximately the same as PET bottles because an activation period (retardation), before the expulsion capacity of the copolyester, reaches its potential of expulsion of 02 total. This delay is not relatively important and can easily be overcome by a variety of techniques. A simple means of 'overcoming the delay or delay is to manufacture the bottle in advance and Then store the bottle for several days (during the activation period) prior to filling. The expulsion copolyester curves eventually raise the support to the PET level after the expulsion capacity of the copolyester is completely decreased. The amount of oxygen reaching the bottle via permeation through the bottle wall is equal to the permeation rate (Y axis in Figure 2) multiplied by the duration of this velocity or permeation range (X axis in Figure 2) . Thus, the amount of oxygen reaching the bottle via permeation through the bottle wall is the area under the curve for any of the three curves in Figure 2. For any given application (bottled product), its tolerance to The presence of oxygen is normally given as a maximum amount of oxygen entered into the cavity of the bottle. The tolerance of the product to oxygen can be given on a relative basis, such as parts per million, but this data is easily converted to a maximum amount of oxygen based on the size of the bottle or the weight of the bottled product. Figure 3 shows areas under the curves similar to the curves in Figure 2. The area under each curve is the same and is equal to the maximum oxygen tolerance of a given product for each of the three curves. The additional reference to Figure 3 shows how the storage time is easily determined for each type of bottle, once the oxygen tolerance, maximum, (area under each curve) is displayed on the axes.

EXAMPLES Bottle Making 20 ounce bottles (433 ce capacity, 31.1 g weight) were manufactured in a single step, long-life, single pass, Nissel 250TH blow molding machine. Only one side of the binary machine was used. A more complete description of the Nissel 250TH machine can be found in the aforementioned US Patent No. 5,141,695. The spindle or screw on the A side of the unit's 24 mm diameter was estimated to store 16 pellets for the used molding device. The B-side screw, of a compression ratio of 2.4 to 1, was also estimated to retain 16 shots when layer B of a bottle construction A-B-A is taken as a target for 10% by weight of the total preform. The conditions were established using Shell 5900 PET as a test layer B because it is similar in viscosity to the ejection copolyester comprising approximately 96% by weight of PET and approximately 4% by weight of PBD. The formulation of copolyester (PET with 4% by weight of PBD) was diluted with PET so that the ejection polyester comprises 25 to 100% by weight of layer B. When the catalyst is present, it is used at 100 ppm of cobalt and benzophenone, when present it is used at 100 ppm, both with respect to the total weight of Layer B (ie, copolyester plus diluent). The cobalt and benzophenone were fed into the apparatus as pre-prepared granules or pellets of concentrate, mixed with the active layer charge. A specific example of the process conditions used is described as follows. The layer A extruder was charged with Shell grade 7207 PET. The layer B extruder was used to melt a dry blend of the following granules or pellets: a) 97 parts of expulsion copolyester PET and 4% by weight of PBD (Modality II-B) b) 2 parts of promoter blue which is a concentrate of 0.5% by weight of Cobalt, as salt of octoate, in PET c) 1 part of white promoter which is a concentrate of 1.0% by weight of benzophenone in PET The concentrates in b) and e) above , were prepared by melting by mixing the appropriate amounts of each component in a twin screw extruder and collecting the products in the form of granules or pellets. The barrel temperatures of the A-side extruder (layer) from the feed passage to the nozzle were adjusted as follows: 265, 265, 265, and 265 ° C. The corresponding B (layer) side temperatures were 250, 250, 270, and 260 ° C. The hot production blocks were adjusted to 270 ° C and the molding temperature to ~ 10 ° C. The period of the total cycle was approximately 32 seconds / part. Microscopic analysis of the bottle composition indicates that the thickness of layer B was approximately 11% of the bottle wall (10% was the target or target). The thickness of layer 3 varied with the position along the bottle, which is thicker near the neck and thinner near the closed bottom end. Adjustments to the processes of placement or serial ordering will be obvious to those skilled in the art, who wish to obtain a different distribution of the thicknesses of the 3 layers.

Examples 1-6 A series of bottles (designated as Examples 1-6) were made having a total sidewall thickness of approximately 0.5 mm (20 mils), weighing approximately 31 grams each, having an adequate volume for contain approximately 12 ounces of beverage, and they have a wall construction of the Three layer bottle (A / B / C). For each of the bottles in the example, the external layer A (PET) was approximately 0.375 itim (15 mils), the intermediate B (ejection layer) was approximately 0.05 mm (2 mils) and the layer Internal C (PET) was approximately 0.075 mm (3 mils). For each of Examples 1-6, the ejection copolyester employed comprises about 4% by weight of PBD segments of MW 1230 and about 96% by weight of polyester segments. Table 3 below further characterizes the composition of the intermediate ejection layer (B) of each example. The oxygen permeation data taken for Bottles of Examples 1-6 were displayed graphically in Figure 4. The data was taken by purging with nitrogen all the air from the bottles of Examples 1-6. Oxygen permeability was measured using a MACON Oxtran test unit that works at room temperature (approximately 22 ° C) for a period of days. The results (Figure 4) show gradual improvement in the oxygen barrier properties of the expulsion copolyester bottles over time. After the activation period of the copolyester of approximately three weeks, the bottles with sufficient oxygen expulsion capacity (ie, at least 50% by weight of the copolyester or more in the intermediate layer B) and with cobalt present at approximately 100 ppm, exhibited perfect oxygen barrier properties a, ie, zero oxygen permeation. Perfect performance was maintained for more than 120 days with no indication of deviation from the zero oxygen permeation when the test was finished after approximately 300 days. The bottles that have a lower percentage of copolyester Table 3 Three-layer Explosive Bottles Examples 1-6 in the intermediate layer B (for example 25% by weight as in Example 2) produced insufficient oxygen expulsion capacity to achieve zero oxygen permeation, but reaches a lower value of reliable state (almost zero). It should be noted that the Y axis of the graph of Figure 4 is graduated in thousandths of a ce of oxygen per day per bottle so that much lower errors and / or misinterpretations will appear as exaggerated deviations.

Examples 7 - 14 The bottles of Examples 7 - 14, other series of bottles, were subjected to a different procedure. Each of these bottles was filled with a gas containing 2% by weight of oxygen as a method to simulate the presence of oxygen in the upper space, and then sealed in a gas-tight manner by adhesively fixing brass or bronze-equipped plates with septa or partitions to the bottles. This could be interpreted as a severe condition of upper space with oxygen when the content of the entire bottle was 2% by weight oxygen, not exactly the lower space above the liquid as is the case for a full bottle. Oxygen% by weight in these series of bottles was observed over a period of days using a MOCON Oxtran test unit at 22 ° C and 100% relative humidity. All bottles of Examples "7-14 contained 100 ppm of cobalt and 100 of benzophenone in layer B. The bottles of Examples 7-14 were further characterized in Table 4.

Table 4 Three Layer Explosive Bottles Examples 7 - 14 The data for Examples 7-14 are plotted in Figure 5 and demonstrate (except for Control Examples 7 and 8 which did not have expulsion copolyester in Layer B) that oxygen is consumed from within the cavity of the bottle The data in Figure 5 were taken at 22 ° C and 100% relative humidity. The data for Examples 7 - 14 are also shown graphically in Figure 6. The data in Figure 6 were taken at 60 ° C and 0% relative humidity. Again the data showed that oxygen is consumed from inside the bottle cavity by the expulsion copolyester in Layer B.

Examples 15-18 As noted previously, it was observed that the dilution of the expulsion copolyester with a diluent such as PET causes the oxygen expulsion capacity to be increased when it is described on a weight basis per unit of copolyester. The data of Examples 15-18 serve to demonstrate this effect. The copolyester films of Examples 15-18 were all segments of 4% by weight of PBD with the remainder of the copolymer comprising polyester segments. For all of Examples 15-18, 100 ppm of benzophenone and 100 ppm of cobalt were also used. The ppm of benzophenone and cobalt refers to the total weight of the film, ie copolyester of expulsion plus diluent. The films are further characterized in Table 5 below.

Table 5 Copolyester Expulsion Films Examples 15 - 18 The oxygen scavenging capacity of the four films of Examples 15-18 was determined using a method similar to that of Examples 12-15 of the North American Application Number 08 / 717,370 filed September 23, 1996. Samples of 5 gram film were used and a desiccant was placed in each of the 500 cc jars to create and maintain a 0% relative humidity environment. The results were shown graphically in Figure 7. As is evident from Figure 7, the ejection copolyester has a higher oxygen expulsion capacity (in terms of quantity ejected per unit weight of copolyester when used mixed with diluent. as Layer B in a wall construction of the A / B / A bottle.

The specification and the examples of this invention have widely described processes for the manufacture of multi-layer bottles of oxygen expelled. Those skilled in the art will recognize that a wide variety of other containers such as cups, bowls, trays, will benefit from the application of this invention and could be considered to be a mode within the scope of the invention. Also, the effectiveness of the expulsion copolyester at 0% relative humidity (see Examples 15-18) shows that it is an effective oxygen scavenger or cleaner, even in a dry environment which makes it suitable for applications in this environment, for example , to pack oxygen-sensitive electronic components.

It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property

Claims (33)

1. A thermoplastic container of substantially zero oxygen permeation, for storing an edible product, characterized in that it has a volume in the range of 0.03-4 liters and a multilayer wall of total thickness in the range of 0.1-2 millimeters and wherein the less a wall layer comprises a block copolycondensate comprising predominantly polycondensate segments and an oxygen expelling amount of oligomeric polyolefin segments wherein the oligomer has a molecular weight in the range of 1,000-3,000.

2. The container according to claim 1, characterized in that the container allows not more than 1 ppm, with respect to the weight of the product, of external atmospheric oxygen to permeate or infiltrate to the product for a period of time in the range of about 30 - 365 days under environmental storage conditions in a temperature range of 4 - 25 ° C and where the period of time is measured from the time in which the container is filled and sealed.

3. The container according to claim 2, characterized in that the period of time is in the range or interval of 60 - 365 days.

4. The container according to claim 2, characterized in that the period of time is in the range or range of 60-180 days.

5. The container according to claim 1, characterized in that the copolycondensate is a copolyester.

6. The container according to claim 5, characterized in that the copolyester comprises 2-12% by weight of oligomeric segments of polybutadiene.

7. The container according to claim 1, characterized in that the container further comprises a base which optionally can be thicker or thicker than the wall and optionally of a monolithic construction.

8. The container according to claim 1, characterized in that the container it also comprises a section for fixing sealing means wherein the section of the container can optionally be thicker or thicker than the wall and optionally of a monolithic construction.

9. The container according to claim 1, characterized in that the container is a bottle.

10. The bottle according to claim 9, characterized in that the wall of the multilayer bottle has a clarity equal to at least 70% the clarity of a monolithic polyester bottle wall of similar total wall thickness.

11. A thermoplastic bottle of almost zero oxygen permeation having a storage cavity of the edible product, the bottle comprises a base which defines the lower part of the cavity of the bottle and a generally cylindrical, multi-layered side wall, fixed to the base and that extends far from the base that forms the wall of the cavity of the bottle and that provides the necessary volume to the cavity of the bottle, the "lateral wall that ends to define an opening in the upper part of the cavity of the bottle suitable for fixing a bottle cap, wherein an inner layer of the side wall is comprised of an oxygen expelling formulation, copolyester, comprising predominantly polyester segments and an amount that expels oxygen from polyolefin oligomer segments , wherein the oligomer has a molecular weight in the range of 1,000-3,000 and wherein the bottle, after filling and capping, has sufficient capacity to expel oxygen (a) to consume and empty the oxygen within the cavity of the bottle, (b) consume and empty oxygen which can enter through the opening of the bottle cap, and (c) consume oxygen from the air which reaches the internal ejection layer, where the oxygen consumption almost complete low (a), (b), and (c) are maintained at least at a level of oxygen depletion, required for a shelf life of the bottled product, of target or target, under a condition of specific storage.

12. The bottle according to claim 11, characterized in that the oxygen expulsion capacity and the storage duration are adjusted optimally and effectively at cost, to meet the requirements of the product by a method selected from the group consisting of (a) ) vary the weight molecular weight of the polyolefin oligomer segments within the range of 1,000 - 3,000, (b) vary the weight% of polyolefin oligomer segments in the ejection copolyester, (c) optional concurrent use of additional oxygen expellers within the wall of the bottle and the lower part, (d) dilution of the polyester for expulsion or cleaning in the internal ejector layer, (e) variation of the extension of the off-center placement of the innermost ejection layer, (f) use of ejector catalysts of oxygen within the bottle wall, (g) optional concurrent use of a bottle cap with oxygen expulsion capacity, (h) use of oxygen, plurality, oxygen ejection layers, (i) vary the amount of oxygen expeller used oxygen, (j) vary the thickness of the ejection layer, and (k) combinations of the preceding.

13. The bottle according to claim 11, characterized in that the copolyester comprises 2-12 weight percent oligomer segments of polybutadiene.

14. The bottle according to claim 13, characterized in that the polyester segments are selected from the group "consisting of PET, PETI, PETN, APET, PEN, PEBT, copolymers of these, combinations of these, and mixtures of the preceding ones.

15. The bottle according to claim 11, characterized in that the base of the bottle also comprises the construction of expulsion or cleaning of the oxygen, of multiple layers, of the side walls.

16. The bottle according to claim 11, characterized in that the duration in storage or shelves as a target, is in the range or interval of 30 - 365 days, and where the storage condition comprises a temperature in the range of 4 - 25 ° C.

17. A process for manufacturing a multi-layer oxygen ejection bottle, characterized in that it comprises the steps of: (i) forming a first resin layer using the apparatus for manufacturing multi-layer bottles, (ii) forming a second layer of resin using the apparatus for making multi-layer bottles, (iii) forming a third layer of resin using the apparatus for manufacturing multi-layer bottles, and (iv) transforming the first, second and third layers of resin into a finished multilayered bottle, using the apparatus for manufacturing bottle bottles. multiple layers; wherein the apparatus has means (A) for separately processing at least two different resins and (B) forming a multi-layer bottle having at least three layers, and wherein at least one of the layers of the bottle comprises a formulation of oxygen, copolyester expelling resin, comprising predominantly polyester segments and an oxygen expelling amount of oligomeric polyolefin segments wherein the oligomer has a molecular weight in the range of 1,000-3,000.

18. The process according to claim 17, characterized in that the first, second and third layers are formed concurrently.

19. The process according to claim 17, characterized in that the first, second and third layers are formed sequentially.

20. The process according to claim 17, characterized in that the copolyester comprises from 2 - 12% by weight of oligomeric segments of polybutadinene of molecular weight in the range of 1,000-3,000 and from 88-98% by weight of polyester segments.

21. The process according to claim 20, characterized in that the polyester segments are selected from the group consisting of PET, PETI, PETN, APET, PEN, copolymers thereof, combinations thereof, and mixtures thereof.

22. The process according to claim 17, characterized in that the bottle is first developed as a multi-layer bottle preform which, therefore, expands to the volume of the final bottle.

23. The process according to claim 22, characterized in that the bottle preforms are subjected to special heat treatment to improve the properties of the resulting bottles.

24. The processed according to claim 22, characterized in that the copolyester comprises from 2 - 12% by weight of oligomeric segments of polybutadiene of molecular weight in the range of 1,000 - 3,000 and from 88 - 98% by weight of polyester segments.

25. The process according to claim 24, characterized in that the polyester segments are selected from the group consisting of PET, PETI, PETN, APET, PEN, copolymers thereof, combinations thereof, and mixtures thereof.

26. The process according to claim 17, characterized in that the bottles are subjected to special heat treatment to improve their properties.

27. The process according to claim 17, characterized in that the finished bottles are stored under an environment with decreased oxygen, compared to the oxygen contained in the air, until they are placed in use.

28. The process according to claim 17, characterized in that the bottle is a bottle of three layers of layer A / B / C construction in wherein the Layer C, which defines the cavity of the bottle is comprised of bottle-forming polyester, virgin or pure, Layer B is comprised of an oxygen scavenger or copolyester cleaner, in accordance with claim 17, and Layer A is comprised of packaging polyester selected from the polyester group consisting of pure polyester, recycled or recirculated polyester, recovered or reformed polyester, and mixtures thereof.

29. The process according to claim 28, characterized in that Layer A is in the range of one to ten times thicker or thicker than Layer C.

30. The process according to claim 17, characterized in that the bottle is a bottle of five layers of layer A / B / C / D / E construction where Layer E, which defines the cavity of the bottle is comprised of polyester of pure packaging, Layers B and D are comprised of a copolyester oxygen expeller of claim 17, Layer C is comprised of packaging or packaging forming polyester, and Layer A is comprised of packaging polyester, and wherein Layers C and A are independently selected from the polyester group consisting of pure polyester, recycled polyester, reformed polyester, and mixtures thereof.

31. A multilayer thermoplastic container or container in which at least one layer comprises a composition comprising (a) a copolyester comprising predominantly polyester segments and an oxygen expelling amount of oligomeric polybutadiene segments wherein the oligomer has a molecular weight in the range of 1,000-3,000 and (b) cobalt in the range of 50-300 ppm, relative to the weight of the layer in which the cobalt is present, wherein the cobalt is provided as an aliphatic cobalt carboxylate.

32. The container according to claim 31, characterized in that the composition further comprises benzophenone in the range of fifty - . 50-500 ppm, relative to the weight of the layer in which the benzophenone is present.

33. The container according to claim 31, characterized in that it has a volume in the range of 0.03-4 liters and a total wall thickness in the range of 0.1-2 millimeters.