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    公开号:ES2569396T9
    申请号:ES04763448.0T
    申请日:2004-07-23
    公开日:2016-06-10
    发明作者:Laurent Degroote
    申请人:Amcor Pty Ltd；
    IPC主号:
    专利说明:

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    DESCRIPTION
    Composition for the manufacture of a packaging device, which has oxygen sequestration properties and reduced opacity
    Invention Sector
    The present invention relates to the packaging sector, in a special way, to the packaging of products which are sensitive to oxygen, and in a more special way, to the packaging of food products and beverages. A main object of the present invention is a new polymeric composition for a packaging article, that is, a package, which exhibits both oxygen sequestration properties and reduced opacity.
    Prior art of the technique
    Thermoplastic polymeric compositions are used extensively, in the packaging industry, for the manufacture of various items for packaging, in order to store oxygen-sensitive products, such as those consisting of food products or beverages.
    The phrase "packaging article", (or article for packaging), as used herein, in this patent application document, refers to any type of article, which is used for storage of any type of material, and in a special way (although not only), food products or beverages. Thus, for example, a packaging article may be a hollow and rigid container, such as that consisting of a bottle, a bottle, or the like, a plastic, flexible container, a film, or a sheet or sheet for a container.
    More especially, a thermoplastic composition, which is widely used, is the one consisting of polyethylene terephthalate (PET - [for its acronym in English, corresponding to polyethylene terephtalate] -). This material has a large number of valuable properties for packaging, but it lacks sufficient gas barrier properties for many applications. In a particular way, due to its oxygen permeability, PET alone is not suitable for packaging food products and beverages, which are sensitive to oxygen such as products consisting of beer, fruit juices, some carbonated beverages of soda, etc. PET is also permeable, likewise, to carbon dioxide, which, in turn, leads to a short shelf life for carbonated products, such as those consisting of carbonated soft drinks, stored in PET containers. .
    In order to improve the gas barrier properties of the packaging products, in a particular way, as regards the barrier properties against oxygen and / or carbon dioxide, it is usual, at present, made of using multi-layer packaging products, and in a particular way, multi-layer containers, which include at least one barrier layer. Thus, for example, in the sector of bottle packaging, a typical and multi-layer common structure, for a rigid and hollow container, is the one consisting of a three-layer wall: two internal and external layers, made of PET, and an intermediate layer, of gas barrier, sandwich, as a "sandwich", between the two layers of PET in question.
    A first known type of barrier layer, is composed, or comprises, polymers which have excellent gas barrier properties, in a particular way, barriers against O2 and / or CO2, and this is referred to, in a general way, as "barrier layer, passive". Among the polymers used to make the passive barrier layers, polyamide homo- or copolymers are used in a common way. Among these polyamides, polyamides called "MXD6" or nylon "MXD6" (polyamide material, specific, manufactured by the Mitsubishi Gas Chemical Company, Japan), namely a poly, are preferably used (m-xylilenadipamide), produced by polycondensation of a diamine component, which is mainly composed of m-xylylenediamine and a dicarboxylic acid component, which is mainly composed of adipic acid.
    US Patent 4,501. 781, assigned to the firm Yoshino Kogyosho Co. Ltd., discloses a multi-layer container, which, for example, has a three-layer structure: an inner layer and a layer external, made of PET; an intermediate barrier layer, passive, which is made of a mixture of PET and a polyamide which contains xylene groups (preferably, MXD6). The ratio factor or ratio of the polyamide which contains xylene groups, in the mixture, corresponds to a value within a range, which ranges from a percentage of 5%, by weight, to a percentage of 50% , by weight, said ratio factor or quotient being, preferably, corresponding to a value within a range, ranging from a percentage of 10%, by weight, to a percentage of 30%, by weight .
    A second known type of barrier layer, which has been developed in a more recent time, is manufactured based on, or this comprises, a polymeric composition, which has oxygen sequestering properties and this is referred to, in a generalized way, like "barrier layer, active". Thus, and generally speaking, an active barrier reacts with oxygen and "captures" the
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    oxygen, when the oxygen penetrates inside the layer. Such a type of barrier layer, active, "is consumed" thus, in a progressive manner, in use.
    Examples of polymeric compositions used for the manufacture of the active barrier layer are described, notably, in the European patent application document EP-A-0 301 719, or in the patent application document European EP-A-0 507 207. The said polymer compositions generally comprise a polymer that can be oxidized and a transition metal catalyst. In the European patent application document, EP-A-0 301 719, the polymers capable of being oxidized in question are polyamides and, in a special way, the MXD6. In European Patent Application Document EP-A-0 507 207, a polymer that can be oxidized, preferred, is that consisting of polybutadiene. In both cases, the transition metal catalysts, which are preferred, are the transition metal salts, and in a particular way, cobalt stearate. Other known metal salts, and which are used for the preparation of said composition are, for example, those consisting of rhodium, manganese, copper, iron salts.
    By means of multi-layer containers, which have at least one gas barrier layer, which comprises a polyamide (such as, for example, the one consisting of MXD6), and a polyester (such as, for example, the consisting of PET), very good results can be obtained, in terms of the shelf life of the packaged products. More particularly, when the barrier layer comprises a polyamide (such as, for example, the polyamide consisting of MXD6), polyester (such as, for example, the polyester consisting of PET), and a catalyst, such as the one consisting of a cobalt salt, the multi-layer container in question, can be used for the storage of oxygen-sensitive products, such as those consisting of beer, fruit juices, and the like. The shelf life of the packaged product depends, in a very wide way, on the amount of polyamide in the container, and on the thickness of the barrier layer.
    US Patent 5,281,260, assigned to the American National Can Company, also teaches the fact that the gas barrier property of the polyester is improved by mixing polyester with polyamide. which contains xylene groups, and a transition metal catalyst. Preferred forms of presentation include PET / MXD6 / Cobalt blends. The US patent U S 5,281 260 in question, discloses, in an additional way, the fact that, a high orientation of the aforementioned mixture, also improve it, also the barrier properties. The explanation provided by the aforementioned patent is the fact that the high orientation of the mixture increases the surface areas and the interface between the PET and the MXD6, so that there are a greater number of sites, in which a reaction or absorption of oxygen takes place.
    On the contrary, a major drawback of the use of a mixture of: polyamide / polyester, and in a particular way, of a mixture of: polyamide containing xylene groups (such as that consisting of MXD6) / PET, for manufacturing of a barrier layer, in an article for packaging, - in a special way ,, in a packaging article, of multiple layers, is the one consisting of an opacity or turbidity (fog) in the barrier layer, due to the high biaxial orientation of the mixture, during the manufacturing process of the article.
    The aforementioned problem of the formation of an opacity or turbidity (mist), occurs, and this is often visible to the eyes, in the case of a layer of polyamide / polyester / which has a "high" polyamide content, is that is, for a quantity of polyamide of at least a percentage of 3%, by weight, in the layer, the worst case being, in terms of opacity or turbidity formation, a mixture corresponding to percentages of 50% 50 , in the layer.
    In the case of a gas barrier layer of a multi-layer article, the polyamide having the barrier properties, is located only in the barrier layer of the multi-layer wall of the article in question, and the concentration of The polyamide, in the barrier, is “high” (compared to a mixture used to make a single layer container), and this is always greater than a percentage of 3%, by weight, in order to achieve the properties of gas barrier, which, in turn, leads to problems in the formation of opacity or turbidity.
    The aforementioned opacity or turbidity formation, on the wall of the container, is obviously detrimental to the entire application, where it is important to have a packaging article, which is transparent, - namely, a packaging article, whose wall does not have any whitish pigmentation, opacity or turbidity, which is visible to the eyes, in order to have a better appearance of the packaged product.
    Said technical problem of the opacity or turbidity formation of the highly oriented polyamide / polyester mixture has been identified, for example, in US Patent U S 6,239,210, assigned to the firm Pechiney Emballage Flexible Europe. In a particular way, US Pat. No. 6,239,210 teaches the fact that the loss of clarity is due to a change in the index of refraction of materials. The technical solution which is recommended in US patent U S 6. 239. 210, in order to reduce opacity or turbidity, is to limit the degree of orientation of the mixture. In a more special way, in the sector
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    of the manufacture of rigid multi-layer containers, US patent US 6,239,210, teaches the fact of selecting the molding process by extrusion and blowing, in order to achieve the reduced degree of orientation required, instead of the process of injection molding, stretching and blowing, which implies higher degrees of orientation of the polymer, and which leads to the formation of opacity or turbidity, in the polyamide / PET mixture.
    Objectives of the invention
    A general and main objective of the present invention is to propose a polymeric composition, for the manufacture of a packaging article, which has a wall, with both, oxygen sequestration properties, and a reduced opacity or turbidity.
    An additional objective of the present invention is to obtain a new polymeric composition, for the manufacture of an article for packaging, and which has gas barrier properties, which are similar, but which exhibits a lower opacity or turbidity, when it is oriented, than those corresponding to a polyamide / PET mixture.
    Summary of the invention
    These objectives are achieved by preforming the composition of claim 1.
    The term x% PETI, as used herein, in this patent application document, and in a special way, in the claims, means a copolymer resin, of polyethylene terephthalate and polyethylene isophthalate, which has a purified isophthalic acid (IPA) content of x moles%. A content of purified isophthalic acid (IPA) of x moles%, means the fact that, during the process of preparing the copolymer, by polymerization, a glycol or a glycol ether (such as, for example, ethylene glycol) With both, terephthalic acid and isophthalic acid, x moles percent of isophthalic acid, have reacted with ethylene glycol.
    The term and% PTEG, as used herein, in this patent application document, and in a special way, in the claims, means a copolymer resin, of polyethylene terephthalate and 1,4-cyclohexanedimethanol, ( CHDM), which has a CHDM content of y moles%. A 1,4-cyclohexanedimethanol (CHDM) content of y moles% means the fact that, during the process of preparing the copolymer, by polymerization, a glycol or a glycol ether (such as, for example, the ethylene glycol), with terephthalic acid, and moles percent of 1,4-cyclohexanedimethanol (CHDM), have reacted with terephthalic acid.
    In a preferred form of presentation, in accordance with the present invention, x and y, are at least equal to 20, and preferably, at least equal to 30.
    In a preferred form of presentation, in accordance with the present invention, the amount of polyamide is a percentage of at least 8%, by weight, and more preferably, this is a percentage of at least 10%
    The polyamides which are suitable for the manufacture of the composition of the present invention can be any polyamide homo- or copolymer (aromatic or aliphatic polyamide). The polyamides which are particularly interesting, are those which contain groups of the formula -arylene-CH2-NH-CO-, conveniently, in units -NH-CH2-arylene-CH2-NH-CO-alkylene-CO -. Especially suitable, as arylene groups, are phenylene groups, of a particular, m-phenylene groups, which may be substituted by alkyl and / or condensed with other aromatic rings, unsubstituted or substituted by alkyl. The alkylene and alkyl groups may conveniently have 1 to 10 carbon atoms, and these may be straight chain or branched chain. The alkylene groups, which are suitable, in a special way, are the n-butylene groups. More particularly, among the polyamides which can be used to make the gas barrier of the preform or container of the present invention, the ace! called MXD6, it is the most appropriate polyamide, due to the high gas barrier properties of this polyamide.
    Fully aliphatic polyamides can also be used, in a special way, those polyamides which contain units -CO (CH2) nCONH (CH2) mNH- or units - (CH2) pCONH (being, n, m, yp, whole numbers, in a usual way equal to 4, 5 or 6).
    Preferably, the polyamides which are used for the preparation of the composition of the present invention are high molecular weight polyamides, and which have, in a particular way, an average, numerical molecular weight, which is greater of 10,000 and having, in a more special way, an average molecular weight, numeric, greater than 15,000.
    In the scope of the present invention, the composition is produced from a mixture, which comprises a polyamide, and a copolymer at x% PETI and / or a copolymer at y% PETG, where, x and y, are at least equal to 5.
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    More particularly, in a variant of the present invention, the polyester which is used in the barrier layer, is composed, in an essential form of a copolymer at x% PETI and a copolymer at y% PETG , where, x and y, are at least equal to 5. In another variant, in accordance with the present invention, the polyester may be a mixture, which comprises a homo- or PET copolymer and a copolymer at x% PETI and a copolymer at y% PETG, where, x and y, are at least equal to 5.
    The term "PET", as used herein, in this patent application document, means, in addition to the specific polyester, consisting of "polyethylene terephthalate", any polyester which are similar, derived from the reaction of the terephthalic acid with a glycol or with a glycol ether, or from the reaction of a non-polymeric terephthalic acid diester, such as, for example, dimethyl terephthalate and diesters that are similar, with a glycol or a glycol ether. Examples of such types of glycols and glycol ethers include cyclohexanedimethanol and dieters thereof, ethylene glycol and dieters thereof, ethylene glycol and dieters thereof, diethylene glycol and dieters thereof, propylene glycol and dieters thereof, 1,3-propanediol at the diesters thereof, butanediols and dieters thereof, pentanediols and dieters thereof.
    Summary description of the drawings
    Other features and advantages of the present invention, will be more evident, upon reading the detailed description of several preferred forms of presentation of the present invention, this description, which is performed by way of non-exhaustive and non-limiting example, and with reference to the accompanying drawings, in which:
    - Figure 1 is a schematic drawing of a multi-layer preform, which has a three layer wall,
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    - Figure 2 is a schematic drawing of a multi-layer bottle, which has been obtained by stretching and blowing molding the preform of Figure 1.
    - Figure 3 shows the index of refraction versus, planar relationship factor for the MXD6 and PET, measured in films manufactured by fusion process, and in films manufactured by stretching process.
    Detailed description of the invention
    The detailed description of the present invention, which is given below, focuses on the use of various examples of a polymer composition of the present invention, to produce a molded container by injection process by stretching by blowing (of a preform or of a bottle). However, however, the fact that, the scope of the present invention, is not limited only to the particular application, should be emphasized, but that this encompasses! same, also, to the use of the composition, for the production of any packaging article.
    Thus, for example, the composition of the invention can be used for the production of packaging articles (either flexible or rigid), by any other type of technique. The present invention can also be used to produce films or sheets or sheets, which are flexible.
    In a particular way, in the sector of multi-layer packaging articles, the present invention is not limited to an article which has a three-layer structure, but, this, can also be applied, in a way more general, to the production of any type of multi-layer packaging article, which has at least one gas layer barrier.
    Multi-layer preform (Figure 1)
    Figure 1 shows a non-limiting example of a multi-layer preform, 1, which has the well-known general form which is described below:
    - a tubular main body, 2, which is closed by a bottom end, 3, in a substantially hemispherical way.
    - a portion by way of neck 4, which includes a collar 5, a threaded thread 6, and an open end, by way of mouth, 7.
    As shown in the enlarged view of Figure 1, the tubular body 2 (and also, also, the end of the bottom, 3), is made of a three-layer wall: an outer layer Lout and an inner layer, Lin, made of a low-cost thermoplastic material, A, and an intermediate thin layer Lb, which is sandwiched, as a sandwich, between the two layers Lout and Lin, and the which is made of a second thermoplastic material, B, which has gas barrier properties.
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    The neck-like portion, 4, of the preform, is of the monolayer type (single layer), and is made, for example, of the first thermoplastic material A. The aforementioned preform 1, is manufactured, according to a standard form, by co-injection (according to a simultaneous and / or sequential form) of the two thermoplastic materials A and B, in an appropriate mold.
    Multilayer bottle, molded by stretching and blowing process (Figure 2)
    The preform 1 is an intermediate product, which has been transformed, in an additional stage, for conversion into a final, hollow and rigid container (such as, for example, a 1 'bottle, which is represented in the Figure 2), by a biaxial stretching process (i.e. radially and longitudinally), in a mold, the tubular body 2 and the bottom end, 3, of the bottom, of the preform, by, for example , the technique of stretch and blow molding, which is well known, in the specialized art of the technique. During the execution of this process, the neck-like portion, 4, of the preform 1, is not stretched, and remains unloaded.
    The injection molding stage and the molding stage by stretching and blowing, can be carried out in two separate phases, by reheating the preform, or it can be carried out, in line, as a single-process stage.
    Examples n ° 1 - 15
    In each of examples 1 to 15, three-layer preforms are described, such as the preform which is represented in Figure 1, which are made of two materials, A and B.
    Material A
    In all of the examples, material A (the inner and outer layers, Lin and Lout of the preform), is a mixture of PET homopollmer (standard grade: less than a percentage of 3%, by weight, of isophthalic acid purified), which is commercially available on the market, by reference 9921W, from VORIDIAN, and which has an intrinsic viscosity of 0.82 +/- 0.02.
    Material B
    In all of the examples, material A (gas barrier layer, LB), is a dry mixture, made from a percentage of 80%, by weight, of a component B1, a percentage of 19.62% , by weight, of MXD6, and a percentage of 0.38%, by weight, of cobalt stearate. Component B1 is different for each of the examples, and this is specified in Table 1, which is given below, below.
    Table 1: Material B - Mix
     Example # #  MATERIAL B - MIX
     Component B 1  MXD6 (1) Cobalt 12
     one  40% PETI (3) - 80% by weight 19.62%, by weight 0.38%, by weight
     2  8% PETI 14) - 80% by weight 19.62%, by weight 0.38%, by weight
     3  8% PETI 14) 70% by weight 32% PETG 15) 10%, by weight 19.62%, by weight 0.38%, by weight
     4  8% PETI 14) 60% by weight 32% PETG (5) 20%, by weight 19.62%, by weight 0.38%, by weight
     5  8% PETI (4) 50% by weight 32% PETG (5) 30%, by weight 19.62%, by weight 0.38%, by weight
     6  8% PETI (4) 40% by weight 32% PETG (5) 40%, by weight 19.62%, by weight 0.38%, by weight
     7  8% PETI (4) 30% by weight 32% PETG (5) 50%, by weight 19.62%, by weight 0.38%, by weight
     8  8% PETI (4) 20% by weight 32% PETG (5) 60%, by weight 19.62%, by weight 0.38%, by weight
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     9  6% PETG (b) - 80% by weight 19.62%, by weight 0.38%, by weight
     10  6% PETG lb) 70% by weight 32% PETG 13 '10%, by weight 19.62%, by weight 0.38%, by weight
     eleven  6% PETG (b) 60% by weight 32% PETG {S> 20%, by weight 19.62%, by weight 0.38%, by weight
     12  6% PETG (b) 50% by weight 32% PETG 10) 30%, by weight 19.62%, by weight 0.38%, by weight
     13  6% PETG (b) 40% by weight 32% PETG 15) 40%, by weight 19.62%, by weight 0.38%, by weight
     14  6% PETG (b) 30% by weight 32% PETG {S> 50%, by weight 19.62%, by weight 0.38%, by weight
     fifteen  6% PETG (b) 20% by weight 32% PETG 10) 60%, by weight 19.62%, by weight 0.38%, by weight
    (1) MXD6, grade 6007 (from MITSUBISHI GAS CHEMICALS) / granules
    (2) Cobalt stearate, marketed under the reference of STEACO 9.5, by SHEPERD CHEMICAL COMPANY / powder
    (3) MITSUI B Resin B-050, marketed by the firm MITSUI CHEMICALS, and which has the intrinsic viscosity of 0.85 / granules
    (4) Resin marketed by DUPONT SABANCI POLYESTER EUROPE, under the reference of OPTRA H, and which has an intrinsic viscosity of 0.84 / granules
    (5) Resin marketed by the company SK CHEMICALS, under the reference of Skigreen S 2008, and which has an intrinsic viscosity of 0.8 / granules
    (6) Resin marketed by VORIDAN, under the reference of PJ003, and which has an intrinsic viscosity of 0.83 / granules.
    Preparation of material A and B
    First, the PET granules (material A) are dried at a temperature of 160 ° C for a period of four hours. The granules of MXD6 are dried separately at a temperature of 80 ° C for a period of four hours, and the granules of component B 1 are dried at a moderate temperature (around 40 ° C , above the temperature Tg (Tg = glass transition temperature).
    A dried mixture (material B) is prepared by mixing, in a mechanical way, in a tumbling drum, dry granules of component B 1 (in a percentage of 80%, by weight) and MXD6 (in a percentage of 19, 62%), and by the addition of cobalt stearate (in a percentage of 0.38%, by weight), in the form of a powdered material, in order to coat the granules, with cobalt stearate. The mixture is maintained, at a temperature of 85 ° C, under the action of dry air, before co-injection.
    Injection stage
    The said mixture (material B) is co-injected in a standard way, in a mold with material A, in order to make a three-layer preform, 1.
    The co-injection stage, to manufacture the preform, is the same for each of examples 1 to 15.
    The co-injection stage is carried out in a co-injection machine of the Battenfeld 1000 type. The co-injection machine in question is equipped with the following devices:
    - a main helical spindle (to inject material A), with a diameter of 35 mm and a ratio factor or ratio L / D, corresponding to a value of 25/1.
    - a second helical spindle (to inject material B), with a diameter of 25 mm and a ratio factor or ratio L / D, corresponding to a value of 25/1.
    The Battenfeld type machine has 3 heating bands, which form three heating zones. As a cooling liquid, water is used, with an inlet temperature <10 ° C, and an outlet temperature <15 ° C.
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    The weight and dimensions of the preforms are the same, for all the examples, and these parameters are compiled in Table 2.
    Table 2: Example of weights and dimensions
     Weight (g)  26
     wt (mm)  3.92
     Wlb (mm)  0.43
     D (mm)  18.14
     l (mm)  75.36
    With reference to Figure 1, the dimensions of the preform, which are mentioned in Table 2, are defined in the manner described below, below:
    - wt, is the wall thickness of multiple layers of the preform;
    - Wlb, is the average thickness of the gas barrier layer, in the preform;
    - d, is the average diameter of the preform;
    - l, is the developed length of the preform, and this is determined by the formula
    Di + Do
    l = ------------------------------
    2
    where, Di, is the length of the internal line (outlined by a bold line, in Figure 1), and Do, is the length of the external line (outlined by a bold line, in Figure 1).
    Blow Molding Stage
    The preforms are stretched biaxially and blow molded, in a standard way (blow molding step). The blow molding stage is the same, for each of the examples.
    In a particular way, the preforms are stretched biaxially and blow molded, in a blow molding and stretching machine, of the "Sidel estretch blow molding machine (SB O / 2®) type, so that the 1 'three-layer bottle of Figure 1, which has a filling volume of 0.5 l. In Figure 2, the straight line, referred to as "FL", defines the upper limit of the volume of filling of the bottle.
    The dimensions of the bottle are the same, for each of the examples. As a non-limiting example, the main dimensions of the bottles are summarized in Table 3.
    Table 3: Bottle dimensions
     Bottle
     D (mm)  70 mm
     L (mm)  208.5
     Bottle
     WT (mm)  0.39
     Wlb (mm)  0.04
     SRh  3.86
     SRl  2.77
     Mr  10.69
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    In Table 3:
    - The dimension (D) is the maximum overall diameter of the bottle;
    - The dimension (L), is the developed length of the surface of the bottle, from the bottom side of the neck ring, and to the end of the bottom of the bottle (outlined by a bold line, in the figure);
    - The dimension (WT), is the average wall thickness of the bottle;
    - The dimension (WLB), is the average thickness of the gas barrier layer (LB), in the bottle;
    - SRh, is the ratio factor or ratio of the stretching of the ring, and this is defined by:
    D
    SRh = -----------------------
    d
    - SRl, is the ratio factor or longitudinal stretch ratio, and this is defined by:
    L
    SRl = -----------------------
    l
    - SR, is the ratio factor or planar stretch ratio, and this is defined by:
    SR = SRl x SRh
    Comparative test bottles tets
    Various test tests were carried out, in the bottles corresponding to examples No. 1 to 15, in order to measure the parameters which are cited below: opacity or turbidity, the yield of the sequestration, mechanical performance (top loading).
    By way of comparison, the same test was carried out on the bottles, in accordance with examples 16 and 17, in the manner described below, below.
    Example No. 16 (belonging to the prior art of the technique)
    It is a single-layer PET bottle (monolayer) molded by injection process by blowing and stretching, which has the same dimensions (except as regards the fact that the bottle in question is of the type single layer or monolayer), and the same weight, as those corresponding to the bottles of examples Nos. 1 to 15. The PET resin, is the same as that corresponding to that used for material A, in the Examples 1 to 15. The test test bottles, corresponding to example 16, exhibit good clarity, but these have poor sequestration properties.
    Example No. 17
    It is a bottle, which has the same weight and the same dimensions as those corresponding to examples 1 to 15. The bottles in question are obtained in a standard way, proceeding to co-inject the same material A (that is, PET resin, which has been used in examples 1 to 15), in order to make the outer and inner layers Lin and Lout of the preform, with material B (internal gas barrier layer) .
    Material B 'is a dry mixture of:
    - a percentage of 80%, by weight, of PET homopollmer (Standard grade: less than a percentage of 3%, by weight, of purified isophthalic acid), marketed under the reference 9921W, by the VORIDIAN firm, and the which has an intrinsic viscosity of 0.82 +/- 0.02 (granules);
    - a percentage of 19.62%, by weight, of MXD6 of grade 6007 (from MITSUBITSHI GAS CHEMICALS) (granules) and,
    - a percentage of 0.38%, by weight, of cobalt stearate, marketed under the reference of STEACO 9.5, from SHEPHERD CHEMICAL COMPANY (in the form of a powdered material).
    The test test bottles, corresponding to example No. 17, exhibit high sequestration properties, but, in turn, however, they exhibit opacity or turbidity, which is visible to the eye, and these do not achieve objective of the present invention, as regards the terms of the level of opacity or turbidity.
    Test methods
    Measurement of opacity
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    The opacity or turbidity is mediated, by using a spectrophotometer (of the Minolta® CM-37000d type), in the portion of the straight wall of the bottle, and by using a standard method, according to ASTMD 1003 .
    Kidnapping test
    The objective of the O2 sequestration test is to control whether the active layer in the vessel wall is effectively preventing the entry of O2.
    The bottles in question are filled, to the brim, with deaerated water - namely, with an O2 content, which is less than 150 ppb -, and these are closed, with an aluminum foil sealed in a watertight way, by induction. These are then stored at a constant temperature, corresponding to a level of 22 ° C +/- 0.5 ° C. The O2 dissolved in the water, is measured every 2 weeks, using a method of the "Orbisphere" type. The general principle of the Orbisphere system is based on the low balance between the gas present in the liquid, and the gas phase. The equipment used is an oxygen sensor of the 311 CC series, with a 2958 A membrane model. The Orbisphere microprocessor, for the measurement of CO2, is the 2640 model.
    First, the bottles are shaken for a period of 3 minutes and then the lining is perforated by means of a needle of the Orbisphere apparatus perforator; Next, we proceed to push the water to be analyzed, through the use of an inert gas, - nitrogen -, towards the oxygen sensor, which contains the membrane. Then, the O2 concentration is calculated automatically, and this is shown on the screen.
    The measurements, which are carried out every two months, allow the monitoring of the evolution of the dissolved O2 inside the different containers produced.
    Test load of the upper load
    The objective of this test test is to determine the vertical load which the bottle can withstand before deformation.
    The test apparatus which is used for the test test in question is the one consisting of a tester tester of the type "TOPLOAD tester INSTRON 1011".
    The vacla bottle, to be tested, is centered and positioned, in a vertical position, on the tester as a tester.
    The loading plate moves down, with a speed of 50 mm / minute, to get in contact with the end of the bottle, and the pressure is increased, in a progressive manner, until the bottle begins to deform . At the first deformation of the bottle (= peak 1), the loading plate returns to its initial position. The higher load value is obtained by reading the load value (kg) on the tester as a TOPLOAD type tester.
    Test Test Results
    Top load
    The totality of the bottles of examples 1 to 17, exhibit a very good and comparable mechanical properties, the top loading being, in each case, the one corresponding to a value within some margins which are located between the 31 kg and 34 kg.
    Kidnapping
    The totality of the bottles of examples 1 to 15 show high sequestration properties, which are comparable to the sequestration properties corresponding to example 17. In a particular way, after a period of six months , the bottles of examples 1 to 15, were still sequestering O2, namely, the residual amount of oxygen dissolved in the water, stored for a period of 6 months, in these bottles, was lower than the corresponding to the starting level of the dissolved O2 just after filling (less than 120 ppb). By comparison, the bottles of Example No. 16 do not exhibit sequestration properties. After a period of only two months, the oxygen dissolved in the water, was corresponding to a value of 5.7 ppm.
    Opacity level
    The results of the opacity or turbidity level test tests are compiled in Table 4, which is given below, below.
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    Table 4: Experimental results - Opacity level
     Example # #  Gas barrier material (B)% by weight Opacity%
     one  40% PETI / MXSD6 + Co 80/20 2.47
     2  8% PETI / MXSD6 + Co 80/20 5.32
     3  8% PETI / 32% PETG / MXD6 + Co 70/10/20 3.74
     4  8% PETI / 32% PETG / MXD6 + Co 60/20/20 3.56
     5  8% PETI / 32% PETG / MXD6 + Co 50/30/20 2.35
     6  8% PETI / 32% PETG / MXD6 + Co 40/40/20 2.39
     7  8% PETI / 32% PETG / MXD6 + Co 30/50/20 1.51
     8  8% PETI / 32% PETG / MXD6 + Co 20/60/20 1.81
     9  6% PETG / MXSD6 + Co 80/20 5.9
     10  6% PETG / 32% PETG / MXD6 + Co 70/10/20 4.62
     eleven  6% PETG / 32% PETG / MXD6 + Co 60/20/20 4.37
     12  6% PETG / 32% PETG / MXD6 + Co 50/30/20 2.93
     13  6% PETG / 32% PETG / MXD6 + Co 40/40/20 2.66
     14  6% PETG / 32% PETG / MXD6 + Co 30/50/20 1.96
     fifteen  6% PETG / 32% PETG / MXD6 + Co 20/60/20 1.84
     16  PET (Monolayer) - comparative example 100 2.2
     17  PET / MXD6 + Co - comparative example 80/20 7.12
    Examples No. 1 to No. 17, in Table 4, correspond to Examples No. 1 to No. 17 in Table 1. In Table 4, the weight percentage of MXD6 is added to the weight percentage of stearate. Cobalt (Co). Thus, for example, example 1, in Table 4, should be read as follows: the mixture is composed of a quantity of PETI, corresponding to a percentage within a range, ranging from 40%, in weight, up to 80%, by weight, and a mixture of MXD6 and cobalt stearate, corresponding to a percentage of 20%, by weight (which corresponds to example No. 1 in Table 1, where the specific amounts of MXD6 and cobalt stearate, are detailed (ie, a percentage of 19.62% of MXD6 + a percentage of 0.38%, by weight, of cobalt stearate = a percentage of 20%, by weight) And so, for example, in example 3, in Table 4, it should be read as follows: the mixture is composed of a quantity of PETI, corresponding to a percentage within some margins, which range from 8 %, by weight, up to 70%, by weight, an amount of PETG, corresponding to a percentage within a few m rgenes, which range from 32%, by weight, to 10%, by weight, and a mixture of MXD6 and cobalt stearate, corresponding to a percentage of 20%, by weight (which corresponds to example No. 3 Table 1, where the specific amounts of MXD6 and cobalt stearate are detailed (ie, a percentage of 19.62% of MXD6 + a percentage of 0.38%, by weight, of stearate of cobalt = a percentage of 20%, by weight).
    The results described above, above, in Table 4, demonstrate the fact that the level of opacity is implemented in Examples No. 1 to No. 15, as compared to the level of opacity or turbidity for the bottles of the Example No. 17. Additionally, the level of opacity or turbidity decreases, when the mole percent (x) of the isophthalic acid is increased, for the PETI copolyester, and / or the mole percent (and ) of the CHDM, for the PETG copolyester, and / or when the amount (in% by weight) of y% PETI is increased and / or the amount of x% PETI is increased, in the barrier layer.
    In a particular way, and as regards the examples No. 5, No. 6, No. 7, No. 8, No. 9, No. 12, No. 13, No. 14 and No. 15, they achieve opacity or turbidity levels which are very low (which are comparable to those of the single layer bottle (monolayer) of example n ° 15, and even with a lower level of opacity or turbidity, in the case of examples No. 7, No. 8, No. 14 and No. 15).
    In addition, the bottles of examples No. 1 to No. 15 exhibit adhesion properties, for the layers, which are higher (compared to those of the bottles of example No. 17), and of a In particular, it is very difficult to proceed to delaminate the layers of the bottles by hand.
    More particularly, the best results - in a particular way, in terms of the level of opacity or turbidity - are obtained when the preform or container of the invention has the following characteristics:
    - the polyester, in the barrier layer, comprises a copolymer of at x% PETI, and a copolymer at y% PETG, being, x e y, at least equal to 5; in a more preferable way, in that case, where, x is equal to 5, and in a preferable way, at least equal to 8, and y, is at least equal to 20, and preferably, so less than 30; preferably, the amount of y% PETG, in the barrier layer, is greater than the amount of x% PETI; ,
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    - the gas barrier layer (Lb), comprises an amount of x% PTI, corresponding to a percentage within a range, ranging from 0% by weight, up to 80%, by weight, and an amount of y% PTI, corresponding to a percentage that goes up to 80%, by weight, being, the amount of x% PETI and y% PETG, at least equal to a percentage of at least 80%, in weight;
    I
    - the amount of copolymer at x% PETI and / or copolymer at y% PETG, in the barrier layer (Lb), corresponds to a percentage of at least 10%, by weight, said quantity being of a preferably, the one corresponding to a percentage of at least 50%, by weight, and more preferably, at least 80%, by weight;
    I
    - x or y, is at least equal to 20, and preferably, at least equal to 30.
    The composition of the present invention, is especially appropriate (but not only), for the manufacture of a molded bottle by means of a process of injection and stretching by blowing, which has high relationship factors or stretching ratios, namely, that have a ratio factors or ratios of longitudinal stretch (SRi), corresponding to a value of 2.5 and / or a ratio factor or ratio of the stretch of the ring (SRh), which is greater than 3, and a factor of ratio or ratio of planar stretch (SR), which is greater than 10. However, however, in the sector of the manufacture of bottles, the composition can also be used for the manufacture of hollow containers, rigid, by using of extrusion and blow molding technique.
    The improvement of opacity or turbidity, which is obtained when the present invention is practiced, can be explained, "a posteriori", as follows:
    The opacity or turbidity, in the bottle of example No. 17, will be generated, mainly, during the biaxial stretching of the preform, due to the difference between the refractive index of the oriented PET, and the refractive index of the oriented MXD6.
    Figure 3 shows the index of refraction, versus ratio factor or planar ratio, for cast cast films, and stretched manufactured films, made of MXD6, and for cast cast films or stretched films, manufactured to PET base. The fact can be derived, from Figure 3, consisting in that, the refractive index of the non-oriented PET, is substantially the same as that corresponding to the refractive index of the MXD6 not stretched, but that, the refractive index of the pEt , it increases rapidly, when the PET is stretched, while the refractive index of the MXD6 remains substantially constant. It can be like that! Thus, from these graphs, the fact that, in the preform, the refractive indices of the MXD6 and the PET, are substantially the same, but, nevertheless, nevertheless, a Once the preform has undergone a stretching process, the PET refractive index becomes much more important than the MXD6 refractive index, in the intermediate gas barrier layer of the bottle in question. This important difference between the Indices of refraction of the two materials, in the barrier layer, is explained by the formation of opacity or turbidity in the bottle, when the preform is being stretched.
    In Examples No. 3 to 16, the use of a copolyester at x% PETI and / or at y% PETG (where, x, y> 5), in the barrier layer, mainly provides the advantage which It is exposed to continuation. The copolyester at x% PETI and / or at y% PETG, in the intermediate barrier layer of the preform, has substantially the same Refractive Index (iR1), as the Refractive Index of the MXD6, and since, the copolyester at x% PETI and / or at y% PETG, exhibits a reduced crystallization rate, the crystallinity of said copolymer, in the intermediate layer of the bottle (after having proceeded to the stretched process), it is still low, and excited Refractive index (IR1), it is not modified in an essential way, when it is stretching the preform; at the end of the bottle, the Refractive Index (IR2) of the oriented MXD6 and the Refractive Index (IR1) of the copolymer at x% PETI, or y% PETG2, are "substantially the same". Thus, in this way, the wall of the bottle is transparent, and exhibits reduced opacity or turbidity.
    In the scope of the present invention, the terms "substantially equal", for the two indices of refraction, (IR1) and (IR2), mean the fact that, the difference between (IR1) and (IR2), are sufficiently reduced, as to avoid the formation of opacity or turbidity which is visible by the eyes, during the stretching process. The range of the extension, for this difference, depends, in a remarkable way, on the thickness of the layer; The larger the thickness of the layer, the smaller the difference should be, in order to avoid the formation of an opacity or turbidity, which is visible by the eyes. As an example of the above, for a barrier layer, which has a thickness of 40 pm, it is preferable that the difference between the Indices of refraction (IR1) and (IR2) is less than one value of 0.04 and, preferably, less than a value of 0.02, in order to avoid the formation of opacity or turbidity.
    The gas barrier layer, in examples No. 1 to No. 15, is an active layer, which exhibits high oxygen sequestration properties. In order to obtain an active barrier, in the material of the gas barrier (B), a person skilled in the specialized art of the technique may consciously substitute cobalt stearate for another metal catalyst of transition, in a sufficient amount, in order that, MXD6, 5 sequester the oxygen, and in a particular way, a metal salt, such as that consisting of cobalt octoate, a rhodium compound, a copper compound , or an iron compound.
    In the scope of the present invention, the inner and outer layers (L0ut and Lin), are not necessarily made of PET, and these can be manufactured based on any thermoplastic material, to provide the required mechanical properties, at Bottles, although, however, the use of a PET homo- or copolymer is preferred, due to cost reasons.
    权利要求:
    Claims (19)
    [1]
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    1. - Composition, which has oxygen sequestration properties and which comprises a polyamide, a polyester, and a transition metal catalyst, wherein the amount of polyamide is at least 3%. , by weight, and the polyester, comprises a copolymer at x% PETI, and a copolymer at y% PETG, being, x and y, at least equal to 5.
    [2]
    2. - Composition, according to claim 1, wherein the amount of polyamide is a percentage of at least 8%, by weight, and preferably, a percentage of at least 10% , in weigh.
    [3]
    3. - Composition, according to claim 1 or 2, wherein, x, is at least equal to 5, and preferably, at least equal to 8 e, and, is at least equal to 20, and in a preferable way, at least equal to 30.
    [4]
    4. - Composition according to any one of claims 1 to 3, wherein the amount of y% PETG is greater than the amount of x% PETI.
    [5]
    5. - Composition according to any one of claims 1 to 4, wherein the polyamide is a polyamide, which contains a xylene group.
    [6]
    6. - Composition, according to composition 5, where polyamide is MXD6.
    [7]
    7. - Composition according to any one of claims 1 to 6, wherein the amount of copolymer at x% PETI and the copolymer at y% PETG is at least 10% by weight. , preferably, a percentage of at least 50%, by weight, and more preferably, a percentage of at least 80%, by weight.
    [8]
    8. - Composition, according to any one of claims 1 to 7, wherein, x or y, is at least equal to 20, and preferably, at least equal to 30.
    [9]
    9. - Composition according to any one of claims 1 to 8, wherein the transition metal catalyst is selected from the group: cobalt compound, rhodium compound, copper compound, iron compound.
    [10]
    10. - Composition, according to claim 9, wherein the transition metal catalyst is a cobalt salt.
    [11]
    11. - Composition, according to claim 10, wherein the cobalt salt is cobalt stearate.
    [12]
    12. - Composition according to any one of claims 1 to 11, wherein the composition is a mixture.
    [13]
    13. - Procedure for the production of a composition according to claim 12, wherein the polyamide granules and the polyester granules are dried separately and then these are mixed, dry, by mixing said dried polyamide granules, said dried polyester granules, and the transition metal catalyst.
    [14]
    14. - Packaging article, manufactured from the composition according to any one of claims 1 to 12.
    [15]
    15. - Multi-layer packaging article, according to claim 14, and which comprises at least one internal barrier layer, wherein said barrier layer (Lb) is manufactured from the composition of a any of claims 1 to 12.
    [16]
    16. - Packaging article, according to claim 15, and comprising at least three layers: said gas barrier layer (Lb), being sandwiched, as a "sandwich", between two layers of non-barrier (Lin ), (Lout).
    [17]
    17. - Packaging article according to claim 16, wherein the two layers of non-barrier (Lin), (Lout), are produced based on a homo- or copolymer of PET.
    [18]
    18. - Packaging article according to any one of claims 14 to 17, and which has an opacity level of less than a percentage of 5%, preferably, less than a percentage of 3%, and of a more preferable form, less than a percentage of 2%.
    [19]
    19. - Use of the composition according to any one of claims 1 to 12, for the production of an inner barrier layer, in a multi-layer packaging article.
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    同族专利:
    公开号 | 公开日
    ES2569396T3|2016-05-10|
    ES2569058T3|2016-05-06|
    WO2005014409A1|2005-02-17|
    WO2005014410A1|2005-02-17|
    EP1651526B1|2016-03-16|
    EP1504999A1|2005-02-09|
    EP1651526A1|2006-05-03|
    EP1651527B1|2016-03-16|
    EP1651527A1|2006-05-03|
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    法律状态:
    优先权:
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    EP03017845|2003-08-05|
    EP03017845A|EP1504999A1|2003-08-05|2003-08-05|Rigid plastic container having gas-barrier properties and high transparency|
    PCT/EP2004/008275|WO2005014410A1|2003-08-05|2004-07-23|Composition for making a packaging article having oxygen-scavenging properties and low haze|
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