DE2147561A1 - Plastic container - Google Patents

Description

PATENTANWÄLTE 8 MUNICH 8O. MAUERKIRCHERSTR. 45

Dr. Barg Dipl.-Ing. Stapf, 8 Manchen 80, MauerkircherstraBe 45 ·

Your reference your letter Our reference date

21 580

Attorney file 21 580

MONSANTO COMPANY St. Louis, Missouri / USA

Plastic container

2 Sep 3 197ί

The invention relates to a plastic container, in particular an elongated container for carbonated beverages with a pressurized inside

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»1272 98 70 43» 3310 Talagrammti BEROSTAPFPATENT MOnchin TELEX 05 24 540 BERG d

Banki Baywitch Vtrainibank MOndim 453100 Poihdiadci MOnchm 653 43

ORIGINAL INSPECTED

Liquid is enclosed, and that of a certain, pressure-resistant and relatively impenetrable thermoplastic material.

Metal cans for storing pressurized liquids, such as B. of beverages containing carbonate, such as so-called soft drinks, beer and the like., have long been known, but their use is not without its disadvantages. For example, these cans are normally unbreakable, but especially when full dented when falling, thereby adversely affecting its appearance to a buyer. There are also metal cans opaque so that the contents cannot be viewed before opening. Such doses also often adversely affected the taste of certain beverages. Furthermore, metal cans are after difficult to destroy for their use and thus pose a serious waste disposal problem.

It therefore made sense to use thermoplastic containers for this purpose, as they are compared to metal cans and also have clear advantages over conventional glass containers. So are thermoplastic Containers generally more vibration-resistant than glass, lower in weight and therefore easier to handle. For example, there goes a pressurized Container made of a thermoplastic material through

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bad treatment breaks it, so it does so without one Explosion and fragments or edges arise due to the nature of the material of the plastic one does not scratch or cut oneself unless an unusually high pressure or force is applied will. In contrast, the fragments or edges of broken glass containers form fragments on which it is very easy to cut yourself even if only very little force or a corresponding pressure is applied.

In contrast to plastics, metal and glass containers therefore show have some very significant drawbacks.

However, while some of the more serious problems encountered in using metal or glass containers for such uses can be overcome by the use of an organic thermoplastic polymer, no commercially available material has been described which is functional for use in a pressurized one Containers, for example for storing gaseous liquids, such as soft drinks or beer or similar products under pressure. This is more surprising than plastic containers which have been known for certain, non- pressurized contents, e.g. for liquid cosmetics, e.g. for shampones, household chemicals, detergents, pharmaceuticals, motor oils, etc., for at least 10 years .

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The commercially available thermoplastics, such as ζ. Β. Polyethylene, Polypropylene, polystyrene, polyvinyl chloride, polyacrylates, polymethacrylates, etc., have one or more disadvantages, such as B. their high cost, low strength under stress, poor taste or odor tolerance with the respective pressurized container contents or an unsatisfactory tightness to liquids and gases when they are used in the form of relatively thin-walled containers.

In order to be able to compete with glass or metal containers in terms of price, properties such as good strength are essential under pressure, high impermeability to gas and / or liquids and good dimensional stability for long periods of time at relatively severe environmental temperatures for the plastic in the form of thin Walls of vital importance.

The disadvantages of the thermoplastic materials heretofore used for pressurized containers have been partially resolved compensated at the expense of an economically justifiable construction of the container. So are from the US patent 3 325 030 narrow-necked bottles known with special Stress-relieving, semicircular base arrangements constructed which, however, require an accessory to keep such containers in an upright position. From US Pat. No. 3,436,007, laminated, many-

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layered wall construction known in which the combination of two or more thicknesses of generally different materials the disadvantages of one or the other Materials. For example, in U.S. Patent 3,029,963, deep, elongated, and curved Hips all over the surface of the body used to add strength to the container walls. Such pronounced However, kin give the container an unusual appearance.

U.S. Patents 3,451,538 and 3,426,102 have thermoplastic materials for packaging environmentally sensitive materials in which the main component is a polymerized nitrile. Even However, this literature reference is not an indication of a possible use for pressurized packaging refer to.

Sum up . the state of the art! that so far no functioning, economically producible a thermoplastic container has been described which can effectively contain a material under bridging, and which in its external appearance does not differ fundamentally from a glass bottle or a metal can.

A container made of polymer material has now been developed.

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which has an improved combination of properties, such as those used for containers for inter pressure Liquids such as B. of beverages including of soft drinks, beer and the like., in the trade for inevitable be considered.

The object of the present invention is therefore to provide an improved, elongated, thermoplastic Container, such. B. a bottle or can containing a carbonated beverage.

Another object of the invention is to provide an improved single use container of the foregoing named type, which is easily destroyed after its use and thereby polluting the environment keeps it low.

Another object of the invention is to provide an improved container of the aforesaid type which has a or can be used several times without this having an adverse effect on the quality of the product or the functionality of the container would be exercised.

Another object of the present invention is to provide a container which is designed so that the Exercise of tension on the container as a result of its pressurized contents is kept as low as possible

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is, and its Aus sere ε from the containers used so far is similar.

The aforementioned tasks are supported by an elongated Fulfilled container for pressurized liquid materials, which consists of a generally cylindrical body consists of a high-strength, easily combustible thermoplastic material, at least 50% by weight of the thermoplastic material by polymerization from a Ethylenically unsaturated monomers with at least one nitrile group in the molecule was made. This container has a side wall, a bottom wall at the lower end of the side wall with a support ring for holding the container in an upright position on a substantially flat surface and a convex portion that extends extends into the interior of the container within the support ring. The length of the container is greater than its diameter and a pressure-resistant closure member lies over the opening formed by the side wall and is connected to the upper one Part of the side wall located in the vicinity of the opening connected.

In a preferred embodiment of the invention, the plastic container has an average wall thickness of 0.3 up to 1.5 mm, contains a carbonate drink at a pressure of 0.3 to 14 kg / cm and has an impermeable Clasp. This container has at least the after

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The method described below has certain properties: Op permeability of less than 4 cnr / day / m / mm-atm. at about 23 ° C; COg permeability of less than 12 cmVday / m / mm-atm. at about 23 ° C; a water permeability of less than 1.6 g / day / m / mm at about 23 ° C; a breaking strength of more than 700 kg / cm ² at 23 ° C;

a stiffness modulus greater than 32,000 kg / cm; less than 7% creep after containing the pressurized beverage for 1 week at 33 ° C, and no appreciable effect on the taste of the beverage after it has been in it for up to 6 months. The container is made of a polynitrile that

a) contains a nitrile group which is functionally at least 66 mol% acrylonitrile is equivalent, and

b) up to 34 Mo 1% of at least one copolymerized monomer which has at least one ethylenically unsaturated bond contains in the molecule.

The container can either be in the form of a narrow-necked bottle, a wide-necked can, or any intermediate form thereof to have. It is preferably made of one piece, is transparent and can either be sufficiently thin-walled for single use or of sufficient thickness and made of a modified thermoplastic so that it can be used several times. The preferred basic wetting of the polymer contains a) 66 to 97 »5 Mo 1% of a polymerized monomer from the group acrylonitrile, methacrylonitrile and their mixtures,

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b) 2.5 "to 34 mol% of at least one copolymerized, Ethylenically unsaturated monomers that do not have a nitrile group contains.

In the following the invention is described in more detail with reference to drawings in which

Fig. 1 is a perspective view of one type of the inventive Container in the shape of a bottle, and

Fig. 2 shows a similar view of a container according to the invention in the form of a can.

Specifically, FIGS. 1 and 2 show elongated containers, generally designated 10, for holding pressurized liquids. The container 10 can either be in the form of a bottle 12, which at its upper end has a relatively narrow opening of about 15 to 40 %. of the diameter at the widest point of the container, or in the form of a can 14, the opening of which is essentially as large as the widest part of the container. Of course, the containers according to the invention can also have openings whose sizes are between these two shapes. In any case, the container 10 consists of a special, pressure-resistant thermoplastic, which will be described in more detail below. As can be seen from the drawing, the containers 12 and 14 preferably have

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although not necessary, there are no reinforcing hips either in the base or in the side walls on what goes through the high strength of the material from which the containers are made is made possible. In some cases for aesthetic reasons Reasons to be attached to ribs, which are then preferably of are round in shape, otherwise they will create areas of high tension in the container. Although the containers 12 and 14 are transparent or shown as transparent, they can also consist of a completely opaque material.

The bottle 12 has a side wall 16 which forms a generally cylindrical body in one piece. The bottom wall 20 is located at the lower end of the side wall 16 and has an annular support part 24, which holds the container upright on a substantially flat surface. The annular support part 24 can be a have round contour or it can form a relatively short, flattened surface that is substantially perpendicular runs to the container axis. The inwardly convex or raised portion 28 extends partially into the interior of the container within the bing 24, its various Eadien a slowly running and show gradual transition and no sharp and abrupt change. An investigation into the plastic in the Base area of the container occurring stresses at an internal pressure of 14 kg / cm that such a convex Arrangement for a lower voltage distribution

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leads in plastic as you get at a bottle which has a relatively flat bottom wall. Me side wall 16 can be a flat, indented Part along its longitudinal direction for applying decorative patterns, such as. B. of markings of the Product with the shoulders of and at each end of a notch running slightly outwards, so that, for example, a label is protected during use of the container.

At the upper end of the side wall 16, the opening formed by the side wall is closed after filling with a pressurized liquid material with ELIfe an impermeable, pressure-resistant closure part, which has an upper wall 32 and a fold 36 running downwards from the hand. In the embodiment shown in FIG. 1, the closure member has the shape of a crown closure, the fold 36 shows numerous, inwardly formed depressions, which abut against a closure ring surrounding the opening at the upper end of the container neck (not shown), and thus the closure physically attach to the container. The material of the closure should of course be made of a liquid material which is inert to the pressurized liquid material within the container, or optionally have a suitable coating or a coating of an inert material on the inner surface of the closure member.

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In the embodiment of the invention shown in Fig. 2, the elongated container is in the form of a can. The fundamental difference compared to FIG. 1 is that the opening at the upper end of the side wall 18 has essentially the same diameter as the side wall 18, it should preferably be 75% or more than the diameter of the side wall 18, that in relation to that narrow neck of the arrangement in FIG. 1 enables rapid filling of the container with the contents. In addition, the can 14 has a base part 22 at the lower end of the side wall 18, which consists of a gradually upwardly and inwardly extending convex part JO within a circularly formed annular support part 26, so that the can on a substantially horizontal surface without assistance of another carrier part is held. Such a support element adversely affects the overall appearance of a type of can to which consumers are accustomed due to the handling of metal containers.

In the case of the can 14, the pressure-resistant closure member is shown in the form of a cover-shaped metal plate, which consists of a top wall 34, which the opening at the top The end of the side wall 18 is covered and consists of a hem 38 exists to connect the upper end of the side wall 18 to the closure part in a pressure-tight manner. That Closure part can have a tear strip 40 on the top wall 34 so that when this is pulled upwards and is removed on the outside, an opening in the closure part

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to drink! The inner surface of the can closure should also be inert to the contents of the container, similar to that described above for bottle 12. Although metal fasteners have been described above, can of course also completely made of plastic closures can be used, which either the Inner or outer surface of the upper end of the container wall Firmly connect by fitting or overlapping. A combination of these two types of connection options can also be selected, provided that this withstands the internal pressure of the contents and is sufficiently impermeable that no container contents are lost goes. The closure can optionally also have an inert, one-piece seal that is used for this purpose helps to withstand the pressure of the content.

The material from which the containers of Eds. 1 and 2 are made is a pressure-resistant, thermoplastic material, of which at least 50% by weight consists of an ethylenically unsaturated Monomers containing at least one nitrile group in the molecule, was polymerized. In a preferred Embodiment, the thermoplastic is a polymer that

a) contains a nitrile group functionality that of those is equivalent as it is present in a polymer containing at least 66 Mo 1% acrylonitrile, and

b) up to 34 mol% of at least one copolymerized monomer contains at least one ethylenically unsaturated

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Has bond in the molecule.

The particularly preferred thermoplastic material comprises

a) 66 to 97 »5 Mo 1% of a polymerized monomer the group aryl nitrile, methacrylonitrile and mixtures thereof, as well as

b) 2.5 to 3% Mo 1% of at least one copolymerized monomer, which has at least one ethylenically unsaturated bond in the molecule. As a copolymerized monomer preferably styrene is used.

The component of the plastic that. is responsible for the protection of the carbonated beverage enclosed within the container, the polymerized nitrile monomer, which is preferably present in an amount which, expressed as Ni trile group functionality, is at least 66 mol% acrylonitrile equivalent, so that properties are obtained, which are required to carbonate overall f beverages such. B. beer, soft drinks, etc., to pack effectively.

In relation to carbonated products- these are properties for medium wall thicknesses of the container between 0.3 to 1.5 mm the following:

1) Sine oxygen permeability of less than 4 cm * / Day / m / mm-atm. at about 23 ° C to avoid a change in the odor of the contents;

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2) a carbon dioxide permeability of less than

12 cm ^ / ^ ag / m / mm-Atm. at about 23 ° C to increase the foamability to preserve the contents for a normal storage period of the filled container;

3) a water permeability of less than 1.6 g / day / m / mm at around 23 ° C, as the main component of most Drinking water is why it is required that the level of the content with a minimal change during normal storage time is maintained; 4) a tensile strength of more than 700 kg / cm at 23 ° C, thus a resistance to the over a relatively wide print area of the content, which is up to

up to 14 kg / cm, the resulting stresses are preserved will;

5) a stiffness modulus greater than 32,000 kg / cm, so the internal pressure without the creation of bulges or Deformation of the container is resisted;

6) a less than 7 % increase in the volume of the container (creep) after holding the pressurized beverage for 1 week at 38 ° C. A higher increase would give the drunkard the impression that the container was poorly filled;

Includes 7) no substantial effect on the taste of the beverage after storage time within the vessel of up to 6 months, which both migration of resin components in the product or an absorption of the product through the plastic.

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The properties listed above are for packaging of pressurized materials. In addition to these, the polymer can have other desirable properties that make it suitable as a container.

It is essential that the upper limit of 97 »5 mol% of the nitrile group-containing polymerized monomers is not exceeded in order to avoid the need for excessive melting temperatures during processing avoid what would lead to degradation of the material.

The invention is described in more detail below using examples. The test results obtained in each case are listed in Table I.

example 1

To make the bottle of fig. 1 is a resin of 90 wt.% C 94 Mo 1%) polymerized methacrylonitrile and 10% by weight (6 Mo1%) of polymerized styrene a common one Trial-type extruders supplied. This existed in the present Case from a single cylinder with a 0.9 m long screw with a diameter of 38 mm, the at its discharge end was connected to a downwardly directed nozzle, which had a 5 mm wide annular outlet opening 13 mm in diameter. It became continuous at a material temperature of about 250 ° C a tubular parison with a wall thickness of 2.5

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extruded downward between opposing mold halves, which were designed so that after blowing a plastic bottle of the type shown in Fig. 1 was obtained, which had a cylindrical body of 50 mm in diameter and 200 mm in total length. At its upper end there was a neck which ran evenly inwards to an opening 15 mm in diameter. To manufacture the bottle, the mold halves are brought together so that they enclose a portion of the extruded parison advancing downwards, which is cut off immediately above the mold. A needle is then inserted into the upper end of the parison held by the mold in order to inflate the bottle into the desired shape. The mold was cooled and the mold halves separated to reveal a plastic bottle that had an average wall thickness of 0.76 mm because the neck was slightly thicker than the best of the bottle. The pressing process was repeated continuously until enough bottles were obtained to carry out the tests described below, some of which were carried out with the bottle and some with a flattened sample obtained by turning the bottle into a 100 mmlanges cylindrical piece cutout, which was cut once longitudinally and yielded a flat sample of 100 χ 150 mm.

In the case of can 14, the extruder was 2 m in length

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and a 90 mm diameter screw. The nozzle had a horizontally running slot, the 2 mm wide opening of which in the vertical direction extended 610 mm in the horizontal direction. The polymer of 94/6 mol% of polymerized methacrylonitrile / styrene polymer was ^{extruded through this slot nozzle at a temperature of about 23Ο 0} C and thereby obtained a web material that was then stretched around the opening of a recess of a die, which in its shape of the of the container of FIG. 2 corresponded. A punch was then guided against the tensioned web in order to pull the part within the tensioned area into the recess of the mold. After the punch was practically, completely inserted into the cavity of the mold, pressurized air was introduced between the partially drawn web and the surface of the punch in order to blow the partially drawn web from the punch outwardly against pre-cooled walls of the cavity, around the To harden plastic and thereby form the can shown in FIG. 2.

The samples obtained, either in the form of a bottle, a jug or a 100 χ 150 mm flat piece, the obtained from either a bottle or a can, the tests described below are subjected to the values listed in Table I were obtained.

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1. Processability of the polymer - This property means the ability of a polymer in the molten state to be processable and extrudable through a nozzle opening and then to be deformable into a structurally good container. The polymer must be able to blow smoothly and remain completely thermoplastic even after deformation, so that waste material can be reused. The blow molding process described above

Bottles obtained from the pressing process must be stiff, closely correspond to the formation of the surface of the mold recess and have a relatively uniform wall thickness without significant weak spots. A polymer that does not (1) flow smoothly after extrusion or remains thermally stable, by a comparatively low level uniform tubular parison or web that (2) after formation of the parison or web not axially stretchable and expandable to the side at least J-fold with regard to the distribution of the material and that (3) after expansion does not remain thermoplastic through and through without localized weak spots, does not meet the conditions set.

2. Oxygen permeability - The oxygen permeability is determined using the flat sample according to ASIH D-14-34-58. For this purpose, a disc with a diameter of 76 mm was cut from the 100 χ 150 un test piece and along its outer band within a

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Permeability cell clamped in such a way that the Chamber inside the cell by the sample was divided into two chamber parts, from all residual gases and steaming were free. One of these chamber parts was exposed to an atmosphere (760 mm Hg) of. pure, dry oxygen filled and the chamber part on the other side of the disc kept under vacuum. After setting the At equilibrium and 24-hours under these conditions at a temperature of 23 ° C, the amount of oxygen was that passes through the disc as measured by its pressure and the oxygen transmission rate expressed in cmVday / m / mm-atm. calculated at about 23 ° C. the Oxygen permeability can also be measured by taking an empty container with one atmosphere made of pure oxygen and closes the container with a special impermeable seal the samples of the gas in the container by means of a hypodermic Needle such as is used for gas chromatographic purposes can be withdrawn. By such a Analysis can measure the amount of oxygen evolved from the container over a period of 28 days will.

3. Carbon dioxide permeability - The procedure is the same as described under 2., with the modification that carbon dioxide is used instead of oxygen.

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4-. Water permeability - The water permeability test is carried out with the bottle or can and measured by filling the container practically full with water at 23 ° C and closing the container with a moisture-proof seal. The filled bottle is then weighed and placed in an airtight chamber containing an atmosphere of circulating air at 50 % relative humidity and 23 ° C. After 28 days or more under these conditions, the amount of water lost from the bottle is measured by removing the bottle again weighs out and calculates the permeability, expressed in g / day / m / mm at about 23 ° C (50 % relative humidity).

5. Toughness - This property is determined by filling several containers with water or carbonated water up to about 25 mm to the upper edge, closing each container with an airtight seal and then allowing it to fall from different heights.

The estimated mean failure height (EKFH) is defined as the height at which 50 % of the bottles break. This method is better known as the Bruceton Staircase Method.

6. Product absorption - This property is defined as the property of the plastic that is not able to absorb the products packed inside the container and is thereby not absorbed

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measured that filling a bottle with a 0.1% solution of peppermint oil in a 75 / 25- ^w ater / alcohol mixture and kept the bottle and its contents for 30 days at a temperature of 50 ° C. After this period, the loss of peppermint oil from the solution is measured by gas chromatography.

7 · Water vapor permeability - The water vapor permeability of the plastic is the property of the plastic to let moisture through the plastic in the vapor state and is determined according to ASTM E-96-6JT. For this purpose, a container is filled with calcium chloride as a desiccant, closed with a moisture-proof seal and weighed. The closed container is then placed in a tree that has an atmosphere of circulating air at 95 % relative humidity and 58 ° C. After 28 days or more, the container is weighed again. The results are used to calculate the water vapor transmission rate expressed in g / day / m / mm at about 38 ° C (95% relative humidity).

8. Stiffness - The stiffness of the plastic is determined using the flat sample and measured by calculating the stiffness modulus of the sample according to ASTM D-74-7-63.

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9. Thermal deformation temperature - The experiment to determine the warm deformation temperature is carried out with the aid of the flat sample and measured according to ASOJM D-1637-61.

10. Impermeability to Product Components - The container of the present invention must retain a plurality of components of the pressurized liquid for extended periods of time without significant loss of one or more of these components of the product from the container. As a general measure of impermeability for product components, two tests have been developed, which are described below:

(a) Permeability for polar liquids - In this experiment the container is filled with pure liquid ethyl alcohol up to 80% of its capacity. The filled bottle is sealed, weighed and placed in a chamber in which an atmosphere of circulating air at 50 % relative humidity and 23 ° C is maintained. The bottle is held under these conditions for 28 days, then weighed again and the weight loss determined, which in turn is used to determine the rate of permeation of ethyl alcohol, expressed in g / day / » ² / mm at about 23 ° C (50 % relative humidity).

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(b) Permeability of Non -Polar Liquids - The degree of ability of a plastic to act as a barrier to non-polar liquids, such as B. liquid hydrocarbons to act is measured by filling the container up to 80% of its capacity with pure hexane, then closing the container, weighing it and placing it in a chamber that has an atmosphere of circulating air at 50 % relative humidity and 23 ° C. The container is kept under these conditions for 28 days, then weighed again to determine the weight loss, which is used to determine the permeability of hexane, expressed in g / day / m ² / mm at about 23 ° C (50 % relative humidity ) to calculate.

11. Tensile strength - the tensile strength of the resin is determined using the flat sample and measured by placing one calculates the tensile strengths of the sample according to ASTM D-747-63.

12. Pasteurization - the container is filled with a pressurized liquid such as B. filled with beer, from 4 ° C, sealed, and subjected to a water bath at a temperature of 63 ⁰ C. When the temperature of the contents reaches 60 ° C, the container is held at this temperature for 1 minute and then removed and placed in a bath at 38 ° C by

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- 25 let it cool down.

I3. Creep - the container is exposed to a pressurized liquid, such as B. carbonated water, filled at 3.5 kg / cm at 23 ° C and sealed. The container is then stored at 38 ° for 1 week. Creep is determined as the permanent increase in volume of the container, which is measured after the test and compared to the original volume.

14 ·. Odor Transmission - The container is filled with a carbonated beverage such as. B. a cola drink or beer, filled and sealed. Then, in the case of the cola drink, the container is filled directly or, in the case of certain beers, after pasteurization at 23 ° C (50 % relative humidity) or at 4 ° C, depending on the drink, for 1, 2, 3 and 6 Months. At the same time, control containers made of glass and metal are kept under the same conditions. After each of the four storage periods, the cola drink and / or the beer is tested by a panel of at least five taste experts and the taste of the drinks is compared with the drinks stored in the control containers. 20 taste determinations are made. If ten or fewer of the taste determinations show a taste difference from the control sample, the taste transfer is considered to be insignificant. Surrender to 11

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15 of these determinations show a difference in taste compared to the control sample, this is considered to be intolerable Transfer of taste viewed. If 16 to 20 of the determinations show a difference, the transfer of taste becomes regarded as very high and also as intolerable. The contents of the test packs will each also be gaschroma to graphically and chemically for the determination of Analyzed components that were leached from the plastic.

15 · Carbonate loss - For this purpose, containers from experiment 14, ie filled with cola drink, are used at 3.5 kg / cm ² or beer at 2.5 kg / cm to determine the CO ^ loss at 23 ° C. The original pressure inside the container is measured with the help of a bottle measuring device for COp pressure and the pressure again after 1, 2 and 3 months.

16. Clarity - The empty container is placed between the two beams of a Hunter-Meter type 25B measuring device and the haze is measured in% and taken as a measure of the clarity.

17. Flammability - The container is exposed to a bun en burner using natural gas / air as fuel until it ignites. The burner is then removed and the combustibility or non-combustibility of the

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Halters noted. During the incineration of the container, the formation of smells and smells is recorded and samples are taken of the smoke and the by-products analyzed for their content. After complete combustion, the ash content will be the residues weighed.

Example 2

The process of Example 1 is repeated with the modification that acrylonitrile is used instead of methacrylonitrile will.

Example 5

The procedure of Example 1 is repeated with the modification that methacrylonitrile-styrene polymer with 15 wt.% an impact modifier is mechanically mixed. This modifying agent contains a Graft copolymer of methacrylonitrile and styrene to 75% by weight butadiene, 18% by weight methacrylonitrile and 7% by weight Styrene terpolymer rubber in which the rubber forms 40% by weight of the graft copolymer and the content of the nitrile group-containing polymerized monomer of the blended materials is 82 mol #.

Example 4-

The procedure of Example 1 is repeated with the modification that the constituent of polymethacrylonitrile on a

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Amount of 50 wt.% (60 mol%) is reduced. This example exhibits a functionality that is less than that which is 66 mole percent acrylonitrile equivalent.

Example 5

The procedure of Example 1 is followed with the modification repeats that the amount of the constituent polymethacrylonitrile is reduced to an amount of 25% by weight (34 Mo 1 #) will. This example serves the same purpose as example 4.

Example 6

The procedure of Example 1 is repeated with the modification that the amount of polymethacrylonitrile is increased an amount of 10 wt% (13 mol%) is decreased. This Example serves the same purpose as Example 4.

Example 7

The process of Example 1 is repeated with the modification that the polymer contains 60% by weight (75 mol%) of polyacrylonitrile and 40% by weight (25 mol%) of polystyrene.

Example 8

The process of Example 1 is repeated with the modification that the polymer is 80% by weight (83 mol%) of poly

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methacrylonitrile, 10 wt.% (10 mol #) polyacrylic acid and Contains 10 wt. # (7 moles #) of polystyrene.

Example 9

The procedure of Example 1 is repeated with the modification, that the polymer is 35 wt. # (44 mol%) polyacrylonitrile, 40 wt. # (40 mol #) polymethacrylonitrile and 25 wt. # Contains (16 moles #) polystyrene.

Example 10

The procedure of Example 1 is repeated with the modification, that the polymer is 80% by weight (78 mol%) of polymethacrylonitrile and 20% by weight (22 mol%) of polymerized methyl vinyl ether contains.

Example 11

The procedure of Example 1 is repeated with the modification that the polymer% (95 mol #) polymethacrylonitrile, 6.5 wt% (5 mol #) polyvinyl acetate containing 93.5 wt...,

Example 12

The process of Example 1 is repeated with the modification that the polymer is 95.5% by weight (95 mol #) of polymethacrylonitrile, and 4.5 weight percent (5 mole percent) polyvinyl chloride.

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Example 15

The process of Example 1 is repeated with the modification that the polymer is 97 »5% by weight of polymethacrylonitrile
and 2.5 wt.% (5 mole%) polyethylene.

Example 14

The process of Example 1 is repeated with the modification that a polyvinyl chloride homopolymer is used instead of the 90/10% by weight methacrylonitrile / styrene polymer. The purpose of this example is to show which
poor results when using a polymer
which does not contain any nitrile groups.

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Table I.

Examples Test I II III IV V VI VII

1. Processability ABA AAAA of the polymer,

where A - compatible
and B - mean less compatible

2. Saueratoff transmission 0.24 0.04 1.2 6.6 40.0 104.0 1.6

ο Atm. at about 23 ° C)

JS 3 · Carbon Dioxide Permeable- 0.6 0.12 2.0 16.0 112.0 280.0 4.8

_> speed (cm3 (day / m ² / mm-

cn Atm. at about 23 ° C)

ü 4. Water permeability 0.36 0.5 0.8 1.3 1.5 1.6 1.2

ο (g / üag / mvmm at about
- "25 ° C and 50% rel.
"* Humidity)

5. Toughness at about 0.3 0.5 3.0 0.2 0.2 0.2 1.0

23 ° C

6. Product absorption <1% <1% 2% 10% 40% 80%

(% Loss)

7- Water vapor permeable- 1.6 1.8 2.4 4 4.8 5.2 5.6

speed (g / day / m2 / mm at approx
38OC and 95% rel. ro

Humidity _*

8. Stiffness (modulus 59 59 55 52 52 52 59 ⁴ ^ 1000 kg / cm ² ) ^

9. Heat foaming temperature (° C) 107 ° 95 ° 95 ° 82 ° 82 ° 82 ° 98 ° <7>

Table I (port setting)

test

VIII

IX

Examples X XI XII

XIII

1. Processability of the A polymer, wherein

A - compatible and B mean »less compatible

2. Oxygen permeability 0.8 (cm ^ / day / mvmm-

Atm. at about 23 ⁰ C)

3. Carbon Dioxide Permeable 2.4 speed Xcm3 / day / m / mm-

Atm. at about 23 ° C)

4. Water permeability 0.6 (g / a? Ag / m <ymm at about

23 ° C and 50 % rel. Humidity)

«" 5 toughness at around 23 ° C

6. Product absorption (% loss)

0.3

7. Steam Tue

speed (g / day / m ² / mm at approx. 380 ο and 95% rel. humidity

8. Rigidity (modulus 1000 kg / cm2)

9 «Vgrme deformation temp.

- 2.0

0.36 0.6 0.16 0.16

1.2

42 42

98 ° 110 ° 110 ¹

0.16

0.72 0.44 0.32 0.32 0.32

1.2

42

110 '

XIV

6.0

0.48 1.8 0.48 0.48 0.48 18.0

0.32

0.3 0.3 0.3 0.3 0.3 1.0

30%

1.2

test

dragonfly I (continued)

Examples II III IV V

VI

—A
CJT

10. Permeability for product components

a. Polar liquids

b. Non-polar liquids

(g / day / m2 / mm at about 23 ⁰ C and 50% relative humidity

11. Tensile strength (kg / cm ² at 23 ⁰ C

12. Pasteurization

13. Chilling behavior

14. Odor transmission to control samples

15. Loss of carbonate after 3 months at about 23 ^° C

16. Clarity

17. Flammability

0.08 0.04

840

0.2
0.08

700

2.0 8.0

63O

Bites 32.0

63O

Bites 40.0

630

Examples I to Uli passed without breakage or deformation - f-

1.5% 1.0% 3.5% 2.0% 2.0% 2.0% 2.0% no no no some very
much very
much no 4A%
90% <1%
80% 1.5%
80% 20%
80% 100%
80% 100%
80% <9%
90% see. see. see. see. see.
JL see. see.

! Table I (continued)

At game

test

VIII

IX

XI

XLI

XII

10. Permeability for product components

a. Polar fluids 0.08

b. Light polar liquids 0.04

(g / day / m ² / mm at about 23 ⁰ O and 50% relative humidity)

O, 08 O, 08 0 , 08 0 .08 0 , 08 2 , 0 0, 04 0, 04 0 , 04 0 , 04 0 , 04 0 , 04

tn 11. Tensile strength

ro (kg / cm2 at 23 ⁰ C)

^ 12. Pasteurization

- * 13 · Creep behavior
ο

- * 14. Odor transmission

versus control samples

770

770

840

840

840

no no no no no no

Carbonate loss after 3 months at about 23 ⁰ G

16. Clarity
17 · Flammability

<c- Examples I through XIII passed without failure
or deformation

1.5% 2.0% 1.0% 1.0% 1.0% 7.0%

very much

see III

90% cf.

90% 90%

see.

80%

see.
I.

see,

80%
see.

Remarks:

I. Self-sustaining, non-polluting, low odor, ash content -C "*

II. No further burning after removal of the flame; non-polluting odor; lower ash - """J content. J £ J

III. No further burning after removal of the flame; HCl is formed during the firing; high ^ Ash content

The container according to the invention must be made of a nitrile polymer are produced, the main component of which is obtained by polymerization from at least one monomer, which contains at least one nitrile group (-CN) in the molecule. This should be polymerized monomers bearing nitrile groups in an amount of at least 50% by weight in the polymer and are preferably present in an amount which, expressed as nitrile group functionality, is 66 mol ^ acrylonitrile, especially preferably between 66 and 97 »5 molar acrylonitrile equivalent is to give the container the combination of chemical and physical properties that is required is to use the container for the packaging of pressurized liquid materials such. B. carbonated beverages etc. to make usable. As a result of the excellent Permeability properties that these polymers show, resulting in an extremely low loss of COp pressure (experiment 15) and the inert properties (experiments 10 and 14-) compared to the content, the inventive Containers without adverse effects on the product that is placed in such a container for the second time, find use again. Although a wall thickness of 0.3 to 1.5 mm is generally required to accommodate products is, for which the containers according to the invention are particularly suitable, should in the event of an intended reuse the average wall thickness of the container must be at least 0.76 mm to avoid additional wear and tear withstand during use. Sa the wall thicknesses

20981S / 1015

fluctuate distributed over the body of the container, the strength ranges given in the present description are before Average values determined by the following formula:

Container

Weight? of the container surface) (, density).

For the purposes of the present invention, however, no area of the container wall should be thinner than 0.2 mm otherwise the properties of the material are not suitable to achieve the critical values described above and buckling or breakage due to internal pressure may occur.

Typical materials which are suitable for use as thermoplastics for the production of the containers according to the invention are acrylonitrile, methacrylonitrile, ethacrylonitrile, propacrylonitrile, cc-chloroacrylonitrile, a-bromoacrylonitrile, a-fluoroacrylonitrile, fumaric acid dinitrile, maleic acid dinitrile, a-cyanididene, vinyl Cyanoacrylic acids, α-cyanoacrylates, such as. B. cc-cyanoacrylic acid esters, such as. B. a- a-methyl acrylate Cyanoacrylsäureäthylester etc., 2,3-dicyanobutene-2, 1,2-dicyanopropen-i, α-Methylenglutarsäurenitril etc. Preferred monomers are acrylonitrile, methacrylonitrile or mixtures thereof. The preferred amount of polymerized acrylonitrile in the polymer is up to 86 mol%, while the preferred amount of polymerized methacrylonitrile is 75 to 95 mol%.

209815/1015

Provided that laier through the finished product no undesirable properties can be imparted theoretically any monomer that contains nitrile groups with the Component of the polymer is copolymerizable, find use for the purposes of the invention. Such a comonomer is preferred, although not necessary, for the improvement of the processability of the thermoplastic present, as in the event that an excess of GN groups is present in the polymer, the material has a relatively high degree of polarity, and the main molecular chains tend to be mutually attracted, reducing the processing properties of the polymer in the melt is decreased. The comonomer tends to reduce this tendency without affecting the barrier properties can be substantially reduced. This comonomer can be present in the polymer up to a content of 40% by weight, preferably 34 mol% and especially preferably in an amount from 10 to 30 molj6 are present. Examples of such monomers are ethylenically unsaturated aromatic compounds such. B. styrene, a-methylstyrene, o-, m- and p-substituted Alkyl styrenes, such as. B. o-methylstyrene, o-lthylstyrene, p-methylstyrene, p-ethylstyrene, o-, m- or p-propylstyrene, o-, m- or p-isopropylstyrene, o-, m- and p-butylstyrene, o-, m- or p-sec-butyl styrene, o-, m- or p-tert-butyl fltyrene etc., α-halogenated styrene, such as. B. a-chlorostyrene, α-bromostyrene, ring-substituted, halogenated styrenes, such as 2. B. o-chlorostyrene, p-chlorostyrene, etc .; ethylenically unsaturated Acids, carboxylic acids, such as. B. acrylic acid, meth-

209815/1015.

acrylic acid, propacrylic acid, crotonic acid, etc. vinyl esters, such as z. B. vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, etc .; Vinyl and vinylidene halides, such as. B. Vinyl chloride, vinyl bromides, vinylidene chloride, vinyl fluoride etc. j vinyl ethers such as B. methyl vinyl ether, ethyl vinyl ether, Propyl vinyl ether, butyl vinyl ether, a-01efine, such as. B. Ethylene, propylene, butene, pentene, hexene, heptene, octene, isobutene and other isomers of the aforementioned compounds.

According to the present invention, up to 40% by weight, preferably 0 to 15% by weight of an impact resistance modifier Material can be used which is compatible with the polymer according to the invention on a high nitrile basis is. The proportion of such materials should be compared to the amount of non-Mtrilgruppe-containing material in the Polymer does not exceed 40% by weight, preferably 15% by weight, if drastic changes in properties are to be avoided. Typical means of modifying the Impact resistance, which can be mixed with the polymer according to the invention, are synthetic or natural rubber components, such as B. polybutadiene, butadiene / styrene copolymers, Isoprene, neoprene, HitriL rubbers, acrylate rubbers, natural rubbers, polymers made from butadiene with acrylonitrile, polymers made from methacrylonitrile with tert-butyl styrene, styrene and mixtures thereof, such as. B. A / Ctyl nitrile / butadiene copolymers, methacrylonitrile / butadiene en-copolymers, acrylonitrile / styrene / butadiene-iDerpolymer-

209815/1015

2U7561

sate, methacrylonitrile / styrene / butadiene terpolymer, methacrylonitrile / tert.-butylst ^ rol / butadiene terpolymers, Acrylonitrile / tert-butylstyrene / butadiene terpolymers, Ethylene / propylene copolymers, chlorinated or fluorinated rubbers etc. This rubber component can be used in the inventive Polymers are incorporated using one of the known methods, for example by direct polymerization of monomers, through polyblends, by grafting the monomer mixture onto a rubber-like molecular main chain, by physically mixing the rubber component, etc. Other tough polymers that are not considered to be Rubber-based materials considered or known can be used as a means of modifying impact strength to serve. This subheading includes polycarbonate, polyethylene, polyethylene / vinyl acetate, polyethylene / vinyl alcohol, polyamides, Polyketones, phenoxy compounds, polyacetals and silicones.

According to the invention, conventional additives such as Dyes, fillers, pigments, plasticizers, stabilizers, processing aids, etc. in the material of the container Find use.

209815/1015

Claims (6)

Plastic container in elongated shape with a wall thickness of 0.3 to 1.5 mm for holding carbonated beverages with a pressure of 0.3 to 14 kg / cm and an impermeable closure, characterized by the following properties: a) an oxygen permeability of less than 4 cmV day / m ² / mm-atm. at about 23 ° C j b) a carbon dioxide permeability of less than 12 cm ⁵ / day / m ² / mm-atm. at about 23 ° G; c) a water permeability of less than 1.6 g / 0 ^{μag / m 2} / mm at about 23 ° Cj d) a tensile strength of more than 700 kg / cm e) a stiffness module of more than 32,000 kg / cm ² } f) a creep of less than 7 # after 1 week of storage the pressurized beverage at 38 ° C; g) no significant effect on the taste of the beverage after storage within the container during of a period up to. 6 months; wherein the container is made from a polynitrile compound which has a SLtrile group functionality which is at least 66 MoISt polyacrylonitrile equivalent and contains up to 34 mol # of at least one copolymerized monomer which has at least one ethylenically unsaturated bond in the molecule.
209815/1015 2. BeMIt he according to claim 1, characterized in that the polynitrile compound 75 Ms 85 mol% acrylonitrile or 7 ^ Ms 95 mol% methacrylonitrile and optionally Ms to 15 wt.% Of an impact-modifying agent. 3. Container according to claim 1, characterized in that at least one copolymerized monomer is styrene or methyl vinyl. 4. Container according to claim 1, characterized in that it has the shape of a bottle or a can for holding a carbonated beverage based on cola or beer. 5. Plastic bottle with an average wall thickness of 0.3 to 1.5 mm for holding a bottle under pressure from 0.3 to 14 kg / cm standing cola beverage with an impermeable closure, characterized by the following minimum properties: a) an oxygen permeability of less than 4 cm ^ / day / m ² / mm-atm. at about 23 ° C; b) a carbon dioxide permeability of less than 12 cmVday / m ² / mm-Atm. at about 23 ° C; c) a water permeability of less than 1.6 g / day / m ² / mm at about 23 ° Cj d) a tensile strength of more than 700 kg / cm about 23 ° C; 209815/1015 2U7561 e) a stiffness modulus greater than 32,000 kg / cm; f) a creep of less than 7% after 1 week of storage the pressurized beverage at about 58 ° C; g) no significant effect on the taste of the beverage after storage in the container during a period of up to 6 months; wherein the container was made of a polymer that 66 to 97 > 5 mol% of a polymerized monomer from the group of acrylonitrile, methacrylonitrile and mixtures thereof and 2.5 to 34 mol% of at least one copolymerized Monomers from the group of ethylenically unsaturated, aromatic compounds, the ethylenically unsaturated Acids, the vinyl ester, the vinyl and vinylidene halides, the vinyl ethers and / or the α-olefins. 6. A method for the protection of carbonated beverages, characterized in that the drink is a Pressure of 0.3 to 14 kg / cm in an elongated plastic container fills, which has an average wall thickness of 0.3 to 1.5 mm and then one impermeable closure tightly connects to the wall of the plastic container, leaving the pressure inside is retained, the container being made from a polynitrile compound that has a nitrile group functionality possesses which is equivalent to that of a polymer containing at least 66 mol% polyacrylonitrile 2 0 9 8 15/1015 2U7561 holds, and up to 34- MolS & at least one copolymerized monomer from the group of ethylenically unsaturated aromatic compounds, ethylenically unsaturated acids, vinyl esters, vinyl and Vinylidene halides containing vinyl ethers and / or the α-01efine, whereby the container has the following minimum properties: a) an oxygen permeability of less than 4 cm ⁵ / day / m ² / aa-atm. at about 23 ° C; b) a carbon dioxide permeability of less than 12 cm ⁵ / g / m ² / mm-AtBi. at about 23 ° C; c) a water permeability of less than 1.6 g / day / m ² / mm at about 23 ° C ₁ d) a tensile strength greater than TOO kg / cm j e) a stiffness modulus greater than 32,000 kg / cm j f) a creep of less than 7 % after storing the pressurized beverage at about 38 ° C for 1 week g) no significant effect on the taste of the beverage after storage within the container for a period of up to 6 months. 209815/1015 Lee rTe i 1 "