CA1060360A

CA1060360A - Multilayered container

Info

Publication number: CA1060360A
Application number: CA283,589A
Authority: CA
Inventors: Emery I. Valyi
Original assignee: Individual
Current assignee: Individual
Priority date: 1976-11-22
Filing date: 1977-07-27
Publication date: 1979-08-14
Also published as: BE857946A; FR2371348A1; DE2742408A1; US4107362A; JPS5365181A; FR2371348B1; CH626582A5; JPS5857315B2; SE7708782L

Abstract

ABSTRACT OF THE DISCLOSURE
A multilayered hollow plastic container having improved resistance to permeation by unwanted gases, especially injection blow molded containers having a preformed inner lining which is applied to a core prior to the formation of the composite parison. One layer is a barrier plastic having substantial but incomplete resistance to gas permeation, and another layer contains a getter material capable of binding unwanted gas uniformly dispersed throughout.

Description

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BACKG~OU~ OF ~HE INVENTION
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The use of partia]ly permeable materials, e.g., one of the so-called gas barrier plastics, presents a novel problem in the packaging of perishable commodities, such as edible oils and ~ats, other foods, carbonated beverages, wine and beer, and also o~ other materials that are affected by continuing exposure to the atmosphere. ~he problem ~ deri~es ~rom the fact that, in contrast to the materia~s customarily used ~or packaging under such conditions, namely glass and metal, these materials are partially permeable and thus do not provide absolute protection because they a~ never completely impervious.
` The art has developed materials that are relatively impervious to given substances. ~hese 'better~ materials tend to be more expensi~e, and despite the added cost even théy ha~e a ~inite permeability.

~ - 2 _ For example, in the field of plastics the approach taken heretofore was to develop barrier pol~ner~ with better permeation impedance for specific substances, such as oxygen carbon dioxide, water vapor, aromatics, etc. These effort~
did meet with considerable success. Thus, for example, the permeation rate of oxy~en was reduced by a factor of several orders of magnitude from polystyrene to the newly developed acrylonitrile copolymers, or to a lesser degree to terephtalic polyesters and polyvinyl chloride. Neverthcless, a definite ~` amount of permeation remain~ ~en in the best plastic due 11 to the molecular arrangement thereof.
Composite blow molded containers have been prepared as described in my prior U.S. Patents 3,719,735 and 3,717,544.
` I According to said patents, previoùsly formed sleeve-like lS liner~ are applied to a blow core of an injection blow molding apparatus, plastic is injected around said liners while upon the cores, and the resultant composite parison consisting of the liner and the in~ected plastic is expanded together ' into conformance with a blow mold. While these composite !' containers represent a considerable improvement due parti-i~ cularly to their ability to combine properties of different plastics, one of which may be a barrier plastic, a definite i~ amount of permeation still remains even in these improved ~ materials.
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Il 1060360 ~s a result, a new factor mu~t be introduced whcnever i~ it is desired to package perishables in plastic or other partially permeable materials, namely shelf-life. Ylhile a metal can or glass jar will lceep its contents unchanged for a practically indefinite period, a time limit, mostly in terms of weeks, must be prescribed for the plastics, modified paper, etc.
Accordingly, it is a principal object of the present `! invention to provide a method for the preparation of multilayeret ~' h~llow plastic container~ having improved resistance to gas permeation, especially air permeation, and also to provide an improved container.
It is a further object of the present invention ,! to provide a method as afor~said which i9 inexpensive and ~ convenient and which utilizes a partially permeable barrier material in an arrangement which significantly increases the i~ resistance of the container to ~as permeation.
i~ Fkrther objects and advantages of the present invention will appear hereinafter.
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'~ SUMMARY 0~ THE IrnVENTION
ii ~l In accordance with the present invention, it has ~l been ~oun~ that the foregoing objects and advantages can be readily obtained. The present in~ention relates to a method ,, 1i .
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Il i060360 of making multilayered hollow plastic containers formed on a core in a mold by molding the plastic around the core in a mold cavity, and preferably including the ~tep of sub-sequently expanding in a blow mold. In accordance with the 5 ; improvement of the present invention, a sleeve is formed at least a portion of which is a carrier containing a getter mat~rial uniformly dispersed therein capable of binding unwanted gas, the sleeve is applied to the core, a barrier plastic layer is formed around said sleeve, said barrier 10 ` plastic having substantial but incomplete resistance to gas i permeation, the sleeve and barrier laycr are then preferably expanded together in a blow mold to form a multilayered hollow plastic container having improved resistance to gas pel~eation, , with the layers being adhered to each other s-lbstantially t5 ` o~er the entire contacting area. In a prelerred embodiment the sleeve is a laminated composite comprising an inner layer which is the carrier containing said getter and an outer layer which is the barrier~ The composite sleeve i5 then ,~ applied to the core and a third plastic layer is pressure 20 ,~ molded therearound. The resultant material is then expanded together in a blow mold to form the container.
j~ The resultant container is a seamless, multilayered, il hollow plastic container having an inner layer of a plastic ~! carrier containing a getter material capable of binding unwanted 25 `,` gas and an outer layer of a barrier plastic ha~ing substantial , _ 5 _ ~j .

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Il 106V360 but incomplete r~sistance to gas permeation, whcrein said I' container has a bottom and slde walls integral therewith ~na l extending therefrom terminating in an open mouth suitable for being closed by a cover having improved resistance to unwanted gas permeation. In a preferred embodiment the container contains three (3) layers, with the innermost being the getter-containing carrier layer, the middle layer being the barrier material and the outer layer being a pressure ` molded plastic. The outer pressure molded layer is preferably " an incxpensive plastic, ~uch as polystyrene or a polyolefin having sufficient mechanical strength to protect the content ,~ of the container.
The getter is a material which is capable of chemicall~
ii binding, absorbing, or adsorbing the unwanted permeating gas.
,, ~hus, for example, an anti-oxidant may be used to absorb and bind oxygen. The carrier containing dispersed getter material is laminated ~Yith a barrier plastic in accord~nce with the i' method of the present invention, wherein the barrier is !l chosen to provide substantial but incomplete resistance to ~ permeation of the unwantea gas. Naturally, the carrier must ~ contain sufficient getter to bind substantially all gas `~ which permeates the barrier. Hence, i~ migration of oxygen is to be prevented the barrier would be a plastic which is il resistant to the migl~ation of oxygen, as an acrylonitrile 1~ containing polymer, and the carrier would contain sufficient ~, .

,. 1060360 , antioxidant to bind us~3tantially all oxygen permea-ting ii th~ barrier.
The resultant compo~itc has grcatly i~proved resis-tance to gas permeation. Naturally, after filling the container a cover should be employed which is also resistant to gas permeation, as a cover of the composite of the prescnt invention or a metal cover. Hence, a container may be fabri-cated in accordance with the presènt invention which is characteriæed by being virtually impervious to gas permeation.
In operation the resultant composite is capable of using a good barrier which ne~ertheless has a finite permeability, permitting comparatively small amounts of the unwanted gAS to migrate therethrough in such a manner that j said unwanted gas, to the e~tent that it so migrates and at the rate of its migration; is "captured" by a getter capable of stopping further migration, i.e., diffusion or ;j other flow of the gas. Obviously, if the barrier were to permit substantial permeation, i.e., if it were a poor barrier, ~ the amount of getter that may be practically juxtaposed thereto ii would be exhausted too soon for practical purposes.
If necessary, a plurality of layers may be employed;
or example, the carrier containing dispersed getter may be sand~Yiched between two barrier layers by providing a sleeve !` that is a laminate with the carrier between two barrier layers. Alterl1atively, one may provide a laminated sleeve . ~ .

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, ~060360 with an lnner carrier and two outer barrier layers, Thus, !! one may desi~n a composite having resistance to a variety of 1~ gases based on the characteristics of the barrier layers i' and/or the gètter. A~ a still further alternativc two or more different getter materials may be used to provide protection against two or more gases together with two or more outer barrier layers, if desired.

BRIE~ DESC~IP~ION OF DRAWINGS

The present invention will be more readily under-~tandable from consideration of the accompanying drawings in uhich:
Figure 1 is a diagrammatic view of- Q forming mold i! ~or forming the plastic sleeve, with the formed sleeve shown ,i in phantom;
~ ~igures 2, 3 and 4 are elevations, partly in section, t~ showing the steps of the process of the present invention, " with Fi~ure 4 including the cover;
1l Fi~ure 5 is a sectional view of another embodiment of a composite sleeve wherein the getter is embedded in the carrier;
i~ Fi~lre 6 is a sectionæl view of a three-layered '; composite sleeve of the present invention;
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j; ~igure 7 i8 an elevation, partly in section, showing the process of the pre~ent invention Ylith a plurality of blow cores moveable in a rotary direction;
~igure 8 is an elevation, partly in section, showing laterally moveable blow cores; and ~igure 9 is a section taken on the line IX _ I~
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"DE~IL~D ~SCRIPTION
ii ~' In the pre~erred embodiment the process of the present invention forms a composite container having an outer layer of plastic material, a second layer within said outer layer, adjacent thereto and adhered thereto of a barrier 15 ` plastic having resistance to gas permeation, and an inner ;~ carrier layer relative to the barrier layer adjacent the i~ barrier layer. The process of the prescnt invention results ; in the layers being sufficiently adhered one to the other I so that delamination will not readily occur.
~, The barrier layer is a plastic material which is capable o~ hindering substantially the permeation of an un~anted gas therethrough. Typical barrier plastics include ~1 acrylonitrile copolymer~, terephthalic polyesters, polyeth~lene ' terephthalates, polyvinylidene dichloride, and the like.
Naturally, the particular barrier or combination of barriers employed depends upon the particular results desired.

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j! The outermost layer is preferably an inexpen~ive ` pla,tic, such as polyolefins, polystyrene, polyvinylchloride or the like, which is injection molded around the laminated ' sleeve to pro~ide additional strength and rigidity to the container at a low cost.
In accordance with the present invention as sho~m in Figure 1, a getter material 1 is incorporated into and uniformly dispersed throughout the carrier 2, with a barrier ~layer 2a laminated thereto. ~his`enables a volume of getter i to be distributed throughout the carrier to provide a lar~e " surface for contact with the unwanted gas. Thus, as shown in ~ re 1, the carrier should be capable of holding the ,~getter uniforn~y distributed throughout the carrier. Naturally, the getter may be placed on the surface of the carrier, as '~ for example sho~ in Figure 5 wherein the getter is embedded in the carrier, so that in the final product the getter is inated between the barrier layer and the carrier.
, ~he getter will usually be an antioxidant i~ its ~ function is to be the pre~ention of oxidation (and ~ancidity), ~ ~or example, butylated hydroxy~nisole, di-tertiary-butyl-paracresol t propyl g~llate, phenylenethiourea, and aldol-~l alpha-naphthyl~ine. Naturally, others will readily appear i~ to one skilled in the art. A substantial number of proprietary '! antioxidants are known to exist, as for example, listed o~
` pages 699 - 703 o~ the Modern Plastics Encyclopedia, Vol. 50, No. 10~, October 1973.
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, - 10 _ V-255 , I~` 10~0360 i' The getter may be designed to react with other ~ases , than oxygen; for example, activated charcoal may be used, or '~ bactericides may be employed to minimize bacteri~ or virus ~ transmission. The getter material may be chosen to sclectively bind virtually any unwanted material. The dispersion of the getter material in an inexpensive carrier suited to receive the dispersion is a particularly convenient and effec-tive procedure for a variety of reasons. It a~oids having ~ to a~nix the ~etter with the barrier and possibly vary the !i desirable properties thereof. It enables one to select an inexpensive carrier which is especially suitable for the particular getter employed, and disperse the getter throughout ` the carrier so that a large volume of getter surface is available for contact with the unwanted molecule. It avoids ~15 ,; having to tamper with the thickness of a possibly expensive barrier layer and utilize on~y so much of t~e barrier layer ~, as is necessary to achieve the desired ~oal.
,` The physical requirements of the getter system relate to the processing characteristics of its components.
~ ~hus, i~ it is desired to produce a sleeve from a film, it will usually ~e necessary to choose the getter with the fact in mind that it must be stable at the temperature at which the carrier may have to be worked for the blending-in of the `I getter; and also at the temperature at which the system has to be processed to convert it into a unitary structure, e.g., "

, 1060360 a film by eY~trusion. The system may of coursc assume other i forms than film; it may, for example, be a pressure molded piece. In any case the lcnown art of preparing the system , will dictate the ~pecifie selection of its components, beyond the basic selection of the chemical function. One particular category of getter may be that of surface active agents, as for example carbon, whereby the carrier would be applied to hold such getter without impeding its surface~ l`he carrier ~ may of course be used to provide characteristics to the lj structure of which it is a part that are per se unrelated to the specific purposes of this invention: it may be colored, -for decorative effect; or, it may be a barrier in its o~n right, as, for example, a polyolefin carrier would naturally 'I be water vapor barriers.
li In accordance with the embodiment shown in Figure 1, a getter material 1 is unifo~lly dispersed throughout a sheet-!~ like carrier 2, as for example, polyethylene, and a barrier layer 2a laminated thereto. ~he getter-containing carrier-~ barrier composite is placed into juxtaposition with a mold 3 ~ having a mold cavity 4 conforming to the desired shape of the sleeve. Vacuum is applied in the mold cavity through connection i~ 5 ~nd carrier 2 is converted to the shape of the mold cavity 4 ji~ to form the cup-like sleeve 6 (shown in phantom in Figure 1) ~I by vacuum formin~, i.e., by a drawing procese that intrin-

2~ s sically produces attenuation of the carrier 2. ~utting means ` (not shown) may cut the formed liner frorn the web.

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~i Naturally, the sleeve may be formed by a wide variety of other ! methods well known in the art. For example, instead of drawing into a mold, th~ material may be drawn by vacuum over ~I a shaped plug, or produced by cooperation of a mold and plug ! as is lcno~l in the thcrmoforming art, or it may be wrapped into a container shape, as is customar~ in the manufacture of paper containers.
Cover 10 (~igure 4) should also naturally provide I resistance to permeation as being formed from the composite j, o~ the present invention. l`he cover may be applicd to the i container by any suitable or convenient method, as by heat '~ sealing or providing the container and cover with mating threaded portions, for example, threaded portions 11 and 12, i respectively. If the container protects against oxygen ~ permeation, for example, entrance of oxygen through the sealed ` cover may be prevented by a variety of methods, as by heat sealing the cover to the container, or by providing a depending i~ barrier flange such as ~lange 13 so that the carrier layer is ; not exposed to the permeating cnviror~ent.
,~ Figures 2, 3 and 4 show the formation of the lined hollow plastic containers of the present invention wherein the previously for~ed sleeve is applied to`a blow core of an i~ injection blow molding apparatus, plastic is injected around ~ said liner Y~hile upon the core, and the resultant composite `25 ` parison consisting of the composite liner and the injected ~ i;
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plastic, expanded together into conformity with a blor~ ~old.
,i Referring to the drawings in more detail, Figure 2 shows ~n extruder or other known injection unit 20 which ~ provides hot molten plastic under pressure to a parison mold assembly. The parison mold assembly consists of the parison mold 21 ~Yhich communicates with the injection unit 20 ~y means o~ runnèr plate 22, a neck or rim mold 23 and the core 24 (which is usually a blow core) whereby the parison mold 21, the neclc mold 23 and the core 24, when assemble~ as sho~n, '~ ~orm th~ parison mold cavity 25 between them. Figure 3 shows il a blow mol~ assembly comprisin~ a blo~Y mold 26 and the neck ~, mold 23 and core 24 previously referred to in conjunction ~ with the parison mold assembly.
!' In operation, liner 6 (prepared as in Figure 1) is applied to the core 24 before said core is placed into `~ parison mold 21. The core, together with the liner, is ` introduced into the parison mold together with nec~ mold 23 ~` and the assembly clamped firmly together by a force transmitted i through platen 27. Hot plastic is then pressed into the 2n ~ parison mold cavity from extruder 20 through runner plate 22, around the sleave 6 which is on the core 24. A parison is thus molded forming a composite structure the inner layers of hich arc comprised of the material of the sleevc 6, namely, ; an innermost carrier layer containing the getter material 1 unifo~y dispersed therein and a second barrier layer sdhered ~ 3 i~
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!--255 ,, , ' !l to while it3 outer layer consis~s of th~ material pressed around that ~leeYc from the extruder 20.
If desired, the core 24 may be heated or conditioned ~ by external heating prior to placing the cool liner thereon.
The parison is then transferr~d into the blow mold 26 r~hile still on the core 24 and within the neck mold 23. The core may be provided with an orifice 28 for pressure fluid, usually air. Orifice 28 may b~ closeable and is shown in the closed ~ po.sition in Figure 2 and in the open position in Figure 3.
~, The core may consist of two compone~ts, the plug or poppet portion 29 and the collar or seat 30, whereby the plug is I axially mo~eable to form a valve opening or orifice 28. In accordance with the present in~ention, the parison will be hot enough ~or blowing upon introduction into the blow mold.
~ The parison is then expanded by means o~ fluid pressure through orifice 28 into conformance Y~ith the blow mold to form container 31. The container 31 is removed from the blow mold 26 upon cooling. The blow mold may be cnnstructed in t~o halves 32 ` and 33 which may be separated, as shown, releasing the expanded ~inished article 31 which contains an inner layer representing the liner 6. The parison mold 21 ana the neck mold 23 may " al~o consist of more than one part each which may be separable , to facilitate the removal of the parison or of the finished '! article, as shown.
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~~' 1060360 Alternatively, one may dispense with the blowing operation and simply mold the container in desired configura_ tion. In a still further emhodiment, one may simply provide an inner, getter~containing carrier with a barrier plastic .
molded therearound, The mechanical operation of the several elements shown in ~i~ures 2 to 4 may be carried out by means dcscribed in my U.S. ~atent No~ 3,0~9~4G~ and in numero~s other patents, such as for exa~ple, U.S. Patent ~o. ~,913,762, U.S. Patent No.
~ 2~29~,716 and others. An apparatus particularly well suited for the purposes of the present invention is described in my , U.S. Patent No. ~e. 27,104~
Frequently a plurality of blow cores are used as l`~ shown in Figure 7 ~hich provides a plur2lity of blow cores ` 41, 4~, 43 and 44 mounted on a turntable 45 rotating on ; vertical shaf~ 46 by driving means 47 and 48. Thus, the blow cores rotate from one station to another, with core 41 being S}lOt~ at the parison molding station in parison mold ~9 ~ covered by liner 50 with injection no~zle 51 in position to ~ inject plastic therearound to fo~ the composite parison.
Core 42 is in the blow molding station in blo-Y mold 52 with i~ the composite parison being expanded into composite article - , 53. The blow mold is shown as being separable by means of '~ pistons 54 and 55. Core 43 is shown in the article removal statioIl with article 53 being shown separat.d therefrom.

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V-255 ~ ' l~ Core ~4 is shown in the liner receiving station for rcceiving Il a liner 26 from liner storage means 56, which is moveable axially by means of piStOII 57 to apply a liner 50 on core 44.
According to ~i~ures 8 and ~, two blow cores 60 and 61, or more if desired, are mounted on a common platen 62 which may be rotated or oscillatèd around shaft 63 by a suitable means such as by rack 64 acting on pinion 65 moving in the direction o~ the arrow, which shaft also serves to guide pl~ten 62 in its movements parallel to the axis of the ` blow cores. As shown in Figure 8, when blow core 60 is in alig~nent with blow mold 66, blow core 61 is in ~lignment with ` liner magazine 67. In operation, platen 62 is moved upward `! in the direction of the arrow and inserted into parison mold l~ 68. The parison is then molded therearound by means of nozzle i 69 and the assembly consisting of platen 62 and two cores 60 and 61 is ~owered. A blow mold 66 is moved into juxta-~j postion with core 60 by means of piston iO, as shown in dot-da~h lines, and the finished article blown therein.
I` The blow mold with the finished article is then removed from ~ the blow core. At the same time, the liner 71 is applied ~i to the core by moving maga2ine 67 into engagement therewith by means of piston 72. The assembly consistin~ of platen 62 ` and blow cores 60 and 61 mounted thereon is rotated around rod 63 in the direction of the arrow so as to repeat the cycle.
` 25 ~I Since the time used to expand the parison on one core is also i` .

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As shown herein, the barrier plastic should be outcrmost ~ith rcspect to the getter-containing carrier ma~erial, ~hus, if oxygen pe~neation into the contents of a container is to be impeded, the barrier layer would provide primary protection against the oxy~en permeation and oxygen permeating the barrier plastic would thell be bound up by the ~ getter, ~; As an alternative embodiment one may use a liner as shown in Figure 5 wherein getter 80, coated with a permeable ~ carrier 81 (or alternativcly uncoated), is embedded in a ;~ carrier plastic 82 and a barrier layer injected therePround ~``, or laminated thereto. As a still ~urther alternative, one i may use a layered liner containing a plurality of layers as shown in ~igure 6 wherein two plastic barrier layers 83 and ~, 84 are placed on either side of a carrier 85 containing a getter 8~ uniformly dispersed throughout, i~ This invention may be embodied in other ~orms or l' carried out in other ways without departing from the spirit ii or essential characteristics thereof. ~he present embodiment i is therefore to be considered as in all respects illustrative and not restrictive, the scope of the invention being j~ indicated by the appended claims~ and all chan~es which come ,' within the ~eaning and range Or equivalency are intended ! to be cmbraced therein.

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Claims

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:-

1. A composite plastic container having improved resistance to unwanted gas permeation characterized by a barrier plastic layer having substantial resistance to said gas permeation, a carrier layer adjacent said barrier layer, the two layers being adhered one to the other substantially over their entire contacting areas, and a uniformly dispersed getter material capable of binding the unwanted gas in an amount sufficient to bind up any unwanted gas permeating the barrier layer, said getter material being carried by said carrier layer, wherein the barrier layer is in the position first exposed to the unwanted gas, whereby the barrier layer provides initial and substantial but incomplete resistance to said gas permeation and gas passing through the barrier layer contacts dispersed getter material and its bound up thereby.

2. A container according to claim 1 wherein the barrier layer is outermost with respect to said carrier layer.

3. A container according to claims 1 - 2 wherein said container is rigid, has a hollow bottle, jar or cup-like configuration and an open neck closed by a cover having resistance to said unwanted gas permeation.

4. A container according to claim 3 wherein said cover includes a depending flange covering the carrier layer so that the carrier layer is not exposed to said unwanted gas.

5. A container according to claims 1 - 2 wherein said getter is uniformly dispersed within said carrier layer, or uniformly dispersed between said carrier layer and barrier layer, or embedded in the barrier layer.

6. A container according to claims 1 - 2 wherein said carrier layer is sandwiched between two barrier layers.

7. A container according to claims 1 - 2 wherein said container is a seamless blow molded container.

8. A container according to claim 7 wherein the inner layer is a previously formed`, sleeve-like liner, the outer layer is injected around said liner, and the inner layer-outer layer composite is expanded together into conformity with a blow mold.

9. A container according to claims 1 - 2 wherein said carrier layer is an inner first plastic carrier containing said getter uniformly dispersed throughout, a second intermediate barrier plastic layer adjacent said first layer, and a third pressure molded outer plastic layer adjacent the second layer, said layers being adhered to adjacent layers substantially over their entire contacting areas, wherein said container has a bottom and side walls integral therewith extending therefrom and terminating in an open mouth suitable for being closed by a cover having improved resistance to unwanted gas permeation.

10. In the method of making multilayered hollow plastic containers formed on a core in a mold by molding the plastic around the core in a mold cavity, the improvement which is characterized by forming a laminated sleeve of a first carrier layer containing a uniformly dispersed getter material capable of binding unwanted gas and a second barrier plastic layer, applying said sleeve to said core, and molding a plastic material around said sleeve and core to form a hollow plastic container having improved resistance to gas permeation.

11. A method according to claim 10 wherein said lined hollow plastic container is subsequently expanded in a blow mold.

12. A method according to claims 10 - 11 wherein said molding is pressure molding.

13. A method according to claims 10 - 12 wherein said first carrier layer is the inner layer and said second barrier layer is outermost with respect to said carrier layer.

14. A method according to claims 10 - 12 including providing a sleeve having an inner barrier layer, a central carrier layer containing said getter, and an outer barrier layer.

A method according to claims 10 - 12 wherein said core is moveable between successive stations to apply said sleeve thereon and to mold a plastic material around said sleeve and core.

16. A method according to claim 15 wherein said core is rotatably moveable or axially moveable.

17 A method according to claim 15 wherein the core is moveable between the further successive stations to expand the sleeve and molded plastic together in a blow mold to form said container, and to remove said container therefrom.

18. A method according to claim 17 including a plurality of cores.