DE1504858A1 - Impermeable packaging - Google Patents

Description

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33 Rue du Prince Albert, Brussels / Belgium.

Impermeable packaging

The invention relates to impermeable packaging, which are impermeable to water vapor, gases or aromatic substances and resistant to chemicals Products are and are in the form of tubes, bottles, passports, squeezable tubes, and the like.

So far, plastic packaging has been in general starting from a single base material, the walls of these packaging are simple and homogeneous.

There is also already a method for producing double-walled bottles (US Pat. No. 3,103,036), but it is a kind of dewar vessel, the two walls being separated by a gas. Moreover, the same plastic is used for the two walls

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Documents (Art. 7 § I Abe. 2 No. 1 Salt 3 of the amendment of 4.9.1967J.

used.

Therefore, when using plastic packaging, the disadvantages of the selected material always had to be considered

it can be accepted without / being remedied. This is especially true for bottles, for which one at the same time good mechanical properties, one increased impermeability to water vapor, gases, oils, Fats and flavorings and good resistance against chemical products, e.g. against oxygen and against moisture to pack sensitive products, such as Food and Chemical Products «

3s it is possible to obtain packaging with good mechanical properties if it is a plastic base Polyvinyl chloride, polyethylene, polypropylene, polystyrene or polycellulose acetate is used, however these packages are impermeable in terms of impermeability unsatisfactory.

The fish polymers with a high content of vinylidene chloride In contrast, have a very high impermeability, but they are poorly suited for making packaging with satisfactory mechanical properties »

It has already been suggested, plastics with good mechanical properties and mixed polymers on the base leg e of vinylidene "to connect to tight packaging to achieve · According to this proposal will be the packaging of rigid plastics ago, then pulls you their inner surface with a Solution or dispersion of a mixed polymer

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based on vinylidene chloride. For example, if you want to manufacture pipes or bottles, this technique has major disadvantages "So the evacuation of solvents or water stops / is a very difficult problem to solve it is very troublesome to obtain an impermeable layer of satisfactory and uniform thickness obtain. So far it does not seem that this technique coating gives satisfactory results in all cases to realize enables

One can do that with the technique of pulling over the Avoid packaging related evils by having two concentric tubes made from different ones at the same time Pressing plastics and making the packaging from the double tube obtained. However, this too Procedure does not allow satisfactory packaging to be obtained in all cases. Actually own generally those obtained from these pipes because of poor surface compatibility of the substances used Packaging the following defects: stripping, poor transparency and fragility,

In contrast to this, it was found that the combination of certain very specific plastics makes it possible to obtain packaging - pipes, bottles, barrels, squeezable tubes - whereby the two concentric layers melt together completely without interrupting the continuity and without disturbing the intermediate layer and consequently represent transparent, impermeable packaging with good mechanical properties. ^{3 u} ^ "- ''

BATH ORIGINAL

_4- ■. 150A858

The invention thus relates to packaging which, in addition to good mechanical properties, has very good mechanical properties increased impermeability to water vapor, Gases, oils, fats and aromatic substances and also good resistance to chemicals Own products ,,

These packs are obtained from two concentric ones and firmly connected extruded tubes, one of which is the mechanical properties the packaging securing tube made of a plastic from the group of polymers and mixed polymers based on vinyl halides and / or Olefins, and the other, the impermeability Securing pipe made of copolymers of vinylidene chloride with a content of 65-95% vinylidene chloride, $ 5-35 Vinyl chloride and optionally acrylonitrile and / or styrene and less than 15 / & one or more conomers with plasticizing or stabilizing properties.

The resins used according to the invention are known. The processes for producing double-walled containers are also known per se.

The novelty and peculiarity of the invention, however, consists in the combination of two clearly defined plastics types that work together to create a double walled package with two layers, arranged concentrically, completely welded to one another without impairing the continuity and none

have weak points in the interface ,, 9 0 9 8 4 2/1311

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This new packaging has good mechanical properties and at the same time an increased impermeability • Permeability to water vapor, gases, CIe, fats and aromatic substances and good resistance to chemical products. Such packaging, soft at the same time have the advantages mentioned above did not exist before.

This also applies to the vessels according to the US patent 2,836,319, "which is not a double-walled container represent in the sense of the invention. Rather, it is a matter of completely different plastics, namely Epoxy resins, coated plastic containers which resins according to the invention are not used

The layer of the packaging ensuring good mechanical properties can be made of polyvinyl chloride, Copolymers based on vinyl chloride, polyethylene, polypropylene and copolymers of ethylene getting produced.

The impermeability of the packaging according to the invention The protective layer can preferably be made of a copolymer of vinylidene chloride with a content of 65-95 » 70-87 $ of vinylidene chloride are produced »The copolymers of vinylidene chloride with vinyl chloride prove to be particularly interesting for this application, but the vinyl chloride can be wholly or partially be replaced by other monomers, such as acrylonitrile and styrene in particular,

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It is also possible to use copolymers of vinylidene chloride containing monomers with plasticizing properties and, if appropriate, stabilizing properties. It has been found that particularly interesting packaging is obtained when the impermeability-ensuring layer consists of a mixed polymer of 65-95 $ vinylidene chloride, less than 35% vinyl chloride and optionally acrylonitrile and / or styrene and less than 15 $ one or several monomers with plasticizing and / or stabilizing properties, selected from the unsaturated, optionally eopoxidized esters of mono- or polycarboxylic acids.

Among the esters mentioned, one can especially enumerate the acrylates and methacrylates of alkyal and epoxyalkyl, the itaconates, pumarates and maleates of dialkyl, dicycloalkyl and diaryl, the itaconates, fumarates and maleates of bis (epoxyalkyl) and of bis (epoxycycloalkyl), the mixed itaconates, fumarates and maleates of alkyl, cycloalkyl or aryl and epoxyalkyl or epoxycycloalkyl, the gaproates, gaprylates, caprates, laurates, myristates, palmitates and stearates of vinyl or allyl, the epoxystearates, epoxytallates, epoxy laurates of vinyl or allyl and the mixed succinates ,

Aaipate ^
Grlutarate, VSebacate of alkyl, cycloalkyl ^ or aryl and vinyl or allyl.

The copolymers of vinylidene chloride with internal Plasticization and internal stabilization have the advantage of not having a migrating and extractable additive to contain.

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The following copolymers used ir

following compositions:

1c 80 parts vinylidene chloride, 17 parts vinyl chloride,

3 parts of 2-J: ethylhexyl acrylate.

2. 80 parts of vinylidene chloride, 14 parts of vinyl chloride, 6 parts of poxystearyl acrylate.

3. 80 parts of vinylidene chloride, 14 parts of vinyl chloride,

5 parts of Tii (2-ethylhexyl) itaconate.

4.7C parts of vinylidene chloride, 26 parts of vinyl chloride,

4 parts of bilsuryl itaconate.

5. bO parts of vinylidene chloride, 12 parts of vinyl chloride,

6 parts of K «cyl- and G-Iycycidyl itaconat,

o «76 parts of vinylidene chloride, 13.5 parts of vinyl chloride,

7 parts of Athyihe xylit ac onat, 1.5 parts of 3-lycidyl- ne t hac r ". ■ 1 at. iim ^ ntxiiiseni ^ qfiigetii ^^

7 75 parts vinylidene chloride, 15 parts vinyl chloride, 10 parts mixed hexyl and slycidyl maleate'iSöSa öixiffi3Stixm3ä5pEcnöd ^^

6c 75 parts vinylidene chloride, 14 parts vinylidene chloride, 6 parts of r- (2-ethylhexyl) funarate, 5 parts of vinyl epoxies t ear at.

SC parts vinylidene chloride, 16 parts vinyl chloride, 4 parts vinyl stearate.

10.77 parts of vinylidene chloride ,. 13 parts vinyl chloride, 1st part acrylonitrile, 7-5 parts vinyl laurate, 1.5 parts ■ m. lyciäylmethaoryläto

11.72 parts vinylidene chloride, 19 parts vinyl chloride, 4 parts each ... iselites vinyl and 2 -.- lth; -lhexylsuecinat,

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12 «75 $ vinylidene chloride and 25 $ vinyl chloride,

Ι3β $ 85 vinylidene chloride and $ 15 vinyl chloride. H. 78 $ vinylidene chloride and 22 $ vinyl chloride.

15. $ 87 vinylidene chloride and $ 13 vinyl chloride.

16. $ 82 vinylidene chloride and $ 13 vinyl chloride as well $ 5 vinyl epoxystearate.

17. $ 83 vinylidene chloride, $ 13 vinyl chloride, and $ 4 dimethyae. itaconate.

18. $ 80 vinylidene chloride, $ 16 vinyl chloride, $ 2 ethylhexyl acrylate and 2 $ grlycidyl methacrylate.

■ ORIGINAL BATHROOM

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1. Division and properties of the bottles "

To bottles with double wall according to the invention to obtain is preferably carried out according to the first of the following processes. You use one Press head that is fed twice by two presses, one of which is the inner layer and the other the outer layer provided. Heads with double axial flux or braids with double soap flux can be used use «It is advisable to use exactly the pressing temperature to choose from each of the substances which the double tube piece form a tight bond between the two pipe sections as soon as they exit the double head to secure «,

The first press is equipped with a common well-known material for processing plastics, which are intended to ensure the rigidity of the bottles. It mixes and melts the polymeric material and then presses it into the outer part of the double head »

The second press is equipped with a well-known one common material for processing mixed polymers based on vinylidene chloride. she mix ^ and melts these copolymers and presses them then in the inner part of the double head.

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In the first part of the concentric double head will be the two plastics at the same time, but separately, gradually brought into tube shape »

In the second part the two molten tubes are brought into intimate contact and then come out of the head under the shape of a piece of tube of homogeneous appearance with a double wall, the two layers of which are made of different materials stick together perfectly. This piece of pipe is immediately shaped into bottles by any known method, for example by shaping under a blown blow. Process using polyvinyl chloride for the outer layer and mixtures or copolymers according to compositions 1, 2, 9 and 13 for the inner layer, bottles with double walls were produced using a concentric double compression head equipped with a clearance of. Core and press nozzle, the diameter of which is 18 mm for the inner core, 22 mm for the outer press nozzle and 19 »6 mm for the intermediate piece, which at the same time plays the role of the press nozzle for the inner part of the head and the core for the outer part ο The bottles obtained are 125 mm high, 55 mm in diameter and weigh on average 28 g. They have a mean total wall thickness of 0.7 mm, of which approximately 0.25 mm is made of Hifsch.poly.mer on the basis of vinylidene chloride. The properties of these bottles can be found in the dragonfly below

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BATH ORIGINAL

Using the same method using the same polymer for the outer layer but starting with mixtures or synthetic polymers according to the compositions 3 »4> 5 * 6 * 7» 8, 10 and 11 for the inner layer, double-walled bottles were made with Using a press head, equipped with a clearance between core and press nozzle, the diameter of which is 17> 4 mm for the inner core, 22.4 mm for the outer press nozzle and 19> 6 am for the intermediate piece. The bottles obtained have a height of 125 mm, a ^{diameter of 55 mm} and an average weight of 35 g. They have a mean total wall thickness of 0.07 mm, of which approximately C. 34 mm is made from the copolymer based on vinylidene chloride. The properties of these bottles also follow in the table.

Imaer following the same procedure assuming a mixture of polyvinyl chloride containing 1 5; j of a Hischpolynier based on butadiene, Styrene and methyl methacrylate for the outer layer and of mixtures or copolymers according to compositions 16, 17 and 18 became double-walled bottles produced by means of a press head, provided with a game of core and press nozzle, the diameter of which is I8mm for the inner core, 22mm for the outer press nozzle and 19.6 mm for the intermediate piece. The bottles have a height of 125 mm »55 mm in diameter and weigh about 28 g. 3They have a mean total thickness of the Wall of 0.7 mm, of which 0.25 mm from the copolymer based on vinylidene chloride <> Their properties are also shown in the table »

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According to a second process, which is used for the production double-walled bottles can be used, a common prease is used to squeeze the inner wall. The pressed tube is cooled, then by pressing with the outer layer by means of a passage encased by an analog press head, such as those used for spinning around pads. It is It is important that the middle core of the core spinning head is equipped with adequate means to handle the inner To condition the drill prior to its coating and to put it in effective way to lead.

Starting from mixed polymers dear compositions 14 and 15 a pipe with a wall thickness of 6.4 mm was pressed out. In that for the passage of the to be wrapped Mouthpiece intended for the object, this tube is inserted through the head. It gets at the press nozzle continuously a uniform layer of molten polyethylene. A pipe section is obtained in this way with double Y / and, the two layers of which stick together. This piece of pipe is then formed into bottles using the blow molding process ο Die Inner layer thickness is about 0.13mm. The properties of the bottles also follow in the table.

A third useful method can be of interest when the two plastics used differ by very different softening temperatures. You press the two tubes separately for and cools them. ' These two tubes are like this

calibrated that they nest in the cold

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can be inserted more easily friction. After inserting the two tubes, the whole thing is warmed up, to make their permanent association. One can also see the tilastic behavior of the substances in question exploit ^ for example, the outer tube can be expanded beforehand and then effected by heating its warm winding on the inner tube. The thus obtained Pipe is then cut into pieces, which after reheating to suitable temperature just like that pipe pieces obtained according to the two other processes can be formed into packaging »

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^ s. properties Schlagfes " activity pass o_L ^ jlvfcX appendix material for H 50 *) Water vapor sour cm nor Hohlensäu- TH times
24 otd 're - Used ^ v. a / day atm. 3
- cm standard file Btof fe ^ v 20 ⁰ O . 24 hours atm. Measurement conditions 2O ⁰ C 38 ° C-90 ^ 20 ° C relative Damp 0.8 speed 5.1 Polyvinyl chloride 0.4 0.03 4th Polyethylene 6.5. 0.02 10.8 I mixed polymer <u <tr \ f ¹ ι ¹ 1.2 <^ p, 01 ^ 0.1 #,1 2 1.2 <^ t) 01 <0.1 <C ⁰ ' ¹ 3 1.2 <; o, oi <0.1 4 ■ 1.2 0.01 (o, i 5 1.2 <0.01 φ, 1 6th 1.2 <0.01 ^, 1 7th 1.2 < ^{0 '01} φι 8th 1.2 <0.01 S , 1 ⁹ 1.2 <to, oi i, i <^, 1 L io 1.2 <0.01 I ' ¹ <6.1 I ¹¹ 1.2 0.01 f ¹ ςύ, ι 12th 0.4 <0.01 ^, 1 13th 1.2 <0.01 ^, 1 α 14
3 - 6.5 0.01 <0.1 ^, 1 ο. 15th
X » 6.5 0.01 % ' ¹ ^ 16
Ό 1.6 <p, oi φι : 17 1.6 <0.01 <^, 1 ί 18 1.6 <p, oi

*) Ss is the drop height in accordance with 505ε sxsctistisch help of precipitated with water at 20 ⁰ C bottles "specific fracture.

**) The character, / ^ L means: noticeably less than ..

BATH ORIGINAL

ι ο υ * + ο ο ο

This table clearly shows the advantages of the inventive Bottles. They have the increased impermeability the copolymers based on vinylidene chloride, but also the mechanical ones Properties of the second plastic used. The permeabilities of the bottles according to the invention are so low that the accuracy of the used 1 ruf ar. par ate was not sufficient to measure it.

In addition, the! 'Tabs are completely homogeneous and transparent. Because of their mechanical properties and their increased impermeability to water vapor, Gases, Cle, fats, flavorings, they are particularly suitable for the packaging of hygroscopic, wassereippf indigenous, oxidizable and / or flavored s Products, such as food, in particular soluble coffee, photographic, cosmetic or chemical products »

2, Manufacture and properties of impermeable pipes.

Starting from polyvinyl chloride for the outer layer and mixtures or copolymers of the preceding Examples of double-walled pipes were made in the following way "

! lan uses two presses, which are connected to a concentric, horizontally arranged double head. The first press is equipped for working with rigid polyvinyl chloride, the second for working with rich vinylidene chloride copolymers "The concentric double head has a play of the core and

BATH ORIGINAL

Presa nozzle, whose diameter is 14.7 mm for the inner Core, 18 mm for the outer press nozzle and 15.4 mm for The intermediate piece is «The outer part is fed with molten, rigid polyvinyl chloride and the inner part Part with mixtures or copolymers based on vinylidene chloride. The intermediate piece also fulfills the role of the core for the outer part of the Head and the press nozzles for the inner part. It's shorter than these other two pieces. Consequently the tubes are brought into intimate contact starting from a certain level inside the head and stick together under the action of the internal pressure in the head.

The pipe comes out of the press die in a horizontal direction and is taken up in a standard egg calibration device under vacuum and continuously calibrated. 35 mm from the mixed polymer be made based on _o e of vinylidene chloride.

In order to obtain a stiff double pipe, a stiff polyvinyl chloride will be used for the outer wall. If you want a less rigid pipe, you will use a less rigid polyvinyl chloride or another O ₃ plastic «
κ? The double-walled tubes have the good properties - ¹ of impermeability and resistance to chemical products such as the bottles described above. They can be used advantageously for the transport of gases, e.g. Town gas, solvents, chemical solutions, liquid foods, and the like can be used.

BATH ORIGINAL

Claims (1)

ητ Claims 1. Produced by pressing out and ^ e ^ eii / steam, • gases, oils, fats and aromas, impermeable and ge & en chemical products, resistant double-walled packaging in the form of ears, bottles, barrels, compressible tubes and the like, labeled by using a plastic from the group of polymers and high polymers on the basis of vinyl halides !! and / or olefins far the (layer which ensures _ö skinning mechanical properties of the packaging, and from a hischpolyr-ier of vinylidene chloride with a content of 65 his 95ί * vinylidene chloride, 5-35 $> vinyl chloride, and optionally acrylonitrile and / or styrene and less than 15? έ of one or more homomers with plasticizing or stabilizing properties for the layer which ensures the impermeability of the packaging, with both layers firmly connected and concentric. 2. Impermeable packaging according to claim 1, characterized in that marked that the the impermeability securing layer made of an Iviscnpolymer des Vinylidene chloride with a content of 70-87 yä of vinylidene chloride consists. 3. · Impermeable packaging according to claim 1, characterized in characterized in that the impermeability-ensuring layer is made of a copolymer of vinylidene chloride with vinyl chloride containing 6i; -95 $ of vinylidene chloride and 35-5 $> of vinyl chloride. 909842/1311 New documents (Art. 7 & I, Paragraph 2, Clause 1, Clause 3 of the Amendment Act of 4.9.196? ^ Ss £ D ORIGINAL H-. Impermeable packaging according to Anajruch 1, a & aurcL geke η η seic Ii η e τ, J ^ ss aie aie aie impermeability securing bcaicnt from one. ii £ ui_ool; -mer aes Vinyiidenciilorids und des VinylcLlorias with a "^ οιιε-ΐΐ at 70-87 $ in vinylidene chloride and 30-" ^: 3? ö in vinyl chloride. 5 ο impermeable packaging according to cn claim 1, äi- ^ ge ken η draw t that aie aie impermeable Security layer made of a mixed polymer made of 65-95 $ vinylidene chloride , / 5-35f ° vinyl chloride and ge ^ eijenenfalis acrylonitrile and / or styrene and v / ess than 15 ° / ° of a OAER rthrcrer monomers having Weichmaehungs- or oti-.bilisiervermcgeri chosen from unsaturated, _o egebenenfalls. epoxidized esters of Hono- oaer polycarboxylic acids. 6ο Impermeable packaging according to claim. 1, characterized in that the impermeability-ensuring layer of a mixed polymer with 65-95 / 0 vinylidene chloride, less than 35 ° vinyl chloride and optionally acrylonitrile and / or styrene and less than 15 $ one or more unsaturated, possibly epoxidized ^ sters of mono - or polycarboxylic acids, chosen from the ücrylaten, Kethacrylaten of alkyl and bp oxy alkyl, the itaconates, i'umaraten and times at the front en dialkyl, Dicycloalk3 ^r l and uiaryl, the itaconates, maleates ffumaraten and bis (epoxyalkyl) and bis ( epoxycycloalkyl), the mixed itaconates, fumarate and maleates of alkyl, cycloalkyl or aryl 909842/131 λ BATH ORIGINAL una ϋρoxyalkyl or epoxycyeioalkyl, the caproates, caprylates, caprates, laurates, MjTistater., palmitates and otearates of vinyl or allyl, the ispoxystearates, ipoxytallates, epoxylaurates of vinyl or allyl and the _o emixed iDUCinates of nltyl, cycloalkyl or aryl and vinyl or allyl. 7. ünaurc ^ lüsüifee packaging according to --nsoraci: 1, thereby ■ £; e Ic e η η a e i c λ η e t, aass die ^ uten mechanical ^ ii ^ e ^ isCiiaften securing ο chi oh ΐ in the general consists of jPolyvinj ^ lcLlorid. 8. ImpenläsBije Verpacicun ^ en nacl: An.-pruuh 1, thereby _& ei ··. e η η ζ ei α h η .e τ, dtsa the aie ^ Uten nechu:; isehen eigensu: -aften sioi.ernae aecnot consist of a ymer "of vinyl chloride. 9. Impermeable packaging according to claim 1, characterized in that the layer securing good mechanical properties a polyethylene. 10. Impermeable packaging according to claim 1, characterized in that the the layer securing good mechanical properties consists of a copolymer of ethylene. 11 * Impermeable packaging according to claim 1, characterized in that the the A layer made of polypropylene which ensures good mechanical properties. 909842/1311 ORIGINAL BATHROOM