GB2151985A

GB2151985A - Laminate and collapsible dispensing container made therefrom

Info

Publication number: GB2151985A
Application number: GB08432397A
Authority: GB
Inventors: Edward A Tavss; Samuel C Temin
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1983-12-30
Filing date: 1984-12-21
Publication date: 1985-07-31
Also published as: FR2557502B1; NO845267L; GB8701497D0; SE8406433D0; NO163764C; ZW21984A1; ZA849956B; GB2151985B; JPS60228145A; GB8432397D0; CA1222686A; DE3445798A1; AU3726385A; DK618284A; NO163764B; DK618284D0; MX170971B; AU564676B2; BR8406757A; PH20780A

Abstract

A laminate of inner and outer layers (11, 16) of fluoropolymer, having sandwiched therebetween a metal foil layer (13) and a paper layer (15) each adhering to its neighbours, is used in fabricating a collapsible dentifrice tube. <IMAGE>

Description

SPECIFICATION Laminated substrate and collapsible dispensing container made therefrom The present invention relates broadly to the container art, and is more particularly concerned with a collapsible dispensing container of laminated wall construction in the body portion thereof, whereby product permeation and absorption, and oxygen absorption, are substantially prevented in all regions of the container structure susceptible thereto.

Collapsible tubes formed of metallic and plastic materials have long been known in the packaging field.

Extruded metal tubes are inherently brittle and repeated use not infrequently results in wall cracks so that product is extruded from a location other than the essentially rigid dispensing orifice. Of the prior art metal tubes, aluminium tubes, while probably being the least brittle, are somewhat limited in their applications since up to the present time it has not been possible to apply to the interior surfaces thereof a completely satisfactory coating, when required to prevent attack and corrosion of the metal by alkaline or acid contents and contamination of the contents by the reaction products. Notwithstanding the relatively brittle nature of a metal tube, the mentioned internal coating operation requires an additional processing step which necessarily increases the cost of the final articles.

Tubes formed of polyethylene and other plastic materials have enjoyed wide commercial success in the packaging of many products; however, certan other products after a time have been noted to deteriorate when contained therein. Plastics as exemplified by polyethylene are permeable to a degree when employed in the wall thicknesses used in tubular containers, and the essential oils embodied in most dentifrices for flavouring purposes are reduced in volume during storage of the container, rendering the dentifrice less palatable. Also, the plastic container wall absorbs oxygen over a period of time and ultimately may decompose the product, which has actually been found to be the case with fluoride-containing tooth pastes.

It has accordingly been proposed to provide a relatively thin metallic foil barrier between the product and the polyethylene tube body to prevent the mentioned loss of essential oils and the absorption of oxygen. The metallic barrier has been suggested as an interlayer between facing sheets of polyethylene, and that a laminate be formed by heat with or without suitable adhesives. However, while a structure of this general character is effective to prevent some product permeation and oxygen absorption through the tube body, and particularly when the inner thermoplastic layer is a copolymer of an olefin and a polar group containing monomer which is co-polymerizable therewith, there remains the possibility of product deterioration albeit to a much lesser extent.

A disadvantage in a polyolefin surface resides in the inability of the surface to readily receive printing or decorative material. In addition, polyolefin has a memory effect; that is, it does not remain compressed when squeezed, a particular disadvantage for dentifrice tubes. To counter such lack of compressibility the metal layer must be relatively thick so that its compressibility is imposed on the plastic.

An object of the present invention lies in the provision of a tubular container having a plurality of adherent layers in the body portion thereof, one of said layers providing a barrier to product migration and oxygen absorption such as a metallic foil and another of said layers being of a material which avoids the above disadvantages.

According to one aspect of the invention, the other layer is a fluoropolymer. The fluoropolymer preferably contains at least 40% by weight of fluorine. The fluoropolymer may be a copolymer or mixture of varying crystallinity or density.

The said other layer will generally be the innermost layer, but it may also comprise the outermost layer, with different additional laminae sandwiched between the inner and outer layers.

Such additional layers may comprise paper and suitable adhesive and bonding agents such as copolymer of ethylene and acrylic acid. The collapsible dispensing container of the present invention may be constructed from the laminated substrate of the present invention by conventional and known apparatus.

Examples of such apparatus and method can be discerned from U.S. patent No.3,832,964, which is incorporated herein by reference.

The invention includes the multi-layer substrate for forming the container.

Afurther aspect of the instant invention is a method of producing laminated tubes in which a tubular bodyis formed of a barrier layer and a fluoropolymer laminated thereto; the laminated tube body is then located on a forming member in adjacency to a barrier member also positioned thereon.

The invention may be carried into practice in various ways and one embodiment will be described by way of example with reference to the accompanying drawings, in which: Figure lisa cross-sectional view of a fragmentary portion of a laminated substrate of the present invention; and Figure 2 is a side elevational view of a collapsible dispensing container embodying the novel concepts of this invention, with portions of the body walls being broken away to more fully illustrate the laminated structure.

Referring now first to Figure 1 of the drawings, a substrate 10 is shown in cross-section whereby to reveal the components of the sandwich that goes to make up the laminated configuration.

The bottommost layer 11 is a fluoropolymer. The second layer 12 thereabove is an adhesive layer which joins the fluoropolymer layer 11 with a third layer 13 which is a metal foil such as aluminium foil. The fourth layer 14 is another adhesive that secures the other surface of the metal foil layer 13 to a paper layer 15. The topmost layer 16 is a fluoropolymer.

The thermoplastic fluoropolymer of the present invention encompass such polymers as copolymers of hexafluoropropane and tetrafluoroethylene; tetrafluoroethylene; copolymer of heptafluoropropyl trifluorovinyl ether and tetrafluoroethylene, polychlorotrifluoroethylene and polyvinylidene fluoride.

Applicable fluoropolymers are disclosed in U.S. Patent 3,194,428 which is incorporated by reference herein. Such copolymers may be made by the method described in U.S. Patent 2,549,935 incorporated by reference herein. They comprise 5-50% by weight of hexafluoropropylene (preferably 5-15%) and 95-50% by weight of tetrafluoroethylene (preferably 95-85%), copolymerized, to form normally solid resins which melt 20-250"F.

These fluoropolymers are particularly useful because they have very low flavour absorption characteristics as can be seen from the following tables where fluoropolymers are compared with polyethylene where the thicknesses of the layers or coating are the same: TABLE I ABSORPTION OF FLAVOUR FROM A DENTIFRICE PASTE (Aging Condition: 1 week at Room Temperature) FlavourAbsorbed ( /O) Copolymer of hexafluoropropene and tetrafluoroethylene (Teflon FEP) 0.2 Tetrafluoroethylene (Teflon TFE) 0.3 Copolymer of heptafluoropropyl trifluorovinyl ether and tetra fluoroethylene (Teflon PFA) 0.2 Polychiorotrifluoroethylene (Halar) 0.4 Polyvinylidene Fluoride (PVDF) 0.9 Polyethylene 2.4 TABLE II ABSORPTION OF FLA VOUR FROM A DENTIFRICE GEL (Aging Condition: 2 weeks at Room temperature) FlavourAbsorbed { /O) Copolymer of hexafluoropropene and tetrafluoroethylene (Teflon FEP) 0.1 Tetrafluoroethylene (Teflon TFE) 0.2 Copolymer of heptafluoropropyl trifluorovinyl ether and tetrafluoroethylene (Teflon PFA) 0.1 Polychlorotrifluoroethylene (Halar) 0.2 Polyvinylidene Fluoride (PVDF) 0.1 Polyethylene 1.0 It is contemplated that within the purview of the invention the adhesives may be a copolymer of ethylene and acrylic acid or methacrylic acid, or sodium or zinc salts thereof in a diluent system.

The metal foil may be preferably aluminium foil.

The paper layer is desirably a kraft paper.

The thickness range of each of the layers is as follows: Fluoropolymer layer 11 - 0.5 mils to 3.0 mils, preferably 1.0 mils; Adhesive layer 12 - sufficient to ensure adherence; Metal foil layer 13 - 0.5 mils to 2.0 mils, preferably 1.0 mils; Adhesive layer 14 - sufficient to assure adherence; Paper layer 15 - 1.5 mils to 2.5 mils, preferably 2.0 mils; Fluoropolymer layer 16 - 3.5 mils to 5.0 mils, preferably 4.0 mils.

The topmost fluoropolymer layer 16 adheres to the paper layer 15 by means of the application of sufficient heat and pressure to the substrate. If the application of heat and pressure is not appropriate a suitable adhesive isto be employed.

Figure 2 is an example of the laminated structure of a collapsible container with the layers being demonstrated as in Figure 1 with layer 11 being inner most and the other layers being of the same materials and in the same order as shown.

It is believed manifest from the foregoing that a collapsible container structure has been provided which substantially reduces the problems heretofore unsolved by the prior art. The laminated substrate and laminated shoulder piece 20 substantially eliminate product permeation and oxygen absorption, and this highly desirable result is achieved by the use of low cost materials which preferably are combined into laminated form in the manner indicated in Figure 2.

The fluoropolymer or copolymer of the outer layers is a thermoplastic capable of fusion during a side seaming step and giving adequate protection to the paper and metallic foil interlayers. The art of seaming of a collapsible dentifrice tube of the general type herein disclosed can be seen in U.S. Patent No. 3,295,725, incorporated herein by reference.

However, the outer layer of fluoropolymer or copolymer and paper may be eliminated if the foil barrier is of sufficient thickness to resist damage; if the tube is made with an overlapping side seam, a thermoplastic material may be caused to flow into the overlapping side seam during the sealing operation.

Further, the outer layer may be paper in a three-ply laminate form of paper, foil and a fluoropolymer or copolymer as described. As the outermost and innermost layers are preferably the same, the folded over overlapped edges of tubes produced from the substrate are conveniently formed by heat bonding. A suitable adhesive can be used when heat bonding is not possible. This modification is in addition to the aforementioned four-ply laminates comprised of - from outside to in - fluoropolymer or copolymer, paper, foil, and fluoropolymer or copolymer; or fluoropolymer or copolymer, foil, paper, and fluoropolymer or copolymer. It is contemplated that suitable adhesives will be employed between the laminae whenever necessary. Similar laminated structures can be employed for such components as shoulder pieces, caps, necks, rods, pistons and dispensing valves, particularly where an interior surface is exposed to the contained dentifrice, and, again, where required, compatible adhesives would naturally be employed.

When cast as a film on the interior surface of a fibre drum used for the storage of flavoured dentifrice, the material will retard favour loss into the drum, thereby extending storage life.

Claims

1. A substrate of layers of materials comprising a first layer of a fluoropolymer, a second layer of metal foil, a third layer of paper and a fourth layer of a fluoropolymer.

2. The substrate of Claim 1, wherein the fluoropolymer is a copolymer of hexafluoropropane and tetrafluoroethylene.

3. The substrate of Claim 1, wherein the fluoropolymer is tetrafluoroethylene.

4. The substrate of Claim 1 or 2, wherein the fluoropolymer is a copolymer of heptafluoropropyl trifluorovinyl ether and tetrafluoroethylene.

5. The substrate of Claim 1 or 2, wherein the fluoropolymer is a copolymer of polychlorotrifluoroethylene and polyvinylidene fluoride.

6. The substrate of any preceding claim, wherein the first layer of the fluoropolymer is secured to the metal foil with an adhesive.

7. The substrate of any of the preceding claims, wherein the third layer of paper is secured to the fourth layer of the fluoropolymer with an adhesive.

8. The substrate of any preceding claim, wherein the first layer of the fluoropolymer is secured to the metal foil with an adhesive and wherein the third layer of paper is secured to the fourth layer of the fluoropolymerwith an adhesive.

9. The substrate of Claim 8, wherein the adhesive is a copolymer of ethylene and acrylic acid.

10. A collapsible paste dispensing container of multi-layer material, of which the innermost layer is a fluoropolymer.

11. A container as claimed in Claim 10, in which the outermost layer is a fluoropolymer.

12. A container as claimed in Claim 10 or claim 11, including an intermediate layer of paper.

13. A container as claimed in any of Claims 10 to 12, including an intermediate layer of metal foil.

14. A collapsible paste dispensing container of layers of materials comprising a first innermost layer of a fluoropolymer, a second layer of metal foil, a third layer of paper and an outermost fourth layer of a fluoropolymer.

15. The container of any of Claims 10 to 14, wherein the fluoropolymer is a copolymer of hexafluoropropane and tetrafluoroethylene.

16. The container of any of Claims 10 to 14, wherein the fluoropolymer is a tetrafluoroethylene.

17. The container of any of Claims 10 to 14, wherein the fluoropolymer is a copolymer heptafluoropropyl trifluorovinyl ether and tetrafluoroethylene.

18. The container of any of Claims 10 to 14, wherein the fluoropolymer is a copolymer of polychlorotrifluoroethylene and polyvinylidene fluoride.

19. The container of any of Claims 13 to 18, wherein a layer of the fluoropolymer is secured to the metal foil with an adhesive.

20. The container of any of Claims 12 to 19, wherein the layer of paper is secured to a layer of the fluoropolymerwith an adhesive.

21. The container of Claim 19 or Claim 20, wherein the adhesive is a copolymer of ethylene and acrylic acid.

22. A substrate of layers of materials substantially as herein specifically described with reference to Figure 1 of the accompanying drawings.

23. A paste dispensing container constructed and arranged substantially as herein specifically described with reference to Figure 2 of the accompanying drawings.