DE3544063A1 - LAMINATE AND DISPENSER MADE THEREOF - Google Patents

Description

description

The present invention relates to containers and, more particularly, to collapsible dispensers, the container portion of which is composed of laminated walls is formed, product permeation and in all susceptible areas of the container

-l 5 -absorption as well as oxygen absorption essentially be suppressed.

In the packaging field, compressible tubes made of metal or plastic have long been known.

2Q tubes made of extruded metal are brittle and longer Use not infrequently leads to wall breaks, so that the goods are essentially rigid from a location other than that Dispenser opening emerges. Of the well-known metal tubes are Aluminum tubes, which are probably the least brittle, are restricted in their scope as it is up it was not possible today to apply a really satisfactory coating to their inner surfaces if it was it was necessary to prevent attack and corrosion of the metal by alkaline or acidic ingredients and contamination

2Q purification of the contents by the reaction products too impede. Apart from the relatively brittle nature of a metal tube, there is also the fact that the inner coating mentioned requires an additional manufacturing stage which necessarily increases the price of the finished article.

Tubes made from polyethylene and other plastics are used to package many materials; it was observed that certain goods perish after a while in such packaging. Plastics such as Polyethylene are to some extent permeable if they are in the wall thicknesses used for tubular containers can be used. Take the essential oils found in most toothpastes for flavoring in volume during storage of the container, making the toothpaste less tasty. Still absorbed the wall of the plastic container over time oxygen, and eventually the product decomposes what has indeed been observed in toothpastes containing fluoride. Another disadvantage of the plastic tube is that their surface is not able to easily accept additional printing or decoration material. Continue to show Plastic tubes, for example those made of polyethylene, have a memory effect; i.e. after expressing do not remain compressed, which is particularly disadvantageous with toothpaste tubes.

Accordingly, in order to cope with the above problems, a metal foil barrier layer has been proposed to be provided between the goods and the polyethylene tube body. This is where the collapsible text problem counteracted by the fact that the metal layer its compressibility transfers to the plastic. Furthermore, the metal foil barrier layer prevents between the goods and the Polyethylene tube body eliminates the aforementioned loss of essential oils and absorption of oxygen. The metal barrier was proposed as an intermediate layer between adjacent sheets of polyethylene, and a laminate is said to be formed by heat with or without suitable adhesives. It is true that creates a structure of this general type that to some extent product permeation and oxygen absorption by the

Tube bodies are prevented, and this is especially true when the inner thermoplastic layer is made of a copolymer Ethylene and a polar group-containing monomer which is copolymerizable with the former. Yet there remains the possibility of deterioration of the goods, albeit to a much lesser extent.

In US Pat. No. 3,295,725, a tube is described in which the aforementioned advantages of an aluminum tube with the advantages of a plastic tube are combined. It is a laminated collapsible dispenser container, comprising both a metal barrier and a polyethylene inner wall. The thermoplastic Layer is roughly described as a polyolefin and a copolymer of an olefin and a polar one copolymerizable therewith Groups containing monomer. With this laminate, the above-described limitations except for Absorption of the essential oils from the toothpastes has been overcome.

From CA-PS 728 525 a laminated tube is known which contains an inner layer made of polyethylene. The problem the absorption of flavor oil by the thermoplastic wall is discussed.

According to other patent applications, surface-treated polymers were examined in the respective products. According to US Pat. No. 4,142,032, tests on films and containers have shown that the barrier properties can be improved by surface treatment with both fluorine and bromine. The manufacture of a tube is but not described; the product does not contain aluminum; and the flavor barrier properties of the Polymers were not recognized.

Also in the üS-PSs 4 2926 151, 4 110 518, 4 020 223, Nos. 3,647,613 and 4,404,256 describe articles comprising fluorine-treated polymers on the surface. In the ÜS-PS 4 2926 151 it is shown that the surfaces the treatment makes them receptive to adhesives, coatings, paints, inks, decorations and the like. In US Pat. No. 4,110,518 it is shown that the surface behaves as an electrical insulator. The treatment according to US Pat. No. 4,020,223 imparts properties that prevent oil stains. Treatment according to U.S. Patent 3,647,613 creates solvent resistance. None of the products described is a tube; none contain an aluminum layer; and in no event has the flavor resistance of these products been recognized.

It is therefore an important object of the present invention to provide a collapsible dispensing container, the Body has a laminated wall structure.

Another object of the invention is to provide a tubular container with a plurality of adherent layers in its body, being a these layers, like a metal foil, represent a barrier against product migration and oxygen absorption and another of these layers is a fluorinated polyethylene or a mixture thereof of different density and is crystallinity. The latter layer forms the inner layer and preferably the outer layer, wherein between these various further laminate layers are arranged.

These further layers comprise paper and suitable adhesives and binders, for example a copolymer of ethylene and acrylic acid.
35

The compressible dispenser according to the invention can be made from the laminate film according to the invention with conventional and known apparatus are produced. Examples of such an apparatus and such a method can be found in US Pat US Pat. No. 3,832,964, which is hereby incorporated by reference into part of the present specification will.

The invention also provides a method for producing laminated tubes in which a The tube body is made from a barrier layer and a fluorinated polyethylene laminated thereon; the laminated tube body is then brought together on a molded part with a barrier part also located on this. 15th

In the following the invention is explained in more detail with reference to figures in which the same numerals always have the same parts mean; show it:

Figure 1 shows a cross section through a piece of a laminate according to the invention and

Figure 2 is a side view of a compressible according to the invention Dispenser container embodying the novel concept according to the invention, with parts

the container wall are removed in order to make the laminate structure visible.

The thermoplastic according to the invention is a fluorinated polyethylene.

First, reference is now made to Figure 1, in which a substrate 10 is shown in cross section, whereby the Components of the sandwich structure are disclosed which make up the laminate assembly.

_ ο -

It can be seen that the lowermost layer 11 is fluorinated Is polyethylene. The second layer 12 above is a layer of adhesive that is the layer of fluorinated Polyethylene joins the third layer 13, which is a metal foil such as an aluminum foil. The fourth Layer 14 is another adhesive that adheres the other surface of the metal foil layer 13 to one Paper layer 15 attached. The top layer 16 is a fluorinated polyethylene.

The fluorinated polyethylenes are particularly suitable because they have very poor flavor absorption properties show what can be seen from the following tables in which fluorinated polyethylenes are compared to polyethylene the thicknesses of the layers or coatings being the same.

- ίο - 35A4063

Table I. Relative flavor absorption by polymers

from flavored toothpaste 5

22 ° C 32 ° C 49 ° C

Aluminum 0.4 0 0.4

On the surface with
Fluorine treated
High density polyethylene

HD-3 (Air Products) 22 37 90

High density polyethylene

HD-O (Air Products) 98 94 100

Low density polyethylene
LD-O (Air Products) 100 94 111

* All numbers refer to low density polyethylene at 22 ° C, arbitrarily set equal to 100 became; the smaller the number, the less flavorant has been absorbed.

Table II

Absorption of undiluted flavor sol by

Polymers
5

Absorption (%)

Aluminum O

The surface is treated with fluorine
High density polyethylene
HD-3 (Air Products) 3.3

High density polyethylene

HD-O (Air Products) 4.8

Low density polyethylene

LD-O (Air Products) 7.9

Low density polyethylene

NA (USD ¹ OO

Ionomer

Surlyn 1707 (DuPont) 15.7

Ionomer

Surlyn 1605 (DuPont) 19.0

Ionomer

Surlyn 1706 (DuPont) 24.3

Table III Absorption of undiluted flavor oil through

Polymers 5

% flavor absorbed

# 74, surface fluorinated low density polyethylene 2.6 No. 76, with fluorine on the surface

(a) treated low density polyethylene 2.6

Cb)
Low density polyethylene '5 _f 5

Low density polyethylene

(Comparison test) ^(a) 5 _f 6 + 0.14 ^(e)

(c) ~

Ionomer 7 _f 4

Ionomer ^(d) 12.2

(a) The low density polyethylene was Lupolen 1804H (BASF)

(b) Tenite 154 (Eastman)

(c) Surlyn 8940 (DuPont)

(d) Surlyn 8920 (DuPont)

(e) n = 3

Table IV

Loss of flavor from flavored Toothpaste on Polymers

Loss of taste pebbles

# 76, surface fluorinated low density polyethylene ^{a) 56

No. 74, polyethylene treated with fluorine on the surface less

Density ^ ^a * 64

Ionomer 88

Ic)
Ionomer 96

Low density polyethylene

(Comparative experiment) ' ^a ' 100

Low density polyethylene ^ 136

* Based on BASF low-density polyethylene as a reference, arbitrarily set equal to 100; ever the smaller the number, the less the loss of flavor from the toothpaste.

(a) The low density polyethylene was Lupolen 1804H (BASF)

(b) Surlyn 8920 (DuPont)

(c) Surlyn 8940 (DuPont)

(d) Tenite 154 (Eastman)

According to the invention, the adhesive can consist of a copolymer Ethylene and acrylic acid or methacrylic acid or their sodium or zinc salts in a diluent system.

The metal foil is preferably aluminum foil.
The paper layer is preferably wrapping paper.

The respective thickness of the layers is in the range of: 12.7 Ai to 76.2, u, preferably 25.4, u for the layer 11 made of fluorinated polyethylene,

sufficient thickness to ensure adhesion for the adhesive layer 12,

12.7 / U to 50.8 / U, preferably 25.4, u for the metal foil layer 13,

sufficient thickness to ensure adhesion for the adhesive layer 14,

38.1 / U to 63.5 / U, preferably 50.8 / U for the paper layer 15 and

88.9, u to 127,

made of fluorinated polyethylene.

88.9 / U to 127.0 / U, preferably 101.6 / U for layer 16

The top layer 16 of fluorinated polyethylene adheres to the paper layer 15 by applying sufficient heat and pressure on the laminate. If the application of heat and pressure is inadequate, an appropriate one is used Adhesive used.

Figure 2 shows an example of a collapsible container from the laminate in which the layers are shown as in Figure 1, the layer 11 being the innermost layer and the other layers are made of the same materials in the same order as shown in FIG.

By the collapsible container of the invention the disadvantages mentioned from the prior art are overcome. The laminated container body and the laminated one Shoulder piece 20 completely prevent product permeation and oxygen absorption.

The outer layer consists of a fluorinated polyethylene made of a thermoplastic material that is used in the side seaming stage is weldable and that provides adequate protection to the paper and metal foil interlayer. the Seaming a collapsible toothpaste tube of the general type described herein is disclosed in U.S. Patent 3 295 725, which is hereby made part of the present description by reference. the Fluorinated polyethylene and paper outer layer can be omitted if the barrier film is sufficient Thickness to withstand damage? in this In this case, a thermoplastic material is introduced into the overlapping seam area during welding of the same.

Furthermore, in the case of a three-layer laminate made of paper, metal foil and a fluorinated polyethylene, as described the outer layer be made of paper. Since the outermost and innermost layers are preferably the same, will the folding edges of the tubes produced are conveniently heat-sealed. A suitable adhesive can be used when heat welding is not possible. This modification is in addition to the four-layered ones mentioned above Laminates made of, from the outside in, fluorinated polyethylene, paper, film and fluorinated polyethylene.

Appropriate adhesives are used between the laminate layers if necessary.

Fluorinated polyethylene can also be used for the shoulder piece, the cap, neck, plunger and assembly of the dispenser valves or for other toothpaste dispensers especially in connection with the internal parts exposed to the toothpaste in the container, and here too, of course, suitable adhesives can be used if necessary.

If the material according to the invention is applied as a film to the inner surfaces of the drums made of fiber material, which are used for storing the flavored toothpastes, then the material according to the invention slows down the loss of flavoring substances in the drums and thereby increases the storage stability.
15th

Various modifications of the invention have been disclosed and these and other changes can be made without departing from the novel concepts of the invention.

Claims (1)

Claims Laminate, characterized by a first layer (11) made of a fluorinated polyethylene, a second layer (13) made of metal foil, a third layer (15) made of paper and a fourth layer (16) made of a fluorinated polyethylene. Laminate according to Claim 1 , characterized in that the first layer (11) made of the fluorinated polyethylene is attached to the metal foil (13) with an adhesive (12). 3. Laminate according to claim 1 , characterized in that the third layer (15) of paper is attached to the fourth layer (16) of the fluorinated polyethylene with an adhesive. 4. Laminate according to claim 1, characterized in that the first layer (11) made of the fluorinated polyethylene is attached to the metal foil (13) with an adhesive and that the third layer (15) made of paper on the fourth layer (16) the fluorinated polyethylene is attached with an adhesive. 5. Laminate according to one of claims 2 to 4, characterized in that the adhesive is a copolymer of ethylene and acrylic acid. 6. A compressible paste dispenser container made of a laminate, characterized by a first inner layer (11) made of a fluorinated polyethylene, a second layer (13) made of metal foil, a third layer (15) made of paper and an outer fourth layer (16) made of a fluorinated one Polyethylene. 7. Container according to claim 6, characterized in that the first layer (11) made of the fluorinated polyethylene is attached to the metal foil (13) with an adhesive (12). 8. A container according to claim 6, characterized in that the third layer (15) of paper is attached to the fourth layer (16) of the fluorinated polyethylene with an adhesive. 9. Container according to claim 6, characterized in that the first layer (11) made of the fluorinated polyethylene attached to the metal foil (13) with an adhesive is and that the third layer (15) of paper on the fourth layer (16) of the fluorinated polyethylene is attached with an adhesive. 10. Container according to one of claims 7 to 9, characterized in that the adhesive is a copolymer of ethylene and acrylic acid.