EP0873942A1 - Packaging tube - Google Patents

Abstract

A packaging tube with a body part made of plastic-containing mono-film or laminate and a head part consisting of a shoulder and a nozzle, has at least the tube body completely covered with a label containing a diffusion barrier layer.

Description

The present invention relates to a packaging tube containing a tube and one Tube head made of shoulder part and spout, the tube made of a plastic Monofilm or a plastic-containing laminate is.

It is known from GB-A 2 139 647, bottles made of plastic material or glass with a To wrap packaging material, such as a shrink film. The packaging material has one by ion plating or sputtering applied coating of certain oxides.

Packaging containers are known from CH-A 681 529, namely cups, trays, bottles and cans made by deep drawing or injection molding and with be wrapped with an enveloping label. The label has a ceramic layer as Barrier layer.

Until anin only substantially dimensionally stable packaging containers have become known are provided with labels with barrier properties.

The object of the present invention is to propose packaging tubes that are simple Wisely and with inexpensive, easily available and easily processable raw materials are and which nevertheless have a high barrier effect against the diffusion of substances such as gases and vapors, from the outside into the tube content or from the tube content to the outside. Above all, it should be prevented that, for example, volatile aromas or fragrances Moisture can escape from the packaging tube or e.g. Moisture from outside in the packaging tube and penetrate the contents of the packaging tube.

This is achieved according to the invention in that at least the entire length of the tube tube is included a label containing a diffusion barrier layer is encased.

All tube bodies or tubes are suitable for packaging tubes according to the present invention from tube with shoulder part, which can be produced by any method. Examples of tube tubes are seamless tube tubes, tube tubes with longitudinal seam or Changing tube tubes. The tube tube materials are advantageously free of metal foils.

The tubes can be produced, for example, by producing the tube and tube then fixing the tube head from the shoulder part and spout on the tube body or in another way that the tube head is integrated directly in the tube production.

Suitable materials for the tube body are, for example, monofilms and laminates thermoplastics or predominantly made of thermoplastics. The thermoplastics are based, for example, on olefin, ester, amide, Styrene or vinyl compounds.

Typical examples are polyethylenes, polypropylenes, polyalkylene terephthalates, such as Polyethylene terephthalate, polyamides, polystyrene or copolymers of polystyrene with Acrylonitrile or polystyrene with butadiene or terpolymers made of polystyrene with synthetic rubbers and acrylonitrile or polyvinyl chloride.

The laminates can have two or more layers of thermoplastic materials, the one another by coextrusion or by lamination with laminating adhesive and adhesion promoters.

The monofilms can be made of sealable material or laminates can be on one or both of the outer sides be sealable. The sealing layers are particularly in Form of sealable outer films.

The monofilms or laminates can be transparent, opaque or opaque. The monofilms or laminates can be colorless, stained or colored through.

Monofilms and laminates with a total thickness of 100 to 700 μm are preferred. Therefore the tube bodies made from these monofilms or laminates have a corresponding one Wall thickness.

The tube head e.g. an injection molded or pressed part made of a thermoplastic Plastic or the tube head can already be integrated in the tube production. Examples of thermoplastic plastics suitable for the tube head are the list the thermoplastic materials to the laminates. Are preferred Tube heads made of polyolefins and especially polyethylenes. The tube heads can be one Have diffusion barrier layer. The diffusion barrier layer can be on the outside of the tube head and expediently arranged as an intermediate layer in the tube head or the diffusion barrier layer can be the innermost layer on the tube head, pointing towards the contents of the tube. Examples of diffusion barrier layers for the tube head are ceramic layers or foil-shaped pads or inlays made of EVOH or acrylic-nitrile copolymers. In case of film-shaped inserts, the diffusion barrier layer can also act as a tamper-evident seal close the spout on the tube head. To remove the contents of the tube then the tamper-evident seal can be broken or pierced to open the opening Expose the spout.

The label according to the present invention, with at least one diffusion barrier layer, can a carrier film coated with the diffusion barrier layer or layers or can be a Be film composite, e.g. from a carrier film and a surface film and the or Diffusion barrier layers or from a carrier film, a surface film and an intermediate film and the diffusion barrier layer or layers.

Diffusion barrier layers produced by vacuum thin-film technology are advantageous ceramic layers applied.

The label can be on the carrier film, resp. between the carrier film and the surface film, a ceramic layer of an oxide produced by vacuum thin-film technology and / or nitrides of metals or semimetals or a mixture of oxides and / or contain nitrides of metals and / or semimetals.

For example, the label can be a carrier film that has the ceramic layer on one side wearing. The label is advantageously arranged on the packaging tube in such a way that the carrier film an outer layer forms on the packaging tube and the ceramic layer forms is located on the side of the carrier film facing the tube body. Becomes a film composite used as a label can expediently by vacuum thin film technology generated ceramic layer on the carrier film or the surface film or on both Films are applied. The ceramic layer is then advantageous between the Carrier film and the surface film arranged, i.e. the layer is on the carrier film side, which faces the surface film or the layer is on the Surface film side facing the carrier film or the layers on the carrier film and the surface film face each other.

Another expedient embodiment is that through the vacuum thin film generated ceramic layer applied to at least one side of at least one film and this film is arranged between the carrier film and the surface film. This intermediate film represents the intermediate film.

The ceramic layer of the oxides can also analogously on the carrier film and / or Surface film, as described, are present and there may be at least one other ceramic Layer on an intermediate film arranged between them.

The composite forming the label is expediently three-layered, made of a carrier film, one Oxide layer and a surface film built.

If necessary, there can be at least one between the carrier film and the surface film another film, another film composite or a laminate as an intermediate film.

Thermoplastic materials can be used for the carrier foils, surface foils and the intermediate foils Polymers, for example from the series on acetal, acrylic, amide, arylene oxide, -sulfone and sulfide, carbonate, cellulose, ester, imide, olefin, styrene and vinyl base be applied. The thicknesses of the individual foils can e.g. from 8 to 2000 µm. The carrier films, surface films and the intermediate films can preferably be made of a polyolefin such as polyethylene or polypropylene, polyester such as polyalkylene terephthalate and in particular containing polyethylene terephthalate, polyvinyl chloride or copolymers said polymers exist or contain them. Axial or biaxial are preferred oriented foils. The thickness of the carrier films, surface films and the intermediate films can e.g. B. between 8 and 2000 microns, suitably between 10 and 600 microns, preferably between 12 and 50 microns and particularly preferably between 12 and 25 microns. As carrier foils, Surface films and intermediate films can also be used in film composites. Especially biaxially oriented polyethylene terephthalate films are preferred as carrier films. Especially biaxially oriented polyethylene films are preferred as surface films. Preferred as The intermediate film is a polyalkylene terephthalate film, in particular polyethylene terephthalate can be used.

If the carrier film is the film used alone, the lower thickness limit is advantageous at 12 µm, while the upper thickness limits have the specified values can.

The intermediate film can be a film, a film composite or a laminate, the Thickness of the intermediate film e.g. 10 to 100 µm, suitably 12 to 25 µm and preferably 12 um amounts to.

The ceramic layer, preferably in a thickness of 5 to 500 nm (nanometers), is preferred from 10 to 200 nm and in particular from 20 to 150 nm, can be on the carrier film, are on the surface film and / or on at least one side of the intermediate film. If several ceramic layers are used, they can have the specified thicknesses have and expediently on the carrier film and on the surface film or on one or both sides of the intermediate film or on one or both sides of the intermediate film and on the surface film or on one or both sides of the intermediate film and are on the carrier film, etc.

If the intermediate film is a film composite or laminate, the ceramic layer can on at least one surface of the films that form the film composite or the laminate, be upset.

Accordingly, it is possible to cover the inside of the carrier film and / or the surface film with the to coat the selected ceramic. Both inner sides can also be coated. It is the outer sides of the carrier film and / or the surface film are technically possible to coat, however, in practice it should be borne in mind that the unprotected ceramic Layer can be easily damaged.

The oxides and / or nitrides of metals or semimetals, for example those of silicon, aluminum, iron, nickel, chromium or lead, can be used as the ceramic layer. This also includes the oxynitrides of the metals or semimetals mentioned. Oxides of silicon of the general formula SiO _x , where x is a number from 1 to 2, or of aluminum of the general formula Al _y O _z , where the factor y / z is a number of 0.2 to 1, are expediently used as the ceramic layer. 5, or mixtures thereof.

The oxides of silicon with the general formula SiO _{x are} preferred, where x is a number from preferably 1.1 to 1.9 and particularly preferably 1.2 to 1.7.

The ceramic layer is expedient, for example, using a vacuum thin-film technique based on electron beam evaporation or resistance heating or inductive Heating applied from crucibles. Electron beam evaporation is preferred. The The methods described can be carried out reactively and / or with ion support. These processes are carried out in such a way that the ceramic evaporates in a vacuum Material on the side of the carrier, intermediate or facing the evaporated material Precipitates the surface film over the entire surface and forms a closed ceramic layer.

The labels can be clear, opaque, or opaque. The labels can be colorless, stained or colored. The labels can be printed, such as a Print, a counter print or a print and a counter print.

a) Tubenkörper

b) keramische Schicht

c) Trägerfolie,

wobei die Schichten b) und c) die Etikette bilden,
oder

a) Tubenkörper

b) Trägerfolie

c) keramische Schicht

d) Oberflächenfolie,

wobei die Schichten b), c) und d) die Etikette bilden,
oder

a) Tubenkörper

b) Trägerfolie

c) keramische Schicht

d) Zwischenfolie

e) Oberflächenfolie,

wobei die Schichten b), c), d) und e) die Etikette bilden.
Gegebenenfalls kann z.B. zwischen den Schichten d) und e) eine zweite keramische Schicht c₁) angeordnet werden.In practice, packaging tubes of the layer structure explained below are particularly preferred:

a) Tube body

b) ceramic layer

c) carrier film,

layers b) and c) forming the label,
or

a) Tube body

b) carrier film

c) ceramic layer

d) surface film,

layers b), c) and d) form the label,
or

a) Tube body

b) carrier film

c) ceramic layer

d) intermediate film

e) surface film,

layers b), c), d) and e) form the label.
If necessary, a second ceramic layer c ₁ ) can be arranged, for example, between layers d) and e).

Packaging tubes according to the present invention with labels that have a carrier film made of oriented polyethylene terephthalate in a thickness of at least 20 µm and advantageously from 36 to 100 µm, a carrier film made of oriented polypropylene in a thickness of at least 20 µm and advantageously from 60 to 120 µm or are advantageous a carrier film made of oriented polyethylene in a thickness of at least 100 microns and advantageously from 100 to 200 microns, each with a diffusion barrier layer made of ceramic material in a thickness of 5 to 500 nm, advantageously made of SiO _x , where x is a number from 1.1 to 1.9 is included.

In practice, the carrier film, the intermediate film or the surface film is in one of the presented above devices for coating. The one to be coated with the ceramic The surface can optionally be pre-coated with an adhesion promoter. It can also the ceramic layer deposited on the surface or the free surfaces the films mentioned are coated with an adhesion promoter. Suitable adhesion promoters are, for example, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, polymerizable polyesters, vinyl pyridine polymers, vinyl pyridine polymers in combination with epoxy resins, butadiene-acrylonitrile-methacrylic acid copolymers, Phenolic resins, rubber derivatives, acrylic resins, acrylic resins with phenol or epoxy resins, or organosilicon compounds, such as organosilanes.

The organosilanes are preferred. Examples include trialkoxysilanes with an amino functional group, Trialkoxysilanes with an epoxy functional group, trialkoxysilanes with an ester functional group, Trialkoxysilanes with aliphatic functional group, trialkoxysilanes with glycidoxy functional group, Trialkoxysilanes with methacryloxy functional group, and mixtures the same. Examples of such organosilanes are -aminoprophyltriethoxysilane and N-b- (aminoithyl) -g-aminopropyltrimethoxysilane, g- (3,4-epoxycyclohexy) ethyltrimethoxysilane, g-glycidoxypropyltrimethoxysilane, and g-methacryloxypropyltrimethoxysilane.

Other suitable adhesion promoters are adhesives or glues, e.g. solvent-based or solvent-free adhesives e.g. the series of nitrile rubber phenolic resins, epoxies, Acrylonitrile-butadiene rubber, urethane-modified acrylics, polyester-co-polyamides, hot-melt polyesters, polyisocyanates crosslinked with hot-melt polyester, polyisobutylene-modified Styrene-butadiene rubbers, urethanes, ethylene-acrylic acid copolymers and Ethylene vinyl acetate copolymers.

Both the carrier film, the surface film and any intermediate films can be printed, be counter-printed and / or colored, this measure even before one any coating with the ceramic can be made. As a printing process all methods known per se and in particular gravure or flexographic printing are suitable.

The packaging tubes according to the present invention can therefore be single or multi-colored have graphic design on the carrier film and / or the surface film and / or optionally at least one intermediate film on the outside in each case and / or the inside is applied by printing or coloring. Is the etiquette translucent, transparent or colorless, the tube laminate can also be printed, counter-printed or colored and these effects can be seen through the label.

After coating the carrier film and / or the surface film and / or if appropriate The coated film can have at least one intermediate film with the ceramic layer be back-laminated with the other film or films. The lamination can be done using Heat and / or with the help of the adhesive and / or the adhesion promoter. The slides can to improve the adhesion also a corona, flame, plasma or ozone treatment get abandoned.

To generate the labels, for example, the carrier film, respectively. the surface and any intermediate films in endless form, i.e. as rolls, using the vacuum thin-film process, are applied with the diffusion barrier layer. If a majority of films is used, these can be laminated, coextruded, etc. with one another get connected. On the side of the label, the tube body at the finished packaging tube facing, can be an adhesive, as mentioned above and in particular a contact adhesive, e.g. by rolling, spraying, brushing, knife coating, brushing or dipping etc. are applied. The label can have an adhesive layer over the entire surface or over part of the surface exhibit. The partial surface adhesive layer can e.g. a regular or irregular Be adhesive pattern. This roll goods can be processed further in a labeling machine will. The individual labels are separated from the endless roll material and connected to the outside of the packaging tube. Joining the etiquette with the tube, the adhesive is already on the roll. Occasionally, an adhesive can only be on the outside of the tube body or on the outside of the tube body.

The packaging tubes come with a label that envelops the outer limits Mistake. The outer limits basically cover the entire tube, i.e. all outer side and any floor surfaces. It is according to the job of the label advantageous if the outside of the container is covered by the label to the extent that none notable areas of the packaging room uncovered or remain unprotected. That's why it may be advantageous to cover the shoulder part of the tube head with the label.

In an advantageous embodiment of the present invention, the tube tube is covered over the entire surface a label containing a diffusion barrier layer. In another advantageous embodiment is the tube and the shoulder part with a label containing a diffusion barrier layer wrapped The label is attached to the designated areas of the packaging tube.

The label can be on the prefabricated tube or on the tube head Tube tube can be fixed. The label can be conveniently attached to the Tube to be set.

The packaging tubes according to the present invention have a high blocking effect the passage of gases such as oxygen, moisture, water vapor, vapors, flavors, Fragrances, etc. The present invention results in packaging tubes with a variety of surprising advantages. For example, thinner laminates used for the tube body, as previously, because the barrier effect of the diffusion barrier with a thickness in the nanometer range, the unwanted access resp. Exit from Fabrics in, respectively. prevents the tube contents to a far greater extent than this one Would increase the layer thickness in the µm range of the tube wall. When using of tubes for slow aging or slow chemical degradation - because of the diffusion of e.g. Oxygen etc. - changing ingredients can be the same Tube bodies can be used for markets with a short or long shelf life. At The tube body is foreseeably long in the manner according to the invention with the Label wrapped. Furthermore, it was surprisingly found that the inventive Packaging tubes also in use, i.e. when deforming to express the contents of the tube maintain their high barrier effect. The ceramic layer, especially there this is embedded between two plastic layers, has a high flexibility and Torsibility on. The content of the packaging tube can therefore be expressed as you like Tube can be rolled up from the rear end without breaking the ceramic layer or would tear. The diffusion barrier layer in the form of a ceramic layer in the The above composition is transparent and shows even when stored for a long time no yellowing or other undesirable color changes.

Claims (12)

Packaging tube containing a tube and a tube head made of shoulder part and spout, the tube being made of a plastic-containing monofilm or a plastic-containing laminate,
characterized in that
at least the tube is completely covered with a label containing a diffusion barrier layer. Packaging tube according to claim 1, characterized in that the tube tube is completely covered with a label containing a diffusion barrier layer. Packaging tube according to claim 1, characterized in that the tube and the shoulder part is covered with a label containing a diffusion barrier layer. Packaging tube according to claim 1, characterized in that between the The entire surface of the packaging tube and the label containing the diffusion barrier layer or an adhesive layer is partially arranged. Packaging tube according to claim 1, characterized in that the tube is a Has longitudinal seam. Packaging tube according to claim 1, characterized in that the tube tube is seamless. Packaging tube according to claim 1, characterized in that the tube is a Is winding body. Packaging tube according to claim 1, characterized in that the label containing the diffusion barrier layer has at least one barrier layer made of a ceramic material, preferably a silicon oxide of the general formula SiO _x or an aluminum oxide of the general formula Al _y O _z or a mixture thereof, where x is a Has a number from 1.1 to 1.9 and the factor y / z is a number from 0.2 to 1.5. Packaging tube according to claim 8, characterized in that the barrier layers have a thickness of 5 to 500 nm (nanometers) made of a ceramic material. Packaging tube according to claim 1, characterized in that the tube tube is free of metal foil. Packaging tube according to claim 1, characterized in that the monofilm or the tube tube laminate has a wall thickness of 100 to 700 µm. Packaging tube according to claim 1, characterized in that the label is a carrier film made of polyethylene terephthalate in a thickness of at least 20 µm and advantageously from 36 to 100 µm, a carrier film made of oriented polypropylene in a thickness of at least 20 µm and advantageously from 60 to 120 µm or a carrier film made of polyethylene with a thickness of at least 100 µm and advantageously from 100 to 200 µm, each with a diffusion barrier layer made of ceramic material with a thickness of 5 to 500 nm, advantageously made of SiO _x , where x is a number from 1.1 to 1 , 9 is included.