WO2020055274A1

WO2020055274A1 - Multilayer thermoplastic sheet and method to produce the same

Info

Publication number: WO2020055274A1
Application number: PCT/PT2018/050030
Authority: WO
Inventors: Alberto MACHADO FERREIRA
Original assignee: Intraplas - Industria Transformadora De Plasticos, Sa
Priority date: 2018-09-10
Filing date: 2018-09-10
Publication date: 2020-03-19

Abstract

The present application relates to a multilayer thermoplastic sheet to be used in Form, Fill and Seal lines to produce breakable multipacks, wherein the thermoplastic is polyethylene terephthalate. Moreover, the present application also relates to a method to produce said sheets by an extrusion process. The sheet of the present application comprises at least three layers, with at least one foamed layer (C), at least one outer layer with a mineral (B) and at least one extra layer with no mineral (A). The incorporation of a mineral into the layers of a thermoplastic multilayer sheet increases its density, but to obtain a density between 0.95 and 0.99 g/cm3, at least one layer of the sheet is foamed. The multipacks produced in the Form, Fill and Seal lines with the presently disclosed multilayer sheets are easily separable, when submitted to flexion, by breaking the areas previously marked for this purpose.

Description

DESCRIPTION

"MULTILAYER THERMOPLASTIC SHEET AND METHOD TO PRODUCE THE

SAME"

Technical field

This application relates to multilayered thermoplastic sheet and a method to produce said sheet.

Background art

Nowadays, the Form, Fill and Seal (FFS) lines installed in the market that produce multipacks run only sheets produced in Polystyrene (PS), since this material has demonstrated that it is the most suitable polymer for its correct operation. The wide temperature range that this polymer offers in its transformation, combined with the ease with which it is possible to detach the packages, by breaking the packs by simple flexion, have been the main reasons why this preferred polymer to be used in the production of these sheets .

Polystyrene has a large range of temperatures during its transformation and that characteristic, combined with the fracture mechanism provided by this material, makes PS an ideal candidate to produce multipacks in FFS lines. Thus, there is a great need to use thermoplastic materials to produce sheets that can be used in FFS lines, without the need to adapt the current production lines, as well as maintaining the properties, such as density and breaking capacity, required for the production of multipacks .

Document US20150266643 describes a packaging material for producing deep-drawn plastics material packagings, particularly of multipack packagings, wherein the material is constructed to be breakable, and packaging produced therefrom. The present technology differs from this document in the sense that it uses polyethylene terephthalate (PET) to produce the multi-layered sheet by extrusion, wherein the minerals are added to the desired layers during the extrusion process .

Document W02017005360A1 discloses a multilayer polymer film for multipacks comprises at least two layers consisting of polyester and additives, wherein a first layer is porous and a second layer contains an inorganic filler. Multipacks thermoformed from the multilayer polymer film are equipped with snap incisions. The present technology differs from this document in the sense that it uses polyethylene terephthalate (PET) to produce the multi-layered sheet by extrusion, wherein the minerals are added to the desired layers during the extrusion process.

Nowadays, whenever thermoplastics other than PS are selected to produce multipacks in FFS lines, minerals are added to the material in order to improve its properties. These minerals are mixed with the thermoplastic material previously to the extrusion to produce the final sheets or films. This extra step increases the time and cost of the process, often leads to deficiencies in homogenization between the minerals and the material, and there is low control over the quantities of minerals added. Additionally, when opting for this strategy, additives are required to improve the homogenization. However, the addition of such additives alter the organoleptic characteristics of the thermoplastic, particularly the smell. Thus, the present application presents a solution to avoid the dependency on polystyrene in the production of multilayer sheets for the production of multipacks in FFS lines, as well as discloses a process to overcome the current drawbacks associated with the incorporation of minerals in order to maintain the breaking characteristics required for multipacks .

Summary

The present application related to a multilayer polyethylene terephthalate sheet with at least three layers, comprising: - at least one foamed layer, at least one outer layer and at least one extra layer;

~ a global density between 0.95 and 0.99 g/cm³ and a thickness between 600 and 1500 pm;

wherein the foamed layer comprises a nucleating agent and a mineral, the outer layers comprise a mineral and the extra layer does not comprise a mineral.

In one embodiment the foamed layer is positioned between at least one outer layer and at least one extra layer.

In another embodiment the foamed layer is positioned between at least two outer layers, and the sheet further comprises at least one extra layer.

In yet another embodiment the outer layers comprise 50 to 95% w/w of polyethylene terephthalate and 5 to 25% w/w of minerals . In one embodiment the foamed layer comprises 70 to 97% w/w of polyethylene terephthalate , 2 to 20% w/w of minerals and 1 to 5% w/w of a nucleating agent.

In another embodiment the extra layer comprises 75 to 95% w/w of polyethylene terephthalate.

In another embodiment the mineral is a powder selected from talc, calcium carbonate, wollastonite, silica or mixtures thereof .

In yet another embodiment the nucleating agent is selected from sodium hydrogen carbonate and citric acid.

In one embodiment at least one layer comprises additives in a percentage up to 25% w/w.

In another embodiment the additives are selected from pigments up to 8% w/w, chain extenders up to 3% w/w, slip agents up to 3%, matting agents up to 10%.

In one embodiment slip agents and matting agents are added to the outer layer or extra layer, and pigments and chain extenders are added to all layers .

The present application also relates to a method of producing the multilayer sheets comprising the following steps:

- preparation of the foamed layer in one twin screw extruder comprising the steps of:

introducing the polyethylene terephthalate to the twin screw extruder;

introducing a mineral to the twin screw extruder; introducing a physical foaming agent to the twin screw extruder;

introducing the nucleating agent to the twin screw extruder;

mixing all components added in the twin screw extruder;

- preparation of the outer layers in a twin screw extruder comprising the steps of:

introducing polyethylene terephthalate to the twin screw extruder;

introducing a mineral to the twin screw extruder; mixing all components added in the twin screw extruder;

- preparation of the extra layers in a twin screw extruder comprising the steps of:

introducing polyethylene terephthalate to the twin screw extruder;

mixing the polyethylene terephthalate; the mixture of the foamed layer prepared in one twin screw extruder is conveyed to the central part of a three channel die and the mixtures prepared in the other twin screw extruders are routed to the outer channels of the die .

In one embodiment the physical foaming agent is a gas selected from carbon dioxide or nitrogen.

In another embodiment the additives are added in a percentage up to 25% w/w.

In yet another embodiment the operating temperature is between 250 and 290 °C. General description

The present application relates to a multilayered thermoplastic sheet to be used in Form, Fill and Seal (FFS) lines to produce breakable multipacks. Moreover, the present application also relates to a method to produce said multilayer sheets by an extrusion process. The multipacks produced in the FFS lines with the presently disclosed multilayer sheets are easily separable, when submitted to flexion, by breaking the areas previously marked for this purpose. The multilayer sheet of the present application comprises at least three layers, wherein at least one layer is foamed.

Currently, the preferred material in FFS lines for multipacks is polystyrene (PS). However, due to the various drawbacks associated with using such material, the present application proposes an alternative material, and method, to produce a multilayered sheet to be used in existent FFS lines, breaking the dependency on polystyrene . The industry of FFS lines is currently highly dependent on this polymeric material and if there is a lack of its availability or its price rises, the industry might stop.

The sheets described herein are made from polyethylene terephthalate (PET), allowing to reduce the consumption of fossil materials, lowering the carbon footprint and lowering the costs of production as well. PET is a cheaper polymer than PS, and when used in the present technology it improves the oxygen and water vapor barrier of the final product as well as increasing the shelf life of the packed product. Additionally, the present application can use recycled PET, which means that products consisting of raw PET can be used to produce the multilayer sheets described herein. This feature in itself represents a sustainable solution in comparison to the current state of the art.

Another advantage in choosing polyethylene terephthalate instead of polystyrene, is that the fat, such as the one present in certain food products that might be packed in the multipacks, compromise the chemical stability of polystyrene, which does not occur with polyethylene terephthalate .

The sheets produced with this polymer do not have the breaking characteristic by themselves, which is necessary for the multipacks produced in FFS lines. PET does not have fragile fracture mechanism at room temperature, or temperatures close to room temperature, which increases the difficulty of breaking each pack from the multipack. Therefore, to produce easily breakable multipacks, the material requires the ability to break after an incision is made in the sheet and flexion is exercised upon the material.

In order to obtain the breaking characteristic, a mineral has to be incorporated into the layers of the multilayer sheet in well-defined and precise percentages. By doing so, a breaking mechanism, similar to the one currently observed in polystyrene sheets, can be achieved in the sheets described herein. However, the incorporation of minerals into the layers increase the density of the final multilayer sheet by lowering its yield per kilogram. Thus, the existence of a foamed layer in the sheets allows to decrease the overall density of the final product, the multi-layer sheet.

The multilayer sheet is produced by a co-extrusion process wherein at least one of the layers is foamed, at least one layer comprises minerals, and at least one layer does not comprise minerals .

The minerals are added directly into the extruder, providing a greater control of the added amounts .

Brief description of drawings

The present technology is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which:

Figure 1 illustrates a schematic representati n of the multilayer sheet wherein the references are: C - foamed layer, B - outer layer, A - extra layer.

Figure 2 illustrates a schematic representation of the multilayer sheet wherein the references are: C - foamed layer, B - outer layers, A - extra layer.

Figure 3 illustrates a schematic representation of the extrusion process to produce the multilayer sheets.

Description of embodiments

Now, preferred embodiments of the present application will be described in detail with reference to the annexed drawings. However, they are not intended to limit the scope of this application.

The present application relates to a multilayer thermoplastic sheet to be used in Form, Fill and Seal lines to produce breakable multipacks. The multilayer sheet of the present application is produced from a thermoplastic, in a preferred embodiment the thermoplastic is polyethylene terephthalate, which is co extruded and foamed in order to obtain a final density of the sheet between 0.95 and 0.99 g/cm³, and a thickness between 600 and 1500 pm. The presently described multilayer sheet comprises at least three layers, wherein at least one layer is foamed.

In order to obtain the breaking characteristic, a mineral has to be incorporated into at least one of the layers of the multilayer sheet. Thus, to ensure that the sheet has the breaking characteristics required to produce multipacks, and can be used in current FFS lines, it is necessary to incorporate the maximum possible amount of minerals in order to increase the dimensional stability of the sheet during the thermoforming process. The higher the mineral content incorporated, the greater dimensional stability is achieved. Additionally, the addition of minerals also provides higher stiffness to the final sheet. A higher mineral incorporation increases the compressing strength, allowing the production of packages with less thickness and equal quality, in comparison to the packages produced nowadays with PS.

The mineral is incorporated in the foamed layer and the outer layers also comprise minerals. However, there is at least one extra layer that comprises 0% of minerals.

In order to facilitate the thermoforming in the FFS lines, it is very important that the amount of mineral in one of the outer layers is zero, otherwise the sheet crystallizes during the thermoforming process, which makes its transformation impossible. In one embodiment the mineral is a powder selected from a list comprising talc (Mg3Si40io (OH) 2) , calcium carbonate (CaCOs) , wollastonite (CaSi03), silica, or mixtures thereof. The chosen minerals require to be as inert as possible, and with a particle size similar to the ones listed herein. Talc is used with a particle size between 4 and 16 pm. CaCo3 is used with a particle size between 1 and 3 pm.

It is well known that the incorporation of a mineral into the layers of a thermoplastic multilayer sheet increases its overall density, therefore in order to obtain an overall density between 0.95 and 0.99 g/cm³, at least one layer of the sheet is foamed. The foamed layer allows to lower the overall density of the multi-layer sheet, since the foamed layer produced through the method herein described presents a density between 0.4 and 0.8 g/cm³. The density of an outer layer comprising minerals is between 1.34 and 1.70 g/cm³, and the density of the extra layer without minerals is between 1.30 and 1.45 g/cm³.

In another embodiment, the foamed layer is positioned between at least one outer layer with minerals and at least one extra layer without minerals, such as Figure 1.

In one embodiment, the foamed layer is positioned between at least two outer layers comprising minerals, and further comprises at least one extra layer without minerals, such as Figure 2.

The expansion of the foamed layer is obtained by the addition of a physical foaming agent into the melted mass of this layer, thus obtaining a foamed layer. In one embodiment the physical foaming agent is a gas, selected from a list comprising carbon dioxide, nitrogen.

The presence of a mineral in the foamed layer is particularly important, not only because the mineral acts as a nucleating agent for the physical foaming agent improving the bubble structure of this layer, but also because minerals improve the fracture mechanism necessary for the presently described sheet .

The composition of the presently disclosed multilayer sheet is as follows:

Outer layer with minerals :

- PET - 50% to 95%;

- Minerals - 5% to 25%;

Extra layer without minerals :

- PET - 75 - 100%

- Minerals - 0%

Foamed layer:

- PET - 70% to 97%;

- Minerals - 2% to 20%;

- Nucleating agent: 1-5%.

In one embodiment, additives can be further added to at least one layer in a percentage up to 25%.

Additives can be pigments in a percentage up to 8%, chain extenders up to 3%, slip agents up to 3%, matting agent up to 10%.

Slip agents are selected from wax, erucamide, oleamide, fatty amide in general, and silica (Si02) . Chain extenders are selected from pyromellitic dianhydride, phenylenebisoxazoline , carbonyl bis ( 1-caprolactam) , diepoxides and tetraepoxides .

Matting agents are selected from inorganic oxides, minerals such as talc and calcium carbonate (CaCOs) .

The nucleating agents are always required in the foaming layer and are selected from sodium hydrogen carbonate and citric acid.

Slip agents and matting agents are used in the outer layers and extra layer, whereas pigments and chain extenders are used in all layers.

In one embodiments, the pigments used is a masterbatch colorant .

All percentages are represented in w/w in relation to all the components comprising the sheet.

The thickness of each of the layers varies according to the thickness and density of the sheet. Additionally, the density of the final sheet varies according to the thickness and density of each layer.

The presently disclosed multilayer sheet is co-extruded in a line with co-rotating twin screw extruders, with direct introduction of the minerals and direct injection of the foaming physical agent into the extruder that processes the foamed layer.

As opposed to the methods used nowadays, wherein the mineral is incorporated into the polymer with additives to produce a formulation in an extrusion step previous to the extrusion process to obtain the final sheet, the present technology proposes the addition of a mineral directly into the extruder with the polymeric material in order to produce the multilayer sheet. The direct introduction of a mineral, without additives, during the extrusion process, allows a greater control and precision on the amount of minerals incorporated into the layers, allows to obtain a sheet with excellent organoleptic characteristics, since the use of additives is one of the main causes of alteration on the organoleptic characteristics of the final product. The incorporation of a mineral as described herein allows to mix the polymer more homogeneously with the mineral and therefore ensure that the properties of the sheet remain constant and homogeneous . The addition of minerals in this manner also eliminates a transformation step, which is the production of a formulation comprising the polymer material and the mineral to be used in the extrusion process afterwards. The elimination of this step enables the overall production process to be energetically and environmentally efficient and consequently economically and environmentally friendly.

The direct introduction of the minerals during the extrusion process also leads to a greater control and precision of the amount of minerals constituting the layer, which is of fundamental importance, since small deviations in these quantities can change the properties of the polymer and completely change final properties of the multilayer sheet. This goal, can only be achieved with the direct incorporation of powdered minerals.

The method to produce the multilayer sheet of the present application comprises the following steps applied in at least three two screw extruders, as seen in Figure 3: - One twin screw extruder to prepare the foam layer comprising the steps of:

- introducing PET to the twin screw extruder;

- introducing a mineral to the twin screw extruder;

- introducing the physical foaming agent to the twin screw extruder;

- introducing a nucleating agent to the twin screw extruder;

- mixing all components added in the twin screw extruder.

In one embodiment, additives are also introduced to the twin screw extruder.

Mixing the PET, mineral, physical foaming agent, nucleating agent, and any additives in the co-rotating twin screw extruder will form a composite mixture, which will be able to be used as the foamed layer of the multilayer sheet.

- A twin screw extruder prepares outer layers comprising the steps of:

- introducing PET to the twin screw extruder;

- introducing a mineral to the twin screw extruder;

- mixing all components added in the twin screw extruder;

- A twin screw extruder prepares the extra layers comprising the steps of:

- introducing PET to the twin screw extruder;

- mixing PET.

In one embodiment, additives are introduced to the twin screw extruders . Mixing the PET, minerals, and any additives in the co rotating twin screw extruder will form a composite mixture, which will be able to form the outer layers of the multilayer sheet .

Mixing the PET and any additives if used, in the co-rotating twin screw extruder will form a composite mixture, which will be able to form the extra layers of the multilayer sheet .

The polymer, mineral and additives are fed through the main inlet (A) of the twin screw extruder, see figure 3.

The extruder barrel is set at a temperature between 250 and 290 °C. Once the extruder/feeding system assembly starts, the polymer is melted by the action of two screws inside the extruder. The twin screws have a 52 L/D design in order to achieve a perfect and homogeneous mix between polymer and mineral without the need of additives.

The introduction of the physical foaming agent, the gas, occurs in the last 10D of the screws from the extruder (B) producing the foamed layer, see Figure 3 section (B) .

The mixture of the foamed layer is conveyed to the central part of a three channel die, especially designed for this multilayer sheet. The mixtures prepared in the other extruders are routed to the outer channels of the die. Up to five layers can come together near to exit of the die. The desired layer configuration is obtained to the change of a selector plug.

In one embodiment the multilayer sheet comprises three layers, such as Figure 1, in an A/C/B structure with a final density between 0.95 and 0.99 g/cm³ wherein the composition is :

Layer A - Layer without mineral:

Layer density - between 1.30 and 1.45 g/cm³;

Thickness - 50 pm and 500 pm;

PET - 75% to 100%;

Additives - 0% a 25%;

Layer B - Layer with mineral :

Layer density - between 1.34 and 1.70 g/cm³;

Thickness - 100 pm and 650 pm;

PET - 50% to 95%;

Minerals - 5% to 25%;

Additives - 0% to 25%;

Layer C - Foamed layer:

Layer density - between 0.40 and 0.8 g/cm³;

Thickness - 200 pm and 900 pm;

PET - 70% to 97%;

Minerals - 2% to 20%;

Nucleating agent: 1 to 5%;

Additives - 0% to 15%.

In one embodiment, such as Figure 2, the multilayer sheet comprises four layers in an A/B/C/B structure, wherein the composition is :

Layer A - Layer without mineral:

Layer density - between 1.30 and 1.45 g/cm³;

Thickness - 20 pm and 100 pm;

PET - 75% to 100%

Additives - 0% a 25%;

Layer B - Layer with mineral : Layer density - between 1.34 and 1.70 g/cm³;

Thickness - 100 gm and 500 gm;

PET - 50% to 95%;

Minerals - 5% to 25%;

Additives - 0% to 25%;

Layer C - Foamed layer:

Layer density - between 0.4 and 0.8 g/cm³;

Thickness - 200 gm and 900 gm;

PET - 70% to 97%;

Minerals - 2% to 20%;

Nucleating agent: 1 to 5%;

Additives - 0% to 15%.

Examples :

Example 1 :

Multilayer sheet comprising three layers with 0.85 mm of thickness and 0.98 g/cm³ of density, in which the comparison is :

Layer A - Layer without mineral:

Layer density- 1.35 g/cm³;

Thickness - 200 gm;

PET - 96%;

Masterbatch - 2%;

Additive: chain extender - 2%;

Layer B - Layer with mineral :

Layer density- 1.46 g/cm³;

Thickness - 280 gm;

PET - 81%;

Mineral : calcium carbonate 15

Masterbatch 2 Chain extender 2

Layer C - Foamed layer:

Layer density- 0.44 g/cm³

Thickness - 370 pm;

PET - 89%;

Mineral: Talc - 7.5%;

Chain extender - 2.5%;

Nucleating agent - 1%;

Physical foaming agent - Nitrogen.

Example 2 :

Multilayer sheet comprising four layers with 0.85 mm of thickness and final density of 0.97 g/cm³, with A/B/C/B structure, in which the comparison is:

Layer A - Layer without mineral:

Layer density- 1.35 g/cm³

Thickness - 50 pm;

PET - 97%;

Masterbatch - 2%;

Additive: slip agent - 1 %;

Layer B - Layers with mineral:

Layer density- 1.46 g/cm³;

Thickness - 200 pm;

PET - 81%;

Mineral: calcium carbonate - 15%;

Masterbatch - 2%;

Additive: Chain extender - 2%;

Layer C - Foamed layer:

Layer density- 0.44 g/cm³ Thickness - 400 mih;

PET - 87 % ;

Mineral: Talc - 7.5%;

Additive: Chain extender - 2.5%; Additive: Nucleating agent - 1%; Masterbatch - 2%

Physical foaming agent - Nitrogen.

Claims

1. A multilayer polyethylene terephthalate sheet with at least three layers, comprising:

- at least one foamed layer, at least one outer layer and at least one extra layer;

a global density between 0.95 and 0.99 g/cm³ and a thickness between 600 and 1500 pm;

2. A multilayer polyethylene terephthalate sheet according to the previous claim, wherein the foamed layer is positioned between at least one outer layer and at least one extra layer.

3. A multilayer polyethylene terephthalate sheet according to claim 1, wherein the foamed layer is positioned between at least two outer layers, and further comprises at least one extra layer.

4. A multilayer polyethylene terephthalate sheet according to any of the previous claims, wherein the outer layers comprise 50 to 95% w/w of polyethylene terephthalate and 5 to 25% w/w of minerals.

5. A multilayer polyethylene terephthalate sheet according to any of the previous claims, wherein the foamed layer comprises 70 to 97% w/w of polyethylene terephthalate, 2 to 20% w/w of minerals and 1 to 5% w/w of a nucleating agent .

6. A multilayer polyethylene terephthalate sheet according to any of the previous claims, wherein the extra layer comprises 75 to 95% w/w of polyethylene terephthalate.

7. A multilayer polyethylene terephthalate sheet according to any of the previous claims, wherein the mineral is a powder selected from talc, calcium carbonate, wollastonite, silica or mixtures thereof.

8. A multilayer polyethylene terephthalate sheet according to any of the previous claims, wherein the nucleating agent is selected from sodium hydrogen carbonate and citric acid.

9. A multilayer polyethylene terephthalate sheet according to any of the previous claims, wherein at least one layer comprises additives in a percentage up to 25% w/w.

10. A multilayer polyethylene terephthalate sheet according to the previous claim, wherein the additives are selected from pigments up to 8% w/w, chain extenders up to 3% w/w, slip agents up to 3%, matting agents up to 10%.

11. A multilayer polyethylene terephthalate sheet according to the previous claim, wherein slip agents and matting agents are added to the outer layer or extra layer, and pigments and chain extenders are added to all layers.

12. Method of producing the multilayer sheets described in any of the claims 1 to 11, comprising the following steps :

- preparation of the foamed layer in one twin screw extruder comprising the steps of: introducing the polyethylene terephthalate to the twin screw extruder;

introducing the nucleating agent to the twin screw extruder;

mixing all components added in the twin screw extruder;

introducing polyethylene terephthalate to the twin screw extruder;

mixing the polyethylene terephthalate;

- the mixture of the foamed layer prepared in one twin screw extruder is conveyed to the central part of a three channel die and the mixtures prepared in the other twin screw extruders are routed to the outer channels of the die .

13. Method according to the previous claim, wherein the physical foaming agent is a gas selected from carbon dioxide or nitrogen.

14. Method according to any of the claims 12 to 13, wherein additives are added in a percentage up to 25% w/w.

15. Method according to any of the claims 12 to 14, wherein the operating temperature is between 250 and 290 °C.