RU2796345C2 - 3d-printed sheet material - Google Patents

Abstract

FIELD: 3D-printing.

SUBSTANCE: invention relates to a 3D-printed sheet material, a method for manufacturing a 3D-printed product, as well as a 3D-printed product, including a corresponding 3D-printed sheet material. The 3D-printed sheet material contains a cellulosic material in the amount of 5 to 55 wt.%, and a particulate inorganic filler material in the amount of ≥45 wt.%, based on the total dry weight of the 3D-printed sheet material. Moreover, the cellulose material is a mixture based on cellulose material containing nanofibrillated and/or microfibrillated cellulose in the amount of ≥55 wt.% and cellulose fibres in the amount of ≤45 wt.%, based on the total dry weight of the mixture based on the cellulosic material.

EFFECT: 3D-printed sheet material with sufficient strength, improved extensibility, uniformly distributed mass and less prone to delamination.

80 cl, 3 dwg, 10 tbl

Description

The present invention relates to a 3D moldable sheet material, a method for making a 3D moldable article, the use of a cellulosic material and at least one particulate inorganic filler material to make a 3D moldable sheet material and to increase the extensibility of a 3D moldable sheet material, the use of 3D-formable sheet material in 3D-forming methods, as well as a 3D-formed product containing, respectively, 3D-formable sheet material.

3D moldable materials are used in a wide variety of applications, such as packaging container, such as drug and cosmetic packaging or food packaging, food product container, such as candy boxes (bonbonnieres), blister packaging, food tray, etc. similar. Paper-like materials, that is, materials containing cellulosic material, are becoming increasingly attractive for such applications due to their various advantages such as recyclability (recyclability), biodegradability and renewability. Such materials are described in a number of documents. For example, JP 2003-293282 A refers to a paper substrate that can be molded at a processing temperature of <60°C without the need for preheating during compressed air molding or vacuum molding, with easy waste treatment or recycling and disposal, and has an environmentally friendly excellent properties. According to current samples for the manufacture of paper substrate, a polyacrylamide system is added to the pulp mass. JP 2006-082384 A relates to a moldable paper that is used as a substrate and an ink-receiving layer that is placed on the moldable paper. The ink-receiving layer applied to the formed paper contains a binding agent to prevent cracking. Particularly preferred binders are described as being a polyurethane copolymer, an acrylic copolymer, an ethylene-vinyl acetate copolymer, and a rubber copolymer. CN 104015450 A refers to a paper material comprising one or more layers, where the paper material can be stretched by at least 5% in the machine direction (machine direction) (MD) and can be stretched by at least 5% in the transverse direction (CD). The paper material is preferably a laminate where the paper materials are bonded to each other through the use of a binder, such as a water-based adhesive layer, such as a water-based adhesive, or PE. A PE or EVOH based layer can also be used as a moisture or gas barrier layer. CN 104015987 A relates to an insert made from a piece of wood designed to produce stretch paper. The liner is used for packaging and has a three-dimensional shape and is made from a piece of wood. The paper material is preferably a laminate where the paper materials are bonded to each other through the use of a binder such as a water-based adhesive layer or polyethylene (PE). The PE layer is also used as a gas barrier layer. US 3,372,084 relates to a post-formable absorbent paper capable of being used in the manufacture of post-formable plastic laminates, comprising in combination: a) a fiber portion containing from 35 to 100% fine fibers selected from plant fibers and synthetic organic fibers, where said fine fibers are characterized by having a specific volume of 75 to 175 cubic micrometers per unit length and an average length of more than 2 mm, b) the remainder of said fiber portion selected from wood pulp for papermaking, c) from 0.5 to 30%, based on the total weight of said fiber portion, an acid acceptor selected from zinc oxide, calcium carbonate and calcium silicate, where said paper is essentially neutral, which is assessed by measuring the pH value of its aqueous extract, which is in the range from 6.8 to 7 .6, while the base number of the aqueous extract is in the range from 0.5 to 3.0. However, methods for forming 3D-shaped products are well known in the art, for example from WO 2015/063643 A1, AU 54281/86 B, GB 2092941 A, US 7681733 B2, US 4637811 A, WO 99/53810 A1, WO 2009/020805 A1, DE 10 2012 201 882 A1, US 1 567 162 and EP 2 829 392 A1.

However, poor 3D formability of sheet materials is a limiting factor for making 3D molded products. This poor 3D formability typically results from limited sheet strength and poor extensibility, as well as possible separation of fillers and cellulosic material.

Thus, there is a continuing need in the art for a 3D formable sheet material that provides good 3D formability. In particular, there is a need for a 3D-formable sheet material having sufficient strength and improved extensibility, as well as having a mass that is uniformly distributed and, as a result, its delamination is difficult.

In accordance with the foregoing, it is an object of the present invention to provide a 3D moldable sheet material that provides good 3D moldability for 3D molded articles. An additional object is to provide a 3D-formable sheet material having sufficient strength, ie where strength is maintained or improved. Another goal is to provide a 3D formable sheet material having extensibility that is maintained or improved. Yet another additional object is to provide a 3D moldable sheet material in which the mass is evenly distributed throughout the sheet material and the separation of components, especially filler and cellulosic material, is complicated.

The above and other goals are solved by the object, which is defined in this document in paragraph 1 of the claims.

Preferred embodiments of the inventive 3D moldable sheet material are defined in the respective dependent claims.

According to one aspect of the present application, a 3D formable sheet material is provided. 3D-formable sheet material contains

a) cellulosic material in an amount of from 5 to 55 wt.%, based on the total dry weight of the 3D-formable sheet material, where the cellulosic material is a mixture based on cellulosic material containing

i) nanofibrillated cellulose and/or microfibrillated cellulose in an amount of ≥55% by weight, based on the total dry weight of the mixture based on the cellulose material, and

ii) cellulosic fibers in an amount of ≤45% by weight, based on the total dry weight of the mixture based on cellulosic material,

and the sum of the amount of nanofibrillated cellulose and/or microfibrillated cellulose and cellulose fibers is 100% by weight, based on the total dry weight of the mixture based on the cellulose material, and

(b) at least one particulate inorganic filler material in an amount of ≥45% by weight, based on the total dry weight of the 3D moldable sheeting,

where the sum of the amount of cellulosic material and at least one particulate inorganic filler material is 100.0 wt%, based on the total dry weight of the cellulosic material and at least one particulate inorganic filler material.

The inventors have surprisingly found that the aforementioned 3D moldable sheet material of the present invention provides good 3D moldability for 3D moldable articles. More specifically, the inventors found that the aforementioned 3D-formable sheet material according to the present invention provides sufficient strength and extensibility, and that the delamination of its mass is difficult.

It should be understood that for the purposes of the present invention, the following terms have the following meanings:

The term "3D moldable" in the context of the present invention refers to a sheet material that can be molded into a 3D molded product by using 3D molding techniques, provided that the product maintains a 3D shape.

The term "3D molded" means that the product retains the 3D shape that was formed when the 3D molded sheet material was formed.

The term "dry state" in relation to at least one particulate inorganic filler material is intended to mean a material having less than 0.3% by weight of water relative to the weight of at least one particulate inorganic filler material. The % water content is determined according to the Coulometric Karl Fischer measurement method, where at least one particulate inorganic filler material is heated to 220° C., and the water content released as vapor and recovered by using a stream of nitrogen gas (at a flow rate of 100 ml/min) is determined in a coulometric Karl Fischer titrator.

The term "dry state" in relation to cellulosic material refers to dry cellulosic material having <0.5% by weight of water relative to the mass of cellulosic material. "Dry cellulosic material" is determined by treating cellulosic material at 103° C. to constant weight in accordance with DIN 52 183.

By "dry state" in relation to 3D-formable sheeting is meant dry 3D-formable sheeting having <0.5% by weight of water relative to the weight of 3D-formable sheeting. The "Dry 3D Formable Sheet" is determined by processing the 3D Formable Sheet at 103°C to constant weight in accordance with DIN 52 183.

When the term "comprising" is used in the description and claims of the present invention, it does not exclude other unspecified elements of primary or secondary functional importance. For the purposes of the present invention, the term "consisting of" is considered to be the preferred embodiment of the term "comprising". If a group is defined hereinafter to include at least some number of embodiments, this should also be understood as disclosing a group that preferably consists of only those embodiments.

Whenever the terms "comprising" or "having" are used, these terms are intended to be equivalent to the term "including" as defined above.

When a noun is used in the singular form, this includes the plural form of that noun, unless otherwise specified.

Terms such as "obtainable" or "determined" and "obtained" or "determined" are used interchangeably. This means, for example, that unless the context clearly dictates otherwise, the term "obtained" is not intended to indicate that, for example, an embodiment is to be obtained by performing, for example, the sequence of steps indicated after the term "obtained", even if such the limited understanding is always encompassed by the terms "obtained" or "determined" as the preferred embodiment.

According to another aspect of the present invention, a method is provided for making a 3D molded article. The method includes the steps:

a) providing 3D formable sheeting as defined herein, and

b) forming a 3D moldable sheet material into a 3D molded article, preferably using thermoforming, vacuum forming, pneumatic (air pressure) forming, deep drawing forming, hydroforming, spherical forming, compression molding, or vacuum/pneumatic forming.

According to one embodiment of the method, the 3D formable sheet material was obtained by

i) providing cellulosic material as defined herein,

ii) forming a pre-sheet consisting of the cellulosic material of step i), and

iii) drying the pre-sheet of step ii) to form a 3D formable sheet material.

In another embodiment of the method, the cellulosic material of step i) is combined with at least one particulate inorganic filler material as defined herein to form a cellulose-inorganic filler material mixture.

According to another embodiment of the method, i) provide cellulosic material in the form of an aqueous suspension, comprising cellulosic material in the range from 0.2 to 35 wt. -%, more preferably, from 0.25 to 20 wt. -%, even more preferably, from 0.5 to 15 wt%, most preferably 1 to 10 wt%, based on the total weight of the aqueous suspension; and/or ii) providing at least one particulate inorganic filler material in powder form, or in the form of an aqueous suspension, containing the inorganic particulate filler material in an amount of from 1 to 80% by weight, preferably from 5 to 78% wt., more preferably, from 10 to 78% wt. and most preferably from 15 to 78% by weight, based on the total weight of the aqueous suspension.

According to one embodiment of the method, the cellulose material is a mixture based on cellulose material, including nanofibrillated cellulose and/or microfibrillated cellulose, which was obtained by nanofibrillation and/or microfibrillation of a suspension of cellulose fibers in the absence of fillers and/or pigments, where preferably nanofibrillated cellulose and/or the microfibrillated cellulose is in the form of an aqueous suspension having a Brookfield viscosity in the range of 1 to 2000 mPa.s at 25°C, more preferably 10 to 1200 mPa.s at 25°C, and most preferably 100 to 600 mPa⋅sec at 25°C, with a content of nanofibrillated cellulose and/or microfibrillated cellulose of 1% wt., based on the total weight of the aqueous suspension.

According to another embodiment of the method, the cellulose material is a mixture based on cellulose material, including nanofibrillated cellulose and/or microfibrillated cellulose, which was obtained by nanofibrillation and/or microfibrillation of a suspension of cellulose fibers in the presence of fillers and/or pigments, where preferably nanofibrillated cellulose and/or the microfibrillated cellulose is in the form of an aqueous suspension having a Brookfield viscosity ranging from 1 to 2000 mPa.s at 25°C, more preferably from 3 to 1200 mPa.s at 25°C, and most preferably from 10 to 600 mPa.s at 25°C, with a content of nanofibrillated cellulose and/or microfibrillated cellulose of 1 wt. %, based on the total weight of the aqueous suspension.

Based on European patent applications EP 2386682 A1, EP 2386683 A1, EP 2236664 A1, EP 2236545 A1, EP 2808440 A1, EP 2529942 A1 and EP 2805986 A1, and from J. Rantanen et al., ʺForming and dewater ing of a microfibrillated cellulose composite paperʺ, BioResources 10(2), 2015, pages 3492-3506, nanofibrillated cellulose and microfibrillated cellulose and their use in paper making are known. However, there is no information regarding their effect on 3D-formable sheet materials.

According to another embodiment of the method, the method further includes step c) moistening the 3D-formable sheet material provided in step a) to a moisture content of 2 to 30% by weight, based on the total dry weight of the 3D-formable sheet material, before and/or during step b) of the method.

According to a further aspect of the present invention, the use of a cellulosic material as defined herein and at least one particulate inorganic filler material as defined herein is provided for making a 3D moldable sheet material. According to another additional aspect of the present invention, the use of a cellulosic material as defined herein and at least one particulate inorganic filler material as defined herein is provided to increase the extensibility of a 3D moldable sheet material, where the increase is achieved in that the case where the 3D-formable sheet material has an increase in stretch, normalized to the level of moisture content, in the range from 0.15 to 0.7% per percent. According to another further aspect of the present invention, the use of the 3D moldable sheet material as defined herein is provided in 3D molding processes, preferably thermoforming, vacuum forming, pneumatic forming, deep drawing forming, hydroforming, spherical forming, compression molding, or vacuum/pneumatic forming. According to another aspect of the present invention, a 3D moldable article is provided, preferably a packaging container, a food container, a blister pack, a food tray, containing the 3D moldable sheet material as defined herein.

According to one embodiment of the present invention, the 3D formable sheet material comprises a) cellulosic material in an amount of 15 to 55 wt %, based on the total dry weight of the 3D formable sheet material, and b) at least one consisting of particles of inorganic filler material in an amount of from 45 to 85 wt. -%, based on the total dry weight of the 3D-formable sheet material.

According to another embodiment of the present invention, the 3D-formable sheet material has a) an increase in elongation, normalized to the level of moisture content, in the range of 0.15 to 0.7% per percent, and/or b) an elongation at break of at least 6 %, preferably from 6 to 16% and most preferably from 7 to 15% and/or c) sheet weight from 50 to 500 g/m ² , preferably from 80 to 300 g/m ² and most preferably from 80 to 250 g/m ² .

According to another embodiment of the present invention, nanofibrillated cellulose and/or microfibrillated cellulose has been obtained by nanofibrillation and/or microfibrillation of a suspension of cellulose fibers in the absence or presence of fillers and/or pigments, where preferably the cellulose fibers of the suspension of cellulose fibers are those contained in the pulp selected from the group consisting of softwood pulp such as spruce pulp and pine pulp, hardwood pulp such as eucalyptus pulp, birch pulp, beech pulp, maple pulp , acacia pulp, and other types of pulp such as hemp pulp, cotton pulp, bagasse or straw pulp, or recycled (recycled) fiber material, and mixtures thereof.

According to one embodiment of the present invention, the cellulosic fibers a) are selected from the group consisting of softwood fibers such as softwood fibers and pine fibers, hardwood fibers such as eucalyptus fibers, birch fibers, beech fibers, maple fibers, acacia fibres, and other types of fibres, such as hemp fibres, cotton fibres, bagasse or straw fibres, or fibers of recycled fiber material and mixtures thereof, and/or b) have a length-weighted average fiber length between 500 µm and 3000 µm, more preferably from 600 µm to 2000 µm, and most preferably from 700 to 1000 µm.

According to another embodiment of the present invention, the at least one particulate inorganic filler material is at least one particulate material containing calcium carbonate, preferably the at least one particulate material containing calcium carbonate is dolomite and/or at least one natural finely divided calcium carbonate (GCC) such as marble, chalk, limestone and/or mixtures thereof, and/or at least one precipitated calcium carbonate (PCC) such as one or more of its modifications , selected from aragonite, vaterite and calcite mineralogical crystalline forms, more preferably at least one particulate inorganic filler material is at least one precipitated calcium carbonate (PCC).

According to another embodiment of the present invention, at least one particulate inorganic filler material has a) a mass median particle sized ₅₀ 0.1 to 20.0 µm, preferably in the range of 0.3 to 10.0 µm, more preferably in the range of 0.4 to 8.0 µm, and most preferably in the range of 0.5 to 4.0 µm, and/or b) specific surface area from 0.5 to 200.0 m²/g, more preferably 0.5 to 100.0 m²/g and most preferably from 0.5 to 50.0 m²/g, which is measured using the nitrogen BET method.

As discussed above, the inventive 3D moldable sheet material includes a cellulosic material and at least one particulate inorganic filler material as described in a) and b). Below in the text, we are talking about additional details of the present invention and, in particular, the above features with features of the invention 3D-formable sheet material.

According to the present invention, the 3D moldable sheet material includes

a) cellulosic material in an amount of from 5 to 55% by weight, based on the total dry weight of the 3D-formable sheet material, and

b) at least one particulate inorganic filler material in an amount of ≥45% by weight, based on the total dry weight of the 3D moldable sheet material.

One requirement for the 3D-formable sheet material of the present invention is that the sum of the amount of cellulosic material and at least one particulate inorganic filler material is 100.0% by weight, based on the total dry weight of the cellulosic material and at least one particulate inorganic filler material.

The 3D-formable sheet material of the present invention includes cellulosic material in an amount of 5 to 55% by weight, based on the total dry weight of the 3D-formable sheet material. Preferably, the 3D-formable sheeting includes cellulosic material in an amount of 15 to 55% by weight, based on the total dry weight of the 3D-formable sheeting. For example, 3D-formable sheet material includes cellulosic material in an amount of from 20 to 45% of the mass. or from 25 to 35% by weight, based on the total dry weight of the 3D-formable sheeting.

In addition, the 3D moldable sheet material includes at least one particulate inorganic filler material in an amount of ≥45 wt %, based on the total dry weight of the 3D moldable sheet material. Preferably, the 3D moldable sheeting includes at least one particulate inorganic filler material in an amount of 45 to 85% by weight, based on the total dry weight of the 3D moldable sheeting. For example, the 3D moldable sheet material includes at least one particulate inorganic filler material in an amount of 55 to 80% by weight. or from 65 to 75% by weight, based on the total dry weight of the 3D-formable sheet material.

In one embodiment, the 3D moldable sheet material is comprised of a cellulosic material and at least one particulate inorganic filler material. In other words, a 3D-formable sheet material consists of

a) cellulosic material in an amount of from 5 to 55 wt. -%, preferably from 15 to 55 wt. -%, more preferably, from 20 to 45 wt. or 25 to 35% by weight, based on the total dry weight of the 3D-formable sheeting, and

b) at least one particulate inorganic filler material in an amount of ≥45 wt%, preferably from 45 to 85 wt%, and most preferably from 55 to 80 wt%. or from 65 to 75% by weight, based on the total dry weight of the 3D formed sheet material,

where the sum of the amount of cellulosic material and at least one particulate inorganic filler material is 100.0 wt%, based on the total dry weight of the cellulosic material and at least one particulate inorganic filler material.

It should be appreciated that the 3D-formable sheeting may include additives that are commonly used in the field of papermaking and, in particular, 3D-formable sheeting.

The term "at least one" additive in the context of the present invention means that the additive includes, preferably consists of, one or more additives.

In one embodiment of the present invention, at least one additive includes, preferably consists of, one additive. Alternatively, at least one additive includes, preferably consists of, two or more additives. For example, at least one additive includes, preferably consists of, two or three additives.

For example, at least one additive is selected from the group consisting of a sizing agent, a paper strength enhancer, a filler (other than at least one particulate inorganic filler material), a filler retention agent such as ^Percol® , a binder, surfactant, biocide, antistatic agent, colorant and flame retardant.

The at least one additive may be present in the 3D-formable sheeting in an amount ranging from 0.01 to 10% by weight, based on the total dry weight of the 3D-formable sheeting. For example, at least one additive may be present in the 3D-formable sheet material in an amount ranging from 0.02 to 8% by weight, preferably from 0.04 to 5% by weight, based on the total dry weight. 3D molded sheet material.

Thus, the 3D formed sheet material may include

a) cellulosic material in an amount of 5 to 55 wt. -%, preferably from 15 to 55 wt. -%, more preferably, from 20 to 45 wt. or from 25 to 35% wt., based on the total dry weight of the 3D-formable sheet material,

b) at least one particulate inorganic filler material in an amount of ≥45 wt%, preferably from 45 to 85 wt%, and most preferably from 55 to 80 wt%. or from 65 to 75% by weight, based on the total dry weight of the 3D-formable sheeting, and

c) optionally, at least one additive in an amount of from 0.01 to 10 wt%, preferably from 0.02 to 8 wt%, and most preferably from 0.04 to 5 wt%, in the calculation on the total dry weight of the 3D formed sheet material,

where the sum of the amount of cellulosic material and at least one particulate inorganic filler material is 100.0 wt%, based on the total dry weight of the cellulosic material and at least one particulate inorganic filler material.

In one embodiment, the 3D formable sheet material consists of

a) cellulosic material in an amount of from 5 to 55 wt. -%, preferably from 15 to 55 wt. -%, more preferably, from 20 to 45 wt. or from 25 to 35% wt., based on the total dry weight of the 3D-formable sheet material,

b) at least one particulate inorganic filler material in an amount of ≥45 wt%, preferably from 45 to 85 wt%, and most preferably from 55 to 80 wt%. or from 65 to 75% by weight, based on the total dry weight of the 3D-formable sheeting, and

c) optionally, at least one additive in an amount of from 0.01 to 10 wt%, preferably from 0.02 to 8 wt%, and most preferably from 0.04 to 5 wt%, in the calculation on the total dry weight of the 3D formed sheet material,

where the sum of the amount of cellulosic material and at least one particulate inorganic filler material is 100.0 wt%, based on the total dry weight of the cellulosic material and at least one particulate inorganic filler material.

Thus, the 3D-formable sheeting preferably includes cellulosic material and at least one particulate inorganic filler material in an amount of ≥90% by weight, based on the total dry weight of the 3D-formable sheeting. For example, the 3D formable sheeting preferably includes cellulosic material and at least one particulate inorganic filler material in an amount of 90 to 99.99% by weight, based on the total dry weight of the 3D formable sheeting. . Preferably, the 3D-formable sheet material includes cellulosic material and at least one particulate inorganic filler material in an amount of from 92 to 99.95% of the mass. or in an amount of from 95 to 99.9 wt. -%, based on the total dry weight of the 3D-formable sheet material. Alternatively, the 3D moldable sheet material is comprised of a cellulosic material and at least one particulate inorganic filler material.

One advantage of the 3D-formable sheeting of the present invention is that it exhibits features of high extensibility as well as high elongation at break, making the 3D-formable sheeting particularly suitable for making 3D-formable articles.

The 3D-formable sheet material in particular shows signs of high or increased extensibility.

In particular, it should be appreciated that the 3D-formable sheet material has an increase in stretch, normalized to moisture content, in the range of 0.15 to 0.7% per percent. For example, a 3D-formable sheet material has an increase in stretch, normalized to the level of moisture content, in the range of 0.15 to 0.6% based on the percentage of moisture in the sheet, and preferably 0.2 to 0.6%.

"Stretch increase normalized to moisture content" means a material property and is determined by the following formula (I)

where d ( moisture ) defines the moisture content range under consideration, that is, the difference between a significant higher moisture level (eg 20%) and a significant lower moisture level (eg 10%);

d ( stretch ) defines the stretch range in the considered moisture content range, that is, the difference between the stretch at a significant higher moisture level and the stretch at a significant lower moisture level.

It should be appreciated that the increased elongation depends on the moisture content of the 3D formed sheeting.

For example, the 3D formable sheet material has an extensibility in the range of 4 to 10%, preferably 5 to 10%, at a moisture content of 10% in the 3D formable sheet material.

Additionally or alternatively, the 3D-formable sheet material has an extensibility in the range of 6 to 18%, preferably 7 to 18%, at a moisture content of 20% in the 3D-formable sheet material.

Extensibility at a particular moisture content can be determined by the following formula (II)

where ʺmoistureʺ is defined as ( X% moisture - % reference moisture ), and % reference moisture refers to a significant lower moisture level.

It should be appreciated that the 3D formed sheet material may also show signs of high or improved elongation at break. For example, the 3D-formable sheet material has an elongation at break of at least 6%, preferably 6 to 16%, and most preferably 7 to 15%.

The 3D-formable sheet material preferably has a sheet weight of 50 to 500 g/m ² , preferably 80 to 300 g/m ² , and most preferably 80 to 250 g/m ² .

Thus, the 3D-formable sheet material preferably has

a) increase in stretch, normalized to moisture content, in the range of 0.15 to 0.7% per percent, more preferably 0.15 to 0.6% per percent, and most preferably 0.2 to 0 .6% per percentage, and/or

b) an elongation at break of at least 6%, more preferably 6 to 16% and most preferably 7 to 15%, and/or

c) a sheet weight of 50 to 500 g/m ² , more preferably 80 to 300 g/m ² and most preferably 80 to 250 g/m ² .

For example, the 3D formable sheet material preferably has

a) increase in stretch, normalized to moisture content, in the range of 0.15 to 0.7% per percent, more preferably 0.15 to 0.6% per percent, and most preferably 0.2 to 0 .6% per percentage, and

b) an elongation at break of at least 6%, more preferably 6 to 16% and most preferably 7 to 15%, or

c) a sheet weight of 50 to 500 g/m ² , more preferably 80 to 300 g/m ² and most preferably 80 to 250 g/m ² .

For example, the 3D formable sheet material preferably has

a) increase in stretch, normalized to moisture content, in the range of 0.15 to 0.7% per percent, more preferably 0.15 to 0.6% per percent, and most preferably 0.2 to 0 .6% per percentage, or

b) an elongation at break of at least 6%, more preferably 6 to 16% and most preferably 7 to 15%, and

c) a sheet weight of 50 to 500 g/m ² , more preferably 80 to 300 g/m ² and most preferably 80 to 250 g/m ² .

In one embodiment, the 3D formable sheet material has

a) increase in stretch, normalized to moisture content, in the range of 0.15 to 0.7% per percent, more preferably 0.15 to 0.6% per percent, and most preferably 0.2 to 0 .6% per percentage, or

b) an elongation at break of at least 6%, more preferably 6 to 16% and most preferably 7 to 15%, or

c) a sheet weight of 50 to 500 g/m ² , more preferably 80 to 300 g/m ² and most preferably 80 to 250 g/m ² .

Preferably, the 3D formed sheet material has

a) increase in stretch, normalized to moisture content, in the range of 0.15 to 0.7% per percent, more preferably 0.15 to 0.6% per percent, and most preferably 0.2 to 0 .6% per percentage, and

b) an elongation at break of at least 6%, more preferably 6 to 16% and most preferably 7 to 15%, and

c) a sheet weight of 50 to 500 g/m ² , more preferably 80 to 300 g/m ² and most preferably 80 to 250 g/m ² .

Next, the components of the 3D moldable sheet material will be described in more detail.

Cellulosic material is a mixture based on cellulose material, including

i) nanofibrillated cellulose and/or microfibrillated cellulose in an amount of ≥55% by weight, based on the total dry weight of the mixture based on the cellulose material, and

ii) cellulose fibers in an amount of ≤45% by weight, based on the total dry weight of the mixture based on cellulose material.

One requirement for a cellulosic material mixture is that the sum of nanofibrillated cellulose and/or microfibrillated cellulose and cellulose fibers is 100% by weight, based on the total dry weight of the cellulosic material mixture.

The use of nanofibrillated cellulose and/or microfibrillated cellulose has the advantage that separation of the at least one particulate inorganic filler material and optional additives becomes more difficult, resulting in a mass in which the individual components are uniformly distributed.

In one embodiment, the cellulosic material mixture includes

i) nanofibrillated cellulose or microfibrillated cellulose, preferably microfibrillated cellulose, in an amount of ≥55% by weight, based on the total dry weight of the mixture based on the cellulose material, and

ii) cellulose fibers in an amount of ≤45% by weight, based on the total dry weight of the mixture based on cellulose material,

and the sum of the amount of nanofibrillated cellulose or microfibrillated cellulose and cellulose fibers is 100% by weight, based on the total dry weight of the mixture based on cellulose material.

Alternatively, the cellulosic material mixture comprises

i) nanofibrillated cellulose and microfibrillated cellulose in an amount of ≥55% by weight, based on the total dry weight of the mixture based on the cellulose material, and

ii) cellulose fibers in an amount of ≤45% by weight, based on the total dry weight of the mixture based on cellulose material,

and the sum of the amount of nanofibrillated cellulose and microfibrillated cellulose and cellulose fibers is 100% by weight, based on the total dry weight of the mixture based on cellulose material.

Thus, the cellulosic material mixture preferably includes nanofibrillated cellulose or microfibrillated cellulose, preferably microfibrillated cellulose, in an amount of ≥55% by weight, based on the total dry weight of the cellulosic material mixture. For example, a cellulosic material mixture includes nanofibrillated cellulose or microfibrillated cellulose, preferably microfibrillated cellulose, in an amount of 55 to 99% by weight, based on the total dry weight of the cellulosic material mixture. Preferably, the cellulosic material mixture comprises nanofibrillated cellulose or microfibrillated cellulose, preferably microfibrillated cellulose, in an amount of 60 to 95% by weight, based on the total dry weight of the cellulosic material mixture.

In addition, the cellulosic material mixture includes cellulose fibers in an amount of ≦45 wt %, based on the total dry weight of the cellulosic material mixture. For example, a cellulosic material mixture includes cellulose fibers in an amount of 1 to 45% by weight, based on the total dry weight of the cellulosic material mixture. Preferably, the cellulosic material mixture comprises cellulose fibers in an amount of 5 to 40% by weight, based on the total dry weight of the cellulosic material mixture.

In one embodiment, the weight ratio of nanofibrillated cellulose and/or microfibrillated cellulose to cellulose fibers in the mixture based on cellulose material, based on dry weight, is from 90:10 to 50:50, more preferably from 90:10 to 60:40, even more preferably 90:10 to 70:30, and most preferably 90:10 to 80:20, such as about 90:10 or about 85:15.

The terms "nanofibrillated cellulose" and "microfibrillated cellulose" refer to a commonly known definition, such as that found in H. Sixta (Ed.), Handbook of Pulp, Wiley-VCH.

Cellulosic mass as a starting material is made from wood or stems of plants such as hemp, flax and manila hemp. Cellulosic pulp fibers are mainly composed of cellulose and other organic components (hemicellulose and lignin). Cellulose macromolecules (consisting of β-D-Glucose molecules linked by a 1-4-glycosidic bond) are hydrogen-bonded to form a so-called fibril (also called an elementary fibril or micelle), which has crystalline and amorphous domains. Several nanofibrils (about 55) form a so-called microfibril. Approximately 250 of these microfibrils form a fibril.

The fibrils are arranged in different layers (which may contain lignin and/or hemicellulose) to form a fiber. Individual fibers are also linked by lignin.

When the fibers are refined under the influence of applied energy, they become fibrillated as the cell walls break through and separate into attached strips, i.e. fibrils. If such tearing continues with the separation of the fibrils from the fiber body, then it leads to the release of the fibrils. The breaking of fibers into microfibrils is called "micro-fibrillation". This process can continue until there are no more fibers, and only nanofibrils remain.

If the process goes further and breaks these fibrils into smaller and smaller fibrils, then they obviously become cellulose fragments. Breaking to nanofibrils can be referred to as "nanofibrillation", where a smooth transition between the two modes can take place.

The term "nanofibrillated cellulose" in the context of the present invention means fibers that are at least partially broken into nanofibrils (also called elemental fibrils).

The term "microfibrillated cellulose" in the context of the present invention means fibers that are at least partially broken into microfibrils. The microfibrillated cellulose preferably has a Brookfield viscosity in the range of 1 to 2000 mPa.s at 25°C, more preferably 10 to 1200 mPa.s at 25°C, and most preferably 100 to 600 mPa.s at 25 °C, when the content of nanofibrillated cellulose and/or microfibrillated cellulose is 1 wt. %, based on the total weight of the aqueous suspension.

In this regard, fibrillation in the context of the present invention means any process that preferentially breaks (breaks) the fibers and fibrils along their longitudinal axis, resulting in a reduction in the diameter of the fibers and fibrils, respectively.

Nanofibrillated and microfibrillated celluloses and their production are well known to the person skilled in the art. For example, nanofibrillated and microfibrillated celluloses and their preparation are described in patent applications EP 2386682 A1, EP 2386683 A1, EP 2236664 A1, EP 2236545 A1, EP 2808440 A1 and EP 2805986 A1, which are hereby incorporated by reference herein, as well as in Franklin W. Herrick, et al. "Microfibrillated Cellulose: Morphology and Accessibility", Journal of Applied Polymer Science: Applied Polymer Symposium 37 , 797-813 (1983), and Hubbe et al. "Cellulosic nanocomposites, review" BioResources , 3(3), 929-890 (2008).

Preferably, nanofibrillated cellulose and/or microfibrillated cellulose is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the absence or presence of fillers and/or pigments.

In one embodiment, nanofibrillated cellulose and/or microfibrillated cellulose is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the absence of fillers and/or pigments. Thus, nanofibrillated cellulose and/or microfibrillated cellulose is free from fillers and/or pigments. Accordingly, the 3D moldable sheet material is free of fillers and/or pigments other than the at least one particulate inorganic filler material in this embodiment.

Nanofibrillated cellulose and/or microfibrillated cellulose, which is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the absence of fillers and/or pigments, is preferably in the form of an aqueous suspension. Preferably, the aqueous suspension has a Brookfield viscosity in the range of 1 to 2000 mPa.s at 25°C, more preferably 10 to 1200 mPa.s at 25°C, and most preferably 100 to 600 mPa.s at 25°C, when the content of nanofibrillated cellulose and/or microfibrillated cellulose 1% wt., based on the total weight of the aqueous suspension.

In an alternative embodiment, nanofibrillated cellulose and/or microfibrillated cellulose is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the presence of fillers and/or pigments.

Fillers and/or pigments are preferably selected from the group consisting of precipitated calcium carbonate (PCC); natural finely divided calcium carbonate (GCC); dolomite; talc; bentonite; clay; magnesite; white pigment satin; sepiolite, ganthite, diatomite; silicates; and their mixtures. Precipitated calcium carbonate, which may have a vaterite, calcite or aragonite crystal structure, and/or natural finely ground calcium carbonate, which may be selected from marble, limestone and/or chalk, are particularly preferred.

In a preferred embodiment, the use of natural finely ground calcium carbonate (GCC) such as marble, limestone and/or chalk as filler and/or pigment may be advantageous.

It will be appreciated that the 3D-formable sheet material may thus include additional fillers and/or pigments in addition to the at least one particulate inorganic filler material. The at least one particulate inorganic filler material and additional fillers and/or pigments may be the same or different. Preferably, the at least one particulate inorganic filler material and the additional fillers and/or pigments are different.

In one embodiment, the weight ratio of nanofibrillated cellulose and/or microfibrillated cellulose to fillers and/or pigments, on a dry weight basis, is 1:10 to 10:1, more preferably 1:6 to 6:1 , usually from 1:4 to 4:1, in particular from 1:3 to 3:1, and most preferably from 1:2 to 2:1, for example 1:1.

Nanofibrillated cellulose and/or microfibrillated cellulose preferably includes fillers and/or pigments in amounts ranging from 5 to 90% by weight, preferably from 20 to 80% by weight, more preferably from 30 to 70% by weight. and most preferably from 35 to 65% by weight, based on the total dry weight of the nanofibrillated cellulose and/or microfibrillated cellulose.

Thus, the cellulosic material of the 3D-formable sheet material preferably includes fillers and/or pigments in amounts ranging from 2 to 85% by weight, preferably from 2 to 70% by weight, more preferably from 3 to 50% by weight. . and most preferably from 5 to 40% by weight, based on the total dry weight of the cellulosic material. It will be appreciated that the fillers and/or pigments result from nanofibrillation and/or microfibrillation of a suspension of cellulose fibers in the presence of fillers and/or pigments.

Nanofibrillated cellulose and/or microfibrillated cellulose, which is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the presence of fillers and/or pigments, is preferably in the form of an aqueous suspension. Preferably, the aqueous suspension has a Brookfield viscosity in the range of 1 to 2000 mPa.s at 25°C, more preferably 3 to 1200 mPa.s at 25°C, and most preferably 10 to 600 mPa.s at 25°C, when the content of nanofibrillated cellulose and/or microfibrillated cellulose 1% wt., based on the total weight of the aqueous suspension.

In a preferred embodiment, the filler and/or pigment particles have a median particle size of 0.03 to 15 µm, preferably 0.1 to 10 µm, more preferably 0.2 to 5 µm, and most preferably 0 .2 to 4 µm, for example 1.6 µm or 3.2 µm.

It will be appreciated that the cellulosic fibers of the suspension of cellulosic fibers from which the nanofibrillated cellulose and/or microfibrillated cellulose is derived are preferably those contained in a pulp selected from the group consisting of softwood pulp such as softwood pulp. pulp and pine pulp, hardwood pulp such as eucalyptus pulp, birch pulp, beech pulp, maple pulp, acacia pulp, and other types of pulp such as hemp pulp, cotton pulp, bagasse or straw pulp, or recycled fiber material, and mixtures thereof.

Nanofibrillated cellulose and/or microfibrillated cellulose is preferably obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the presence of fillers and/or pigments.

The mixture based on cellulose material additionally contains cellulose fibers.

The cellulosic fibers present in the cellulosic material mixture are preferably selected from the group consisting of softwood fibers such as softwood fibers and pine fibers, hardwood fibers such as eucalyptus fibers, birch fibers, beech fibers, maple fibers, acacia fibres, and other types of fibres, such as hemp fibres, cotton fibres, bagasse or straw fibres, or recycled fibres, and mixtures thereof.

It should be appreciated that the cellulose fibers present in the mixture based on the cellulose material may be from the same or different fibers from which the nanofibrillated cellulose and/or microfibrillated cellulose is derived. Preferably, the cellulose fibers present in the mixture based on cellulose material come from various fibers from which nanofibrillated cellulose and/or microfibrillated cellulose is obtained.

In one embodiment, the cellulosic fibers present in the cellulosic material mixture are eucalyptus fibers.

It should be appreciated that the cellulose fibers of the suspension of cellulose fibers from which the nanofibrillated cellulose and/or microfibrillated cellulose is obtained and the cellulose fibers may be the same or different. Preferably, the cellulose fibers of the suspension of cellulose fibers from which nanofibrillated cellulose and/or microfibrillated cellulose are derived and the cellulose fibers are different.

Preferably, the cellulosic fibers present in the cellulosic material mixture have a length-weighted average fiber length of 500 µm to 3000 µm, more preferably 600 µm to 2000 µm, and most preferably 700 to 1000 µm.

Another essential component of the 3D moldable sheet material of the present invention is at least one particulate inorganic filler material.

The term "at least one" particulate inorganic filler material in the context of the present invention means that the particulate inorganic filler material includes, preferably consists of, one or more particulate inorganic filler materials.

In one embodiment of the present invention, at least one particulate inorganic filler material includes, preferably consists of, one particulate inorganic filler material. Alternatively, at least one particulate inorganic filler material includes, preferably consists of, two or more particulate inorganic filler materials. For example, at least one particulate inorganic filler material includes, preferably consists of, two or three particulate inorganic filler materials.

Preferably, the at least one particulate inorganic filler material comprises, more preferably consists of, one particulate material.

The term at least one "particulate" inorganic filler material in the context of the present invention refers to a solid compound that comprises, preferably consists of, an inorganic filler material.

The at least one particulate inorganic filler material may be a particulate natural, synthetic or mixed inorganic filler material such as an alkaline earth metal carbonate (e.g. calcium carbonate or dolomite), a metal sulfate (e.g. barite or gypsum) , metal silicate, metal oxide (for example, titanium dioxide or iron oxide), kaolin, calcined (calcined) kaolin, talc or mica, or any mixture or combination thereof.

Particularly good results with respect to elongation and elongation at break are obtained when at least one particulate inorganic filler material is at least one particulate material containing calcium carbonate.

The term "material containing calcium carbonate" refers to a material that contains at least 50.0% of the mass. calcium carbonate, based on the total dry weight of the material containing calcium carbonate.

According to one embodiment of the present invention, the at least one particulate calcium carbonate containing material is selected from dolomite, at least one natural finely divided calcium carbonate (GCC), at least one precipitated calcium carbonate (PCC), and mixtures thereof.

"Dolomite" in the context of the present invention is a calcium magnesium carbonate mineral having the chemical composition CaMg(CO ₃ ) ₂ ('CaCO ₃ MgCO ₃ '). The mineral dolomite contains at least 30.0% of the mass. MgCO ₃ , based on the total weight of dolomite, preferably more than 35.0 wt. -%, more preferably, more than 40.0 wt. -%, usually from 45.0 to 46.0 wt. _MgCO3 .

"Natural finely ground calcium carbonate" (GCC) in the context of the present invention is calcium carbonate obtained from sources of natural origin, such as limestone, marble or chalk, and subjected to wet and/or dry processing, such as grinding, sieving and/ or fractionation, for example, using a cyclone separator or classifier.

According to one embodiment, the GCC is dry milled. According to another embodiment of the present invention, GCC is obtained by wet milling and subsequent drying.

In general, the grinding step can be carried out using any commonly used grinding device, for example, under conditions in which refining mainly occurs as a result of collisions with the secondary body, for example, in one or more devices selected from: ball mill, rod mill, vibratory mill, roller crusher, impact centrifugal mill, vertical bead mill, attritor mill, pin mill, hammer mill, pulverizer mill, shredder, ungrouper, cutting machine, or other such equipment known to a person skilled in the art. areas. In the case where the calcium carbonate-containing material includes a wet-milled calcium carbonate-containing material, the grinding step may be carried out under self-grinding conditions and/or by grinding in a horizontal ball mill and/or other such processes known in the art. specialist. The wet-worked calcium carbonate-containing pulverized material thus obtained can be washed and dewatered by well-known processes, for example using flocculation, filtration or forced evaporation before drying. The subsequent drying step may be carried out in one step, such as spray drying, or at least two steps. It is also common for such calcium carbonate material to be treated in a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities.

In one embodiment, the GCC is selected from the group consisting of marble, chalk, limestone, and mixtures thereof.

"Precipitated calcium carbonate" (PCC) in the context of the present invention is a synthesized material, usually obtained by precipitation after the reaction of carbon dioxide and lime in an aqueous medium or by precipitation of a source of calcium ions and carbonate ions in water. PCC may include one or more crystalline forms selected from aragonite, vaterite and calcite mineralogical crystalline forms. Preferably, PCC has a single crystal form selected from aragonite, vaterite and calcite mineralogical crystal forms.

Aragonite usually has an acicular shape, where vaterite refers to a hexagonal crystal system. Calcite can form scalenohedral, prismatic, spherical, and rhombohedral shapes. PCC can be obtained in various ways, for example, precipitation by carbon dioxide, using the lime-soda process, or using the Solvay process, in which PCC is a by-product of ammonia production. The resulting PCC slurry can be mechanically dewatered and dried.

Preferably, the at least one particulate inorganic filler material is a calcium carbonate-containing particulate material which is at least one precipitated calcium carbonate (PCC), preferably at least one precipitated calcium carbonate (PCC) of aragonite , vaterite or calcite mineralogical crystalline form.

In addition to calcium carbonate, the at least one particulate calcium carbonate-containing material may further comprise metal oxides such as titanium dioxide and/or aluminum trioxide, metal hydroxides such as aluminum trihydroxide, metal salts such as as sulfates, silicates such as talc and/or kaolin clay and/or mica, carbonates such as magnesium carbonate and/or gypsum, satin white pigment and mixtures thereof.

According to one embodiment of the present invention, the amount of calcium carbonate in at least one particulate containing calcium carbonate material is ≥50.0 wt%, preferably 90.0 wt%, more preferably ≥95.0 wt%. and most preferably ≥97.0% by weight, based on the total dry weight of the calcium carbonate-containing material.

Preferably, at least one particulate inorganic filler material, preferably at least one particulate material containing calcium carbonate, has a mass median particle size d ₅₀ of 0.1 to 20.0 µm, preferably in the range from 0.3 to 10.0 µm, more preferably in the range from 0.4 to 8.0 µm, and most preferably in the range from 0.5 to 4.0 µm, for example, 2.7 µm, which is measured by the sedimentation method .

Throughout this document, the "particle size" of the calcium carbonate-containing filler material or other particulate materials is described by its particle size distribution. The value of d _x means the diameter relative to which x % by weight of the particles have diameters less than d _x . This means that the value of d ₂₀ reflects the particle size, relative to which 20% of the mass. all particles are less than the specified diameter, and the value of d ₉₈ reflects the particle size, relative to which 98% of the mass. of all particles are less than the specified diameter. The value of d ₉₈ is also considered as ʺmaximum diameter of 98% of the mass. all particles (top cut)ʺ. The value of d ₅₀ thus means the mass-median particle size, that is, 50% of the mass. all grains are smaller than this particle size. For the purpose of the present invention, the particle size is given as the weight median particle size d ₅₀ unless otherwise indicated. To determine the value of the mass median particle size d ₅₀ or the value of the maximum size of 98% of the mass. all d ₉₈ particles, the Sedigraph ^TM 5100 or 5120 instrument from Micromeritics, USA can be used. This method and this tool are known to the skilled person and are commonly used to determine the grain size of fillers and pigments. The measurement is carried out in an aqueous solution containing 0.1% of the mass. Na ₄ P ₂ O ₇ . Samples are subjected to dispersion using a high-speed stirrer and an ultrasonic generator.

At least one particulate inorganic filler material, preferably at least one particulate material containing calcium carbonate, may have a maximum diameter of 98% by weight. all particles, for example, below 40.0 µm. Preferably, at least one particulate inorganic filler material, preferably at least one particulate material containing calcium carbonate, has a maximum diameter of 98 wt%. all particles below 30.0 µm and more preferably below 20.0 µm.

Additionally or alternatively, the at least one particulate inorganic filler material, preferably the at least one particulate calcium carbonate containing material, has a specific surface area of 0.5 to 200.0 m ² /g, more preferably, from 0.5 to 100.0 m ² /g, and most preferably from 0.5 to 50.0 m ² /g, as measured by the nitrogen BET method.

The term "specific surface area" (in m ² /g) of at least one particulate containing calcium carbonate material in the context of the present invention is determined using the BET method, which is well known to the person skilled in the art (ISO 9277:1995).

It should be appreciated that the 3D-formable sheeting is preferably free of layers/layers containing polymeric materials that are suitable for improving the extensibility and elongation at break of the sheeting. Thus, the 3D-formable sheet material is preferably free of (synthetic) polymeric materials such as polyethylene (PE), polypropylene (PP), poly(ethylene vinyl alcohol) (EVOH) and the like.

According to another aspect of the present invention, a method is provided for obtaining a 3D moldable article. Where the method includes the steps:

a) providing 3D formable sheeting as defined herein, and

b) molding the 3D moldable sheet material into a 3D molded article.

With regard to the definition of 3D-formable sheeting and its preferred embodiments, reference is made to the statements above when considering the technical features of the 3D-formable sheeting of the present invention.

Forming a 3D molded sheet material into a 3D molded article can be undertaken using all methods and process lines well known to one of skill in the art with respect to molding 3D molded articles. However, it should be appreciated that the blow molding (stamping) processes according to DIN 8583 are generally not suitable for forming a 3D moldable sheet material into a 3D molded article.

The 3D molded articles are preferably formed by a stretch-compression molding according to DIN 8584 or a stretch molding according to DIN 8585.

Forming a 3D moldable sheet material into a 3D molded article is preferably performed using thermoforming, vacuum forming, pneumatic (air pressure) forming, deep drawing forming, hydroforming, spherical forming, compression molding, or vacuum/pneumatic forming. These methods are well known to the person skilled in the art in relation to the molding of 3D molded articles.

Preferably, the 3D moldable sheet material that is molded into the 3D molded article should have a specific moisture content to facilitate the molding process in step b). In particular, it is preferable that the 3D-formable sheeting provided in step a) has a moisture content of ≥2% by weight, based on the total dry weight of the 3D-formable sheeting. However, if the moisture content exceeds the specific value, the quality of the resulting 3D-molded article usually deteriorates. Thus, it is preferable that the 3D-formable sheeting provided in step a) has a moisture content of ≦30 wt %, based on the total dry weight of the 3D-formable sheeting.

Thus, the 3D-formable sheeting provided in step a) preferably has a moisture content in the range of 2 to 30% by weight, based on the total dry weight of the 3D-formable sheeting. For example, the 3D-formable sheet material provided in step a) preferably has a moisture content in the range of 6 to 25% by weight. or from 10 to 20% by weight, based on the total dry weight of the 3D-formable sheet material.

In the case where the moisture content of the 3D-formable sheet material provided in step a) is ≤2 wt%. or ≥30 wt. %, based on the total dry weight of the 3D-formable sheet material, the 3D-formable sheet material, respectively, may be moistened.

In one embodiment, the method thus further includes step c) moistening the 3D-formable sheet material provided in step a) to a moisture content of 2 to 30% by weight, based on the total dry weight of 3D - formed sheet material. Preferably, stage c) is carried out so that the 3D-formable sheet material is moistened to a moisture content of from 6 to 25% of the mass. or from 10 to 20% by weight, based on the total dry weight of the 3D-formable sheet material.

It will be appreciated that the moisture content after wetting is determined in accordance with common practice, that is, the moisture content is preferably not determined directly after wetting. Preferably, the moisture content after wetting is only determined when the 3D-formed sheet material has reached an equilibrium moisture content. Methods for obtaining and determining such an equilibrium moisture content are well known to the person skilled in the art.

For example, the moisture content is determined at least 30 minutes after wetting the 3D-formable sheeting. Preferably, the moisture content is determined after 30 minutes - 24 hours, for example, after 1 hour - 24 hours, after wetting the 3D-formable sheeting.

Moisturizing step c) is preferably carried out before and/or during process step b). In one embodiment, the humidification step c) is carried out before and during the process step b). Alternatively, the moisturizing step c) is carried out before or during the process step b). For example, the stage of humidification c) is carried out before the technological stage b).

Wetting the 3D formed sheet material can be undertaken using all methods and tools well known to one of skill in the art with regard to wetting materials. For example, wetting the 3D-formable sheet material can be done using spraying.

Preferably, the 3D formable sheet material is obtained by

i) providing cellulosic material as defined herein,

ii) forming a pre-sheet consisting of the cellulosic material of step i), and

iii) drying the pre-sheet of step ii) to form a 3D formable sheet material.

If the 3D-formable sheet material includes additives, then the cellulosic material is combined with the additives in step i).

In one embodiment, the cellulose material is combined with at least one particulate inorganic filler material as defined herein to form a mixture of cellulose and inorganic filler material. It should be appreciated that this embodiment is preferably applied when the cellulosic material does not contain filler and/or pigments. If the 3D-formable sheet material includes additives, then the cellulose material is combined with at least one particulate inorganic filler material and additives in step i) to form a mixture of cellulose and inorganic filler material.

With regard to the definition of cellulosic material, at least one particulate inorganic filler material, additives and their preferred embodiments, reference is made to the statements above when considering the technical features of the 3D-formable sheet material of the present invention.

The cellulosic material is preferably provided in the form of an aqueous suspension. For example, in the form of an aqueous suspension containing cellulosic material in the range of 0.2 to 35 wt. %, more preferably 0.25 to 20 wt. %, even more preferably 0.5 to 15 wt. %, most preferably from 1 to 10% wt., based on the total weight of the aqueous suspension.

In one embodiment, the cellulosic material is nanofibrillated cellulose and/or microfibrillated cellulose, which is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the absence or presence of fillers and/or pigments.

If the cellulosic material is nanofibrillated cellulose and/or microfibrillated cellulose, which is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the presence of fillers and/or pigments, then the fillers and/or pigments and at least one particulate inorganic filler material may be the same. In other words, the fillers and/or pigments are at least one particulate inorganic filler material. In this embodiment, the cellulosic material is thus preferably not further combined with at least one particulate inorganic filler material.

In another preferred embodiment, the cellulose material is nanofibrillated cellulose and/or microfibrillated cellulose, which is obtained by nanofibrillation and/or microfibrillation of a suspension of cellulose fibers in the absence or presence of fillers and/or pigments, and the cellulose material is further combined with at least one from particles with an inorganic filler material.

In either case, the cellulosic material provided includes fillers and/or pigments and/or the cellulosic material is combined with at least one particulate inorganic filler material such that the 3D formable sheet material includes at least one particulate inorganic filler material in an amount of ≥45 wt %, based on the total dry weight of the 3D moldable sheeting.

If the cellulosic material is combined with at least one particulate inorganic filler material, the at least one particulate inorganic filler material is provided in powder form, ie in dry form, or in the form of an aqueous suspension.

If at least one particulate inorganic filler material is provided in the form of an aqueous suspension, then the aqueous suspension contains the particulate inorganic filler material preferably in an amount of 1 to 80% by weight, more preferably 5 to 78% by weight. , even more preferably from 10 to 78% of the mass. and most preferably from 15 to 78% by weight, based on the total weight of the aqueous suspension.

In one embodiment, the cellulosic material is provided in the form of an aqueous suspension and at least one particulate inorganic filler material is provided in the form of an aqueous suspension.

Alternatively, the cellulosic material is provided in the form of an aqueous suspension and at least one particulate inorganic filler material is provided in powder form.

An aqueous "slurry" or "suspension" in the context of the present invention contains insoluble solids and water and may typically contain large amounts of solids and thus may be more viscous and generally may have a higher density than the liquid from which it is derived.

The term "aqueous" slurry or suspension refers to a system where the liquid phase contains, preferably consists of, water. However, said term does not exclude that the liquid phase of the aqueous slurry or suspension contains minor amounts of at least one water-miscible organic solvent selected from the group consisting of methanol, ethanol, acetone, acetonitrile, tetrahydrofuran, and mixtures thereof. If the aqueous slurry or suspension comprises at least one water-miscible organic solvent, then the liquid phase of the aqueous slurry contains at least one water-miscible organic solvent in an amount of from 0.1 to 40.0% by weight, preferably from 0.1 to 30.0% wt., more preferably, from 0.1 to 20.0% wt. and most preferably from 0.1 to 10.0% by weight, based on the total weight of the liquid phase of the aqueous slurry or suspension. For example, the liquid phase of an aqueous slurry or suspension consists of water. If the liquid phase of the aqueous slurry or suspension consists of water, then the water to be used may be any available water, such as tap water and/or deionized water.

The cellulosic material is combined with at least one particulate inorganic filler material and optional additives in any order. Preferably, at least one particulate inorganic filler material and optional additives are added to the cellulosic material.

Cellulosic material is a mixture based on cellulose material, including nanofibrillated cellulose and/or microfibrillated cellulose.

Preferably, the cellulose material is a mixture based on cellulose material, including nanofibrillated cellulose and/or microfibrillated cellulose, which is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the absence or presence of fillers and/or pigments.

In the case where nanofibrillated cellulose and/or microfibrillated cellulose is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the absence of fillers and/or pigments, the nanofibrillated cellulose and/or microfibrillated cellulose is preferably in the form of an aqueous suspension having a Brookfield viscosity in the range of 1 up to 2000 mPa.s at 25°C, more preferably from 10 to 1200 mPa.s at 25°C, and most preferably from 100 to 600 mPa.s at 25°C, when containing nanofibrillated cellulose and/or microfibrillated cellulose 1% wt., based on the total weight of the aqueous suspension.

In the case where nanofibrillated cellulose and/or microfibrillated cellulose is obtained by nanofibrillating and/or microfibrillating a suspension of cellulose fibers in the presence of fillers and/or pigments, the nanofibrillated cellulose and/or microfibrillated cellulose is preferably in the form of an aqueous suspension having a Brookfield viscosity in the range of 1 up to 2000 mPa.s at 25°C, more preferably from 3 to 1200 mPa.s at 25°C, and most preferably from 10 to 600 mPa.s at 25°C, when containing nanofibrillated cellulose and/or microfibrillated cellulose 1% wt., based on the total weight of the aqueous suspension.

An aqueous suspension of nanofibrillated cellulose and/or microfibrillated cellulose preferably contains nanofibrillated cellulose and/or microfibrillated cellulose in an amount of from 0.2 to 35 wt%, more preferably from 0.25 to 20 wt%, even more preferably from 0, 5 to 15 wt. -%, most preferably from 1 to 10 wt. -%, based on the total weight of the aqueous suspension.

Methods for obtaining nanofibrillated and microfibrillated celluloses are well known to the person skilled in the art. For example, methods for producing nanofibrillated and microfibrillated celluloses are described in patent applications EP 2386682 A1, EP 2386683 A1, EP 2236664 A1, EP 2236545 A1, EP 2808440 A1 and EP 2805986 A1, which are hereby incorporated herein by reference, and also in Franklin W. Herrick, et al. "Microfibrillated Cellulose: Morphology and Accessibility", Journal of Applied Polymer Science: Applied Polymer Symposium 37 , 797-813 (1983), and Hubbe et al. "Cellulosic nanocomposites, review" BioResources , 3(3), 929-890 (2008).

It will be appreciated that the term "mixture of cellulose and inorganic filler material" refers to a mixture of cellulosic material of at least one particulate inorganic filler material and optional additives. Preferably, the mixture of cellulose and inorganic filler material is a homogeneous mixture of cellulose material of at least one particulate inorganic filler material and optional additives.

The mixture of cellulose and inorganic filler material is preferably an aqueous suspension containing cellulosic material, at least one particulate inorganic filler material, and optional additives. In one embodiment, the aqueous suspension of a mixture of cellulose and inorganic filler material has a solids content in the range of 0.3 to 35 wt%, more preferably 0.5 to 30 wt%, even more preferably 0.7 up to 25 wt. -%, most preferably, from 0.9 to 20 wt. -%, based on the total weight of the aqueous suspension.

According to step ii) of the process, a preliminary sheet is obtained, consisting of a mixture of cellulose and inorganic filler material of step i).

Forming step ii) may be undertaken using all methods and techniques well known to the person skilled in the art with respect to forming a pre-sheet from a mixture of cellulose and inorganic filler material. Forming step ii) may be carried out using any conventional forming machine, for example, under conditions that produce a continuous or discontinuous pre-sheet from a mixture of cellulose and inorganic filler material, or using other such equipment known to a person skilled in the art. For example, shaping may be carried out in a paper machine as described in J. Rantanen, et al., Forming and dewatering of a microfibrillated cellulose composite paper. biores. 10(2), 2015, 3492-3506.

The pre-sheet of a mixture of cellulose and inorganic filler material may be subjected to a water reduction step in the pre-sheet. Such a water reduction step may be carried out during or after, preferably after, process step ii). Such a water reduction step may be undertaken using all methods and techniques well known to one of skill in the art with respect to reducing the water content of the presheet. The step of reducing the water content can be carried out by any conventional method, for example, by pressure, by vacuum during wet pressing, by gravity or by suction, resulting in a pre-sheet having a water content that is reduced compared to the water content before the stage of water reduction, or using other such equipment known to the person skilled in the art.

Unless otherwise specified, the term "water reduction" refers to a process whereby only a portion of the water is removed from the pre-sheet, resulting in a pre-dried pre-sheet. In addition, the "pre-dried" pre-sheet can be further defined by its total moisture content, which, unless otherwise indicated, is a value that is greater than or equal to 5 wt%, preferably greater than or equal to 8 wt%, more preferably, greater than or equal to 10 wt. -%, and most preferably from 20 to 60 wt. -%, based on the total weight of the preliminary sheet.

Thus, the method preferably further comprises step iv1) removing water from the preliminary sheet of step ii).

In one embodiment, the removal of water in step iv1) is carried out under pressure, preferably under a pressure in the range of 10 to 150 kPa, more preferably under a pressure in the range of 20 to 100 kPa, and most preferably under a pressure in the range of 30 to 80 kPa.

Alternatively, the method further comprises the step iv2) of wet pressing the pre-sheet of step ii).

In one embodiment, the pre-sheet obtained in step iv1) is further subjected to a wet pressing step in order to further reduce the water content. In this case, the method further includes step iv2) of wet pressing the pre-sheet of step iv1).

The wet pressing step iv2) is preferably carried out at a pressure in the range of 100 to 700 kPa, preferably a pressure in the range of 200 to 600 kPa, and most preferably a pressure in the range of 300 to 500 kPa. Additionally or alternatively, the wet pressing step iv2) is carried out at a temperature in the range of 10 to 80°C, preferably at a temperature in the range of 15 to 75°C, and more preferably at a temperature in the range of 20 to 70°C.

Preferably step iv2) of wet pressing the pre-sheet of step ii) or step iv1) is carried out at a pressure in the range of 100 to 700 kPa, preferably a pressure in the range of 200 to 600 kPa, and most preferably a pressure in the range of 300 up to 500 kPa, and at a temperature in the range from 10 to 80°C, preferably at a temperature in the range from 15 to 75°C, and more preferably at a temperature in the range from 20 to 70°C.

According to step iii), the preliminary sheet of step ii) or step iv1) or step iv2) is dried to obtain a 3D-formable sheet material.

The term "drying" refers to a process in which at least a portion of the water is removed from the pre-sheet, resulting in a 3D-formable sheet material. In addition, the "dried" 3D-formable sheet material can be further defined by its total moisture content, which, unless otherwise indicated, is less than or equal to 30 wt. -%, preferably less than or equal to 25 wt. -%, more preferably less than or equal to 20% by weight, and most preferably less than or equal to 15% by weight, based on the total weight of the dried material.

Such a drying step may be undertaken using all methods and techniques well known to the person skilled in the art with respect to drying the pre-sheet. The drying step may be carried out by any conventional method, for example by pressure, by gravity or by suction, resulting in a pre-sheet having a water content that is reduced compared to the water content prior to drying, or with using other such equipment known to the person skilled in the art.

In one embodiment, step iii) is carried out by compression drying. For example, using compression drying at a pressure in the range of 50 to 150 kPa, preferably a pressure in the range of 60 to 120 kPa, and most preferably a pressure in the range of 80 to 100 kPa, and/or at a temperature of in the range of 80 to 180°C, preferably at a temperature in the range of 90 to 160°C, and more preferably at a temperature in the range of 100 to 150°C.

In one embodiment, step iii) is carried out by compression drying at a pressure in the range of 50 to 150 kPa, preferably a pressure in the range of 60 to 120 kPa, and most preferably a pressure in the range of 80 to 100 kPa, and at a temperature in the range of 80 to 180°C, preferably at a temperature in the range of 90 to 160°C, and more preferably at a temperature in the range of 100 to 150°C.

In view of the very good results for 3D moldable sheeting as defined above, a further aspect of the present invention relates to the use of cellulosic material as defined herein and at least one particulate inorganic filler material as defined herein to make 3D - formed sheet material.

Another aspect of the present invention relates to the use of a cellulosic material as defined herein and at least one particulate inorganic filler material as defined herein to increase the extensibility of a 3D moldable sheet material, where the increase is achieved when The 3D-formable sheet material has an increase in stretch, normalized to the level of moisture content, in the range of 0.15 to 0.7% per percent. The increase in stretch, normalized to the level of moisture content, is preferably determined according to formula (I) defined above.

In one embodiment, the increase is achieved when the 3D-formable sheeting has an increase in elongation normalized to moisture content in the range of 0.15 to 0.6% per percent, and most preferably 0.2 to 0.6% per cent. The increase in stretch, normalized to the level of moisture content, is preferably determined according to formula (I) above.

In one embodiment, the 3D-formable sheeting has an extensibility in the range of 4 to 10%, preferably 5 to 10%, at a moisture content of 10% in the 3D-formable sheeting. Additionally or alternatively, the 3D moldable sheet material has an extensibility in the range of 6 to 18%, preferably 7 to 18%, at a moisture content of 20% in the 3D moldable sheet material. Extensibility is preferably determined according to formula (II) above.

Yet another additional aspect of the present invention relates to the use of 3D moldable sheeting as defined herein in 3D molding processes. Preferably, the present invention relates to the use of a 3D-formable sheet material as defined herein in thermoforming, vacuum forming, pneumatic forming, deep drawing forming, hydroforming, spherical forming, compression molding, or vacuum/air forming.

A further aspect of the present invention relates to a 3D molded article, preferably a packaging container, food container, blister pack, food tray, including(s) a 3D moldable sheet material as defined herein.

With regard to the definition of cellulosic material of at least one particulate inorganic filler material, 3D formable sheeting and preferred embodiments thereof, reference is made to the statements above when considering the technical features of the 3D formable sheeting of the present invention.

Description of figures

1 shows microfibrillated cellulose obtained in the presence of GCC (natural finely divided calcium carbonate) particles.

Figure 2 shows microfibrillated cellulose obtained in the absence of filler and/or pigments.

3 refers to a diagram showing the relationship between stretch and moisture content.

The following examples may further illustrate the invention, but are not intended to limit the invention to the exemplary embodiments. The examples below show the 3D moldable sheet material and its excellent and good mechanical properties such as tensile and elongation at break according to the present invention:

EXAMPLES

Measurement methods

The following measurement methods are used to evaluate the parameters given in the examples and claims.

Solids content of aqueous suspensions such as samples containing suspended pigments and cellulose

The slurry solids content (also referred to as "dry weight") is determined using an MJ33 moisture analyzer from Mettler-Toledo, Switzerland, with the following settings: drying temperature 160°C, automatic shutdown if the weight does not change by more than 1 mg, after time period 30 sec, standard drying from 5 to 20 g of suspension.

Moisture contents

Moisture content (% wt.)=100 (% wt.) - solids content (% wt.)

Particle size in the case of mineral particles

Mass Median Particle Sized ₅₀ used in this document, as well as the maximum size for 98% of the particle massd ₉₈ determined based on measurements made with the Sedigraph™ 5120 instrument from Micromeritics Instrument Corporation. The method and tools are known to the person skilled in the art and are commonly used to determine the grain size of fillers and pigments. The measurement is carried out in an aqueous solution containing 0.1% of the mass. Na₄P₂O₇. Samples are subjected to dispersion using a high-speed stirrer and an ultrasonic generator. To perform measurements on dispersed samples, no additional dispersing agents are added.

Fiber length measurement

Length-weighted average fiber length was determined using a Kajaani FS 200 instrument (Kajaani Electronics Ltd, now Valmet, Finland). The method and tool is known to the person skilled in the art and is commonly used to determine the morphological parameters of the fiber. The measurement is carried out for a solids content of approximately 0.010% of the mass.

The device for determining the degree of grinding (Device Shopper-Rigler)

The degree of Schhopper-Rigler freeness (°SR) is measured according to Zellcheming Merkblatt V/7/61 and standardized according to ISO 5267/1.

Brookfield viscosity

The Brookfield viscosity of aqueous suspensions is measured one hour after preparation and after one minute of agitation at 25°C ± 1°C at 100 revolutions per minute (rpm) using a Brookfield RVT-type viscometer equipped with an appropriate disc stem, such as a 1- 6.

Light microscopy to distinguish between MFC types

Photomicrographs are taken using a light microscope using the bright field method in transmitted light.

Film Forming Machine: Scandinavian Type Laboratory Sheet Forming Machine

The apparatus described in SCAN-CM64:00 "Preparation of laboratory sheets for physical testing" is used, some modifications are made (J. Rantanen et al., "Forming and dewatering of a microfibrillated cellulose composite paper", BioResources 10(2), 2015, page 3492 -3506).

Film Forming Machine: Laboratory Sheet Forming Machine "Rapid-Köthen-Type"

Use the apparatus described in ISO 5269/2 ʺPreparation of laboratory sheets for physical testing - Part 2: Rapid Köthen methodʺ, apply some modifications, for more details see the method section ʺMFC filler composite films produced with ʺRapid Köthen Typeʺ laboratory sheet formerʺ.

Tensile Testing Machine (Tensile and Tensile Tester)

An L&W tensile and tear tester (Lorentzen & Wettre, Sweden) is used to determine elongation at break according to the procedures described in ISO 1924-2.

Equipment and technique for 3D molding

A laboratory press with P300-type press plates (Dr. Collins, Germany) was used for molding. The pressure, temperature, and pressing time period are adjusted accordingly.

Two aluminum stamps are used. The first mold has outer dimensions of 16 cm x 16 cm x 2.5 cm and a die matrix portion of a circular segment with a diameter of 10 cm and a depth of 1 cm providing linear stretch levels of approximately 3%. A second mold with outer dimensions of 16 cm x 16 cm x 3.5 cm and a die die portion that is a circular segment with a diameter of 10 cm and a depth of 2 cm providing linear stretch levels of approximately 10%.

Flexible rubber sheets with dimensions of 20 cm × 20 cm × 1 cm, made of EPDM (ethylene-propylene-diene monomer rubber)

1. Material

Compound of microfibrillated cellulose (MFC) and filler

Compound microfibrillated cellulose (MFC) and filler is obtained by processing 40% of the mass. pre-treated with enzymes (Buckman Maximyze 2535) and mechanically (disk refiner, to a degree of grinding> 60 ° SR) pulp for chemical processing together with 60% of the mass. filler based on GCC ( ^Hydrocarb® 60) at 55% solids in a co-rotating twin screw extruder. The quality of microfibrillation is described by the image obtained using a microscope in Fig.1.

Microfibrillated cellulose (MFC) without filler

Microfibrillated cellulose (MFC) is used, which is described from the microscopic image in FIG. 2. It is commercially available in the form of a suspension with a solids content of 3.8 wt%.

Pulp hardwood pulp

Once dried commercial eucalyptus pulp with a length-weighted average fiber length of 0.81 mm.

Cellulosic mass of soft woods

Single dried softwood pulp (pine) with a length-weighted average fiber length of 2.39 mm.

GCC, Hydrocarb ^® 60 (available for purchase from Omya International AG, Switzerland)

Use a suspension of dispersed pigment based on natural finely divided calcium carbonate (GCC) with a solids content of 78% of the mass. and median by weight particle size d ₅₀ 1.6 μm.

PCC, Syncarb ^® F0474 (available for purchase from Omya International AG, Switzerland)

Use a suspension of non-dispersed pigment based on precipitated calcium carbonate (PCC) with a solids content of 15% of the mass. and median by weight particle size d ₅₀ 2.7 µm.

percol ^® 1540, BASF (Germany)

2. Ways

Obtaining samples of microfibrillated cellulose (MFC), obtained in the presence of a filler, for microscopy

A small sample (0.1 g) of the wet (approximately 55 wt %) MFC-filler compound (described in the 'Material' section) is placed in a glass beaker and 500 ml of deionized water is added. A kitchen blender is used to help separate the fibers and calcium carbonate particles. Then, 2 ml of a 10% (by weight) hydrochloric acid solution was added to dissolve the calcium carbonate, then the resulting mixture was mixed with a kitchen blender for 2 minutes. A few drops of this suspension are transferred to a microscope slide and dried in an oven at 120°C.

Preparation of MFC samples for microscopy

Approximately 1 g of unfilled microfibrillated cellulose ( MFC) as described in the 'Material' section above (solid content 3.8% by weight) is placed in a glass machine and 500 ml of deionized water is added. A kitchen blender is used for 2 minutes to separate the fiber material. A few drops of this suspension are transferred to a microscope slide and dried in an oven at 120°C.

Pulp making of hardwood

Once dried eucalyptus pulp mass is disintegrated (pulverized) according to ISO 5263-1 and diluted to a solids content of 1.5% of the mass. No refining is used.

Production of refined hardwood pulp

Once dried eucalyptus pulp mass is disintegrated (pulverized) according to ISO 5263-1 and diluted to a solids content of 3% wt. A laboratory disc refiner (Escher Wyss, now Voith, Germany) is used to prepare 30° SR eucalyptus pulp.

Pulp production of softwoods

The once dried softwood pulp is disintegrated (pulverized) according to ISO 5263-1 and diluted to a solids content of 1.5% by weight. No refining is used.

Production of refined softwood pulp

The once dried softwood pulp is disintegrated (pulverized) according to ISO 5263-1 and diluted to a solids content of 1.5% by weight. A laboratory disc refiner (Escher Wyss, now Voith, Germany) is used to prepare softwood pulp at a freeness of 25°SR.

Obtaining a batch for forming a film without MFC

According to formulations on a dry weight basis, blends of hardwood pulp or softwood pulp or refined softwood pulp, optional GCC and/or PCC particles, and deionized water, with a final solids content substances 1% wt. under high shear conditions (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) for a mixing time period of 15 minutes.

Obtaining a liquid suspension of the compound based on MFC and filler

Deionized water is added to the compound with a solids content of 55% of the mass. in such an amount to obtain a solids content of 10% of the mass. High shear mixing (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) is carried out for 15 minutes to disperse the compound, followed by further dilution with deionized water to achieve the desired solids content (5% wt., 4% wt., 2.5 wt%, 1 wt%) again using a high shear mixing step for 15 minutes (Pendraulik, 2000 rpm).

Obtaining a mixture for forming a film with a compound based on MFC and a filler

According to formulations on a dry weight basis, blends of MFC compound slurry and 1 wt % solids filler, hardwood pulp or softwood pulp and deionized water to a final solids content of 1 % wt. under high shear conditions (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) for a mixing time period of 15 minutes.

Obtaining an MFC suspension without filler

Deionized water is added to the MFC slurry in such an amount to obtain the desired solids levels (2% wt., 1% wt.), mixed under high shear conditions (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) for 15 minutes to ensure proper mixing.

Obtaining a mixture for forming a film with MFC without filler

Based on formulations on a dry weight basis, blends are prepared containing MFC, PCC and/or GCC, eucalyptus or softwood pulp, and deionized water, with a final solids content of 1% under high shear conditions. effort (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) over a mixing time period of 15 minutes.

Composite films based on MFC and filler obtained using a laboratory sheet-forming machine "Scandinavian Type"

To obtain films, a modified laboratory sheet-forming machine "Scandinavian Type" is used. The appropriate amount of prepared batch required to obtain a film weight of typically 200 g/m ² is loaded into the upper section, which is tightly connected to the membrane, which is the upper part of the lower section. The top section is capped and an overpressure of 0.5 bar is applied to accelerate the removal of water through the membrane. No vigorous agitation or further dilution is used. After molding, the sheets are made, as is known in the art, by placing them between two absorbent paper sheets and then pressed for 260 seconds at 420 kPa. To dry the sheets, an additional hot pressing step was used using four sheets placed between two absorbent paper sheets at a temperature of 130° C. and a pressure of 95 kPa. For physical testing, the sheets are placed in an air-conditioned chamber and a wetting procedure is used for shaping.

Composite films based on MFC and filler obtained using a laboratory sheet-forming machine

methodʺ используется со следующими модификациями: используют проволочное сито с размером ячейки 50 мкм. Никакую воду для разбавления не добавляют. Никакой воздух для смешивания не используют. По истечении 5 секунд после заполнения, открывают клапан для отведения воды и создают вакуум в течение 25 секунд. Листы подвергают прессованию с помощью пресса для формования листов (PTI, Austria) и затем сушат между впитывающими листами бумаги при 115°C в течение 8 минут.Sheet forming procedure according to ISO 5269/2 ʺPreparation of laboratory sheets for physical testing - Part 2: Rapid

methodʺ is used with the following modifications: a wire sieve with a mesh size of 50 µm is used. No dilution water is added. No mixing air is used. After 5 seconds after filling, open the valve to drain the water and create a vacuum for 25 seconds. The sheets were pressed with a sheet press (PTI, Austria) and then dried between absorbent paper sheets at 115° C. for 8 minutes.

Rewet Sheets for Forming Tests

Based on the moisture content present (100 - solids content in % wt.), the desired amount of deionized water is sprayed onto composite films based on MFC and filler using an aerosol can to obtain a moisture content of 6.25% wt., 8% wt. ., 10% wt., 15% wt. or 20% of the mass. Composite films based on MFC and filler with the same composition and the same moisture level are stored for 24 hours in a closed plastic bag to reliably ensure uniform moisture distribution.

3D molding

For 3D molding, some stack must be prepared, from bottom to top: first comes the lower part of the press with the press plates, then the aluminum die, where the casting mold is located face up, the sheet/film/material to be molded, a pack of rubber plates (3-4 to form 1 cm deep, 5-6 to form 2 cm deep) and finally the upper part of the press with press plates. In the press used, the lower part is movable and can be heated to the desired temperature. Before molding tests are started, the appropriate die is placed in a heated press to reach the desired temperature. Pressure, process dynamics (speed and time period), temperature must be adjusted accordingly.

3. Experiments

a) Viscosities of MFC suspensions

Table 1 Sample Suspension solids content
[wt%] Brookfield viscometer rod size Brookfield Viscosity (at 100 rpm and 25°C) Suspension of compound based on MFC and filler 10 No. 4 730 mPa⋅s Suspension of compound based on MFC and filler 5 No. 2 50.0 mPa⋅s Suspension of compound based on MFC and filler 2.5 No. 1 19.5 mPa⋅s MFC without filler 3.8 Can't be measured MFC without filler 2 No. 6 1800 mPa⋅s MFC without filler 1 No. 4 470 mPa⋅s

b) Properties of composite sheeting based on MFC and filler at various levels of moisture content

The properties of the resulting sheet materials are also shown in FIG. 3.

table 2 Compound Elongation at break, rms ^[1] 10% Elongation at break, rms ^[1] 20% Stretch increase normalized to moisture level [% per percent] Cellulose mass of hardwood, 200 g/m ² 2.1% 2.5% 0.04 Cellulose mass of hardwood (refined), 200 g/m ² (A) 3.0% 4.2% 0.12 Pulp pulp of softwood (refined), 200 g/m ² (B) 4.4% 5.6% 0.12 80% wt. pulp of softwood (refined) + 20% of the mass. GCC, 200 g/ ^m2 (C) 3.6% 4.1% 0.05 80% wt. pulp of softwood (refined) + 20% of the mass. PCC, 200 g/ ^m2 (D) 3.3% 4.7% 0.14 60% wt. pulp of softwood (refined) + 40% of the mass. PCC, 200 g/ ^m2 (E) 3.3% 4.6% 0.13 80% wt. pulp of softwood (refined) + 20% of the mass. PCC, 100 g/ ^m2 (F) 3.3% 4.6% 0.13 5% wt. pulp of hardwood, 30% of the mass. MFC, 65% wt. PCC, 200 g/ ^m2 (G) 7.3% 12.3% 0.5 5% wt. pulp of hardwood, 45% of the mass. MFC, 50% wt. PCC, 200 g/ ^m2 (H) 7.1% 10.2% 0.31 20% wt. pulp of hardwood, 30% of the mass. MFC, 50% wt. PCC, 200 g/ ^m2 (I) 4.9% 7.5% 0.26 ^[1] r.v.: moisture content.

c) 3D molding experiments

(1) 3D molding parameters

Sheets obtained using a laboratory sheet-forming machine "Scandinavian Type". It is advisable to use a lower molding pressure.

Table 3 Compound 3D Molding Options Mold depth Result 90% wt. compound MFC-filler, 10% wt. hardwood pulp, 200 g/m ² , s.v. ^[1] 8% 10 bar, 10 sec, 70°C 1 cm cracked specimen 90% wt. compound MFC-filler, 10% wt. hardwood pulp, 200 g/m ² , s.v. ^[1] 8% 10 bar, 7 sec, 120°C 1 cm cracked specimen 90% wt. compound MFC-filler, 10% wt. hardwood pulp, 200 g/m ² , s.v. ^[1] 8% 3.8 bar, 20 sec, 70°C 1 cm good sample 90% wt. compound MFC-filler, 10% wt. hardwood pulp, 200 g/m ² , s.v. ^[1] 8% 3.8 bar, 10 sec, 120°C 1 cm good sample ^[1] r.v.: moisture content.

(2) Reference samples

-Типʺ.Sheets obtained with the ʺRapid-

-Type.

Table 4 Compound 3D Molding Options Mold depth Result Refined hardwood pulp, 0.05% wt. Percol ^® 1540, based on the total dry weight of cellulosic material, 200 g/m ² d.m. ^[1] 8% 3.8 bar, 10 sec, 120°C 1 cm cracked specimen 80% wt. refined pulp of hardwood, 20% of the mass. GCC, 0.05 wt. Percol ^® 1540, calculated on the total dry weight of cellulosic material and inorganic filler material, 200 g/m ² d.h. ^[1] 8% 3.8 bar, 10 sec, 120°C 1 cm cracked sample Refined softwood pulp, 0.05% wt. Percol ^® 1540, based on the total dry weight of cellulosic material, 200 g/m ² d.m. ^[1] 8% 3.8 bar, 10 sec, 120°C 1 cm good sample 80% wt. refined pulp of softwood, 20% of the mass. GCC, 0.05 wt. Percol ^® 1540, calculated on the total dry weight of cellulosic material and inorganic filler material, 200 g/m ² d.h. ^[1] 8% 3.8 bar, 10 sec, 120°C 1 cm cracked specimen ^[1] r.v.: moisture content.

(3) Series 1 compound, basic conditions

Sheets obtained using a laboratory sheet-forming machine "Scandinavian Type".

Table 5 Compound 3D Molding Options Mold depth Result Cellulose mass of hardwood, 200 g/m ² , s.v. ^[1] 8% 3.8 bar, 10 sec, 120°C 1cm cracked specimen 5% wt. pulp of hardwood, 30% of the mass. MFC, 65% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 8% 3.8 bar, 10 sec, 120°C 1 cm good example 5% wt. pulp of hardwood, 45% of the mass. MFC, 50% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 8% 3.8 bar, 10 sec, 120°C 1 cm good sample, but cracking starts 20% wt. pulp of hardwood, 30% of the mass. MFC, 50% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 8% 3.8 bar, 10 sec, 120°C 1 cm good example ^[1] r.v.: moisture content.

(4) Series 2 compound, heavy duty and 15% by weight moisture.

Sheets obtained using a laboratory sheet-forming machine ʺScandinavian typeʺ.

Table 6 Compound 3D Molding Options Mold depth Result Cellulose mass of hardwood, 200 g/m ² , s.v. ^[1] 15% 3.8 bar, 10 sec, 120°C 2 cm cracked specimen 5% wt. pulp of hardwood, 30% of the mass. MFC, 65% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 15% 3.8 bar, 10 sec, 120°C 2 cm good sample, not fully molded ^[1] r.v.: moisture content.

(5) Series 3 compound, heavy duty and 20 wt% moisture.

Sheets obtained using a laboratory sheet-forming machine ʺScandinavian typeʺ.

Table 7 Compound 3D Molding Options Mold depth results Cellulose mass of hardwood, 200 g/m ² , s.v. ^[1] 20% 3.8 bar, 10 sec, 120°C 2 cm cracked specimen 5% wt. pulp of hardwood, 30% of the mass. MFC, 65% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 20% 3.8 bar, 10 sec, 120°C 2 cm good sample, not fully molded ^[1] r.v.: moisture content.

(6) Series 4 compounds, intensive mode, various compositions at a moisture content of 10% wt.

Sheets obtained using a laboratory sheet-forming machine ʺScandinavian typeʺ.

Table 8 Compound 3D Molding Options Mold depth Result 5% wt. pulp of hardwood, 30% of the mass. MFC, 65% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 10% 6.0 bar, 10 sec, 120°C 2 cm cracked specimen 5% wt. pulp of hardwood, 45% of the mass. MFC, 50% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 10% 6.0 bar, 10 sec, 120°C 2 cm cracked specimen 20% wt. pulp of hardwood, 30% of the mass. MFC, 50% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 10% 6.0 bar, 10 sec, 120°C 2 cm cracked specimen ^[1] r.v.: moisture content.

(7) Series 5 Compound, Heavy Duty, Various Compositions at 20 wt.

Sheets obtained using a laboratory sheet-forming machine ʺScandinavian typeʺ.

Table 9 Compound 3D Molding Options Mold depth Result 5% wt. pulp of hardwood, 30% of the mass. MFC, 65% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 20% 6.0 bar, 10 sec, 120°C 2 cm good example 5% wt. pulp of hardwood, 45% of the mass. MFC, 50% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 20% 6.0 bar, 10 sec, 120°C 2 cm cracked specimen 20% wt. pulp of hardwood, 30% of the mass. MFC, 50% wt. PCC, 200 g/ ^m2 , s.v. ^[1] 20% 6.0 bar, 10 sec, 120°C 2 cm good sample, not fully molded ^[1] r.v.: moisture content.

Claims (105)

1. 3D-formable sheet material, including a) cellulosic material in an amount of from 5 to 55 wt.%, based on the total dry weight of the 3D-formable sheet material, where the cellulosic material is a mixture based on cellulosic material containing i) nanofibrillated cellulose and/or microfibrillated cellulose in an amount of ≥55 wt.%, based on the total dry weight of the mixture based on cellulose material, and at the same time nanofibrillated cellulose and/or microfibrillated cellulose obtained by nanofibrillation and/or microfibrillation of a suspension of cellulose fibers in the absence or presence of fillers and/or pigments, wherein the cellulosic fibers of the cellulosic fiber suspension are recycled fiber material; And ii) cellulose fibers in an amount of ≤45% by weight, based on the total dry weight of the mixture based on cellulose material, moreover, the sum of the amount of nanofibrillated cellulose and/or microfibrillated cellulose and cellulose fibers is 100 wt. -%, based on the total dry weight of the mixture based on cellulose material, and the cellulose fibers are obtained from recycled fiber material; And (b) at least one particulate inorganic filler material in an amount of ≥45% by weight, based on the total dry weight of the 3D moldable sheeting, wherein the sum of the amount of cellulosic material and said at least one particulate inorganic filler material is 100.0% by weight, based on the total dry weight of the cellulosic material and said at least one particulate inorganic filler material. 2. The 3D-formable sheet material according to claim 1, wherein the nanofibrillated cellulose and/or microfibrillated cellulose is obtained by nanofibrillation and/or microfibrillation of a suspension of cellulose fibers in the absence of fillers and/or pigments. 3. The 3D-formable sheet material according to claim 1, wherein the nanofibrillated cellulose and/or microfibrillated cellulose is obtained by nanofibrillation and/or microfibrillation of a suspension of cellulose fibers in the presence of fillers and/or pigments. 4. The 3D formable sheet material of claim 2, wherein the 3D formable sheet material includes a) cellulosic material in an amount of 15 to 55% by weight, based on the total dry weight of the 3D-formable sheeting, and b) said at least one particulate inorganic filler material in an amount of 45 to 85% by weight, based on the total dry weight of the 3D moldable sheet material. 5. The 3D formable sheet material according to claim 3, wherein the 3D formable sheet material has a) increase in stretch, normalized to moisture content, in the range of 0.15 to 0.7% per percent moisture, and/or b) an elongation at break of at least 6%, and/or c) a sheet weight of 50 to 500 g/m ² . 6. The 3D moldable sheet material of claim 2, wherein said at least one particulate inorganic filler material is at least one particulate material containing calcium carbonate. 7. The 3D-formable sheet material of claim 6, wherein said at least one particulate material containing calcium carbonate is precipitated calcium carbonate. 8. The 3D moldable sheet material of claim 7, wherein the precipitated calcium carbonate is selected from one or more of its modifications selected from the group consisting of aragonite, vaterite, and calcite mineralogical crystal forms. 9. The 3D-formable sheet material of claim 3, wherein said at least one particulate material containing calcium carbonate is precipitated calcium carbonate. 10. The 3D moldable sheet material of claim 9, wherein the precipitated calcium carbonate is selected from one or more of its modifications selected from the group consisting of aragonite, vaterite, and calcite mineralogical crystal forms. 11. The 3D-formable sheet material of claim 6, wherein said at least one particulate material containing calcium carbonate is dolomite. 12. The 3D-formable sheet material of claim 9, wherein said at least one particulate material containing calcium carbonate is dolomite. 13. The 3D-formable sheet material of claim 6, wherein said at least one particulate material containing calcium carbonate is at least one natural finely divided calcium carbonate. 14. The 3D moldable sheet material of claim 13, wherein said at least one natural finely divided calcium carbonate is selected from the group consisting of marble, chalk, limestone, and mixtures thereof. 15. The 3D-moldable sheet material of claim 2, wherein said at least one particulate inorganic filler material comprises both precipitated and natural finely divided calcium carbonate containing materials. 16. The 3D-formable sheet material of claim 2, wherein said at least one particulate inorganic filler material has a) a mass median particle size d ₅₀ of 0.1 to 20.0 µm, and/or b) specific surface area from 0.5 to 200.0 m ² /g, which is measured using the nitrogen BET method. 17. The 3D-moldable sheet material of claim 9, wherein said at least one particulate material containing calcium carbonate is at least one natural finely divided calcium carbonate. 18. The 3D moldable sheet material of claim 17, wherein said at least one natural finely divided calcium carbonate is selected from the group consisting of marble, chalk, limestone, and mixtures thereof. 19. The 3D-moldable sheet material of claim 3, wherein said at least one particulate inorganic filler material comprises both precipitated and natural finely divided calcium carbonate containing materials. 20. The 3D-formable sheet material of claim 3, wherein said at least one particulate inorganic filler material has a) a mass median particle size d ₅₀ of 0.1 to 20.0 µm, and/or b) specific surface area from 0.5 to 200.0 m ² /g, which is measured using the nitrogen BET method. 21. A method for manufacturing a 3D molded article, wherein the method includes the steps a) providing the 3D-formable sheet material of claim 2, and b) forming a 3D moldable sheet material into a 3D molded article by a method selected from the group consisting of thermoforming, vacuum forming, pneumatic forming, deep drawing forming, hydroforming, spherical forming, compression molding, and vacuum/pneumatic forming. 22. The method according to claim 21, where the 3D-formable sheet material is obtained as a result i) providing cellulosic material according to claim 2, ii) forming a pre-sheet consisting of the cellulosic material of step i), and iii) drying the pre-sheet of step ii) to form a 3D formable sheet material. 23. The method of claim 21, wherein the cellulosic material of step i) is combined with at least one particulate inorganic filler material, wherein said particulate inorganic filler material is at least one particulate material comprising calcium carbonate. 24. The method of claim 23 wherein said at least one particulate calcium carbonate containing material is precipitated calcium carbonate. 25. The method according to claim 24, wherein the precipitated calcium carbonate is selected from one or more of its modifications selected from the group consisting of aragonite, vaterite and calcite mineralogical crystalline forms. 26. The method of claim 23, wherein said at least one particulate calcium carbonate containing material is dolomite. 27. The method of claim 23, wherein said at least one particulate calcium carbonate containing material is at least one naturally occurring finely divided calcium carbonate. 28. The method of claim 27, wherein said at least one natural finely ground calcium carbonate is selected from the group consisting of marble, chalk, limestone, and mixtures thereof. 29. The method of claim 23 wherein said at least one particulate inorganic filler material comprises both precipitated and natural finely divided calcium carbonate containing materials. 30. The method of claim 21, wherein the cellulosic material of step i) is combined with at least one particulate inorganic filler material, wherein said at least one particulate inorganic filler material has a) a mass median particle size d ₅₀ from 0.1 to 20.0 μm, and/or b) a specific surface area from 0.5 to 200.0 m ² /g, which is measured using the nitrogen BET method. 31. The method according to claim 21, where i) the cellulosic material is provided in the form of an aqueous suspension containing the cellulosic material in the range of 0.2 to 35% by weight, and/or ii) said at least one particulate inorganic filler material is provided in powder form, or in the form of an aqueous suspension, containing the inorganic particulate filler material in an amount of from 1 to 80% by weight, based on the total weight aqueous suspension. 32. The method according to claim 21, where the cellulose material is a mixture based on cellulose material, including nanofibrillated cellulose and / or microfibrillated cellulose, which is obtained by nanofibrillation and / or microfibrillation of a suspension of cellulose fibers in the absence of fillers and / or pigments, while the nanofibrillated cellulose and/or microfibrillated cellulose is preferably in the form of an aqueous suspension having a Brookfield viscosity in the range of 1 to 2000 mPa.s at 25° C., with a nanofibrillated cellulose and/or microfibrillated cellulose content of 1 wt %, based on the total weight of the aqueous suspension. 33. A method for manufacturing a 3D molded product, where the method includes the steps a) providing the 3D-formable sheeting of claim 3, and b) forming a 3D moldable sheet material into a 3D molded article by a method selected from the group consisting of thermoforming, vacuum forming, pneumatic forming, deep drawing forming, hydroforming, spherical forming, compression molding, and vacuum/pneumatic forming. 34. The method according to claim 33, where the 3D-formable sheet material is obtained as a result i) providing cellulosic material according to claim 3, ii) forming a pre-sheet consisting of the cellulosic material of step i), and iii) drying the pre-sheet of step ii) to form a 3D formable sheet material. 35. The method of claim 34, wherein the cellulosic material of step i) is combined with at least one particulate inorganic filler material, wherein said particulate inorganic filler material is at least one particulate material comprising calcium carbonate. 36. The method of claim 35, wherein said at least one particulate calcium carbonate containing material is precipitated calcium carbonate. 37. The method according to claim 36, wherein the precipitated calcium carbonate is selected from one or more of its modifications selected from the group consisting of aragonite, vaterite and calcite mineralogical crystalline forms. 38. The method of claim 35, wherein said at least one particulate material comprising calcium carbonate is dolomite. 39. The method of claim 35, wherein said at least one particulate calcium carbonate containing material is at least one natural finely divided calcium carbonate. 40. The method of claim 39, wherein said at least one natural finely ground calcium carbonate is selected from the group consisting of marble, chalk, limestone, and mixtures thereof. 41. The method of claim 35 wherein said at least one particulate inorganic filler material comprises both precipitated and natural finely divided calcium carbonate containing materials. 42. The method of claim 33, wherein the cellulosic material of step i) is combined with at least one particulate inorganic filler material, wherein said at least one particulate inorganic filler material has a) a mass median particle size d ₅₀ from 0.1 to 20.0 μm, and/or b) a specific surface area from 0.5 to 200.0 m ² /g, which is measured using the nitrogen BET method. 43. The method according to claim 33, where i) the cellulosic material is provided in the form of an aqueous suspension containing the cellulosic material in the range of 0.2 to 35% by weight, and/or ii) said at least one particulate inorganic filler material is provided in powder form, or in the form of an aqueous slurry, containing the inorganic particulate filler material in an amount of from 1 to 80% by weight, based on the total weight aqueous suspension. 44. The method according to claim 33, where the cellulose material is a mixture based on cellulose material, including nanofibrillated cellulose and / or microfibrillated cellulose, which is obtained by nanofibrillation and / or microfibrillation of a suspension of cellulose fibers in the presence of fillers and / or pigments, while the nanofibrillated cellulose and/or microfibrillated cellulose is preferably in the form of an aqueous suspension having a Brookfield viscosity in the range of 1 to 2000 mPa.s at 25° C., with a content of nanofibrillated cellulose and/or microfibrillated cellulose of 1 wt %, based on the total weight of the aqueous suspension. 45. The method according to claim 33, where the cellulose material is a mixture based on cellulose material, including nanofibrillated cellulose and / or microfibrillated cellulose, which is obtained by nanofibrillation and / or microfibrillation of a suspension of cellulose fibers in the presence of fillers and / or pigments, while the nanofibrillated cellulose and/or microfibrillated cellulose is preferably in the form of an aqueous suspension having a Brookfield viscosity in the range of 1 to 2000 mPa.s at 25° C., with a content of nanofibrillated cellulose and/or microfibrillated cellulose of 1 wt %, based on the total weight of the aqueous suspension. 46. A 3D molded article comprising the 3D moldable sheet material of claim 2. 47. The 3D molded article of claim 46, wherein said article is a container. 48. The 3D molded article of claim 46, wherein said article is a food container. 49. The 3D-molded article of claim 46, wherein said article is a blister pack. 50. The 3D molded article of claim 46, wherein said article is a food tray. 51. A 3D molded article comprising the 3D moldable sheet material of claim 3. 52. The 3D molded article of claim 51, wherein said article is a container. 53. The 3D molded article of claim 51, wherein said article is a food container. 54. The 3D-molded article of claim 51, wherein said article is a blister pack. 55. The 3D molded article of claim 51, wherein said article is a food tray. 56. A 3D molded article comprising the 3D moldable sheet material of claim 6. 57. The 3D molded article of claim 56, wherein said article is a container. 58. The 3D molded article of claim 56, wherein said article is a food container. 59. The 3D-molded article of claim 56, wherein said article is a blister pack. 60. The 3D molded article of claim 56, wherein said article is a food tray. 61. A 3D molded article comprising the 3D moldable sheet material of claim 7. 62. The 3D molded article of claim 61, wherein said article is a container. 63. The 3D molded article of claim 61, wherein said article is a food container. 64. The 3D-molded article of claim 61, wherein said article is a blister pack. 65. The 3D molded article of claim 61, wherein said article is a food tray. 66. A 3D molded article comprising the 3D moldable sheet material of claim 9. 67. The 3D molded article of claim 66, wherein said article is a container. 68. The 3D molded article of claim 66, wherein said article is a food container. 69. The 3D-molded article of claim 66, wherein said article is a blister pack. 70. The 3D molded article of claim 66, wherein said article is a food tray. 71. A 3D molded article comprising the 3D moldable sheet material of claim 13. 72. The 3D molded article of claim 71, wherein said article is a container. 73. The 3D molded article of claim 71, wherein said article is a food container. 73. The 3D-molded article of claim 71, wherein said article is a blister pack. 75. The 3D molded article of claim 71, wherein said article is a food tray. 76. A 3D molded article comprising the 3D moldable sheet material of claim 17. 77. The 3D molded article of claim 76, wherein said article is a container. 78. The 3D molded article of claim 76, wherein said article is a food container. 79. The 3D-molded article of claim 76, wherein said article is a blister pack. 80. The 3D molded article of claim 76, wherein said article is a food tray.

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