Patent Grant
11932740
The present invention relates to a 3D-formable sheet material, a process for the preparation of a 3D-formed article, the use of a cellulose material and at least one particulate inorganic filler material for the preparation of a 3D-formable sheet material and for increasing the stretchability of a 3D-formable sheet material, the use of a 3D-formable sheet material in 3D-forming processes as well as a 3D-formed article comprising the 3D-formable sheet material according.
3D-formable materials are used in a great variety of applications such as packaging container, e.g. medical and cosmetic packaging or food packaging, food container, e.g. candy boxes, blister pack, food tray and the like. Paper-like materials, i.e. materials comprising a cellulosic material, are becoming more and more attractive for such applications due to their various advantages such as recyclability, biodegradability and renewability. Such materials are described in a number of documents. For instance, JP 2003-293282 A refers to a paper substrate moldable at <60° C. processing temperature without requiring preheating during pressurized air molding or vacuum molding, easily carrying out disposal treatment or recycling and utilization and having environmentally excellent properties. According to the working examples a polyacrylamide system is added to the pulp for preparing the paper substrate. JP 2006-082384 A refers to a formable paper that is used as a substrate and an ink receiving layer which is disposed on the formable paper. The ink receiving layer applied on the formable paper comprises a binding agent in order to prevent cracking. Especially preferred binding agents are described as being a polyurethane copolymer, an acrylic copolymer, an ethylene-vinyl acetate copoylmer and a rubber copolymer. CN 104015450 A refers to a paper material comprising one or more layers, wherein the paper material can be extended for at least 5% in a machine direction (MD) and can be extended for at least 5% in a cross direction (CD). The paper material is preferably a laminate, wherein the paper materials are bonded to each other by using a binder, such as a water-based adhesive layer, e.g. water-based glue, or PE. The PE or EVOH layer can be also used as moisture or gas barrier layer. CN 104015987 A refers to an insertion piece formed by a piece of extensible paper wood. The insertion piece is used for packaging and is in a three-dimensional shape and formed by a piece of wood. The paper material is preferably a laminate, wherein the paper materials are bonded to each other by using a binder, such as a water-based adhesive layer or PE. The PE layer is also used as gas barrier layer. U.S. Pat. No. 3,372,084 refers to a post-formable absorbent paper adaptable to use in preparing post-formable plastic laminates comprising in combination: a) a fiber portion containing from 35 to 100% of fine fibers selected from vegetable fibers and synthetic organic fibers, said fine fibers being characterized by having a specific volume of 75 to 175 cubic microns per unit length and an average length of greater than 2 mm, b) the remainder of the said fiber portion being selected from paper making wood pulps, c) from 0.5 to 30%, based on the total weight of said fiber portion, of an acid acceptor selected from zinc oxide, calcium carbonate and calcium silicate, said paper being essentially neutral, as measured by the pH of its water extract ranging from 6.8 to 7.6 with the alkali number of the water extract ranging from 0.5 to 3.0. Also methods for forming 3D-shaped articles are well known in the art, e.g. from WO 2015/063643 A1, AU 54281/86 B, GB 2 092 941 A, U.S. Pat. No. 7,681,733 B2, U.S. Pat. No. 4,637,811 A, WO 99/53810 A1, WO 2009/020805 A1, DE 10 2012 201 882 A1, U.S. Pat. No. 1,567,162 and EP 2 829 392 A1.
However, poor 3D-formability of sheet materials is a limiting factor for preparing 3D-formed articles. This poor 3D-formability typically originates from a limited strength of the sheet material and poor stretchability as well as the possible separation of fillers and cellulose material.
Therefore, there is a continuous need in the art for a 3D-formable sheet material which provides good 3D-formability. In particular, there is a need for a 3D-formable sheet material having sufficient strength and improved stretchability as well as having a which mass is homogeneously distributed and such that its separation is complicated.
Accordingly, it is an objective of the present invention to provide a 3D-formable sheet material which provides good 3D-formability for 3D-formed articles. A further objective is to provide a 3D-formable sheet material having sufficient strength, i.e. the strength is maintained or improved. Another objective is to provide a 3D-formable sheet material having a stretchability which is maintained or improved. An even further Objective is to provide a 3D-formable sheet material in which the mass is homogeneously distributed throughout the sheet material and the separation of the components, especially of the filler and cellulosic material, is complicated.
The foregoing and other objectives are solved by the subject-matter as defined herein in claim 1.
Advantageous embodiments of the inventive 3D-formable sheet material are defined in the corresponding sub-claims.
According to one aspect of the present application a 3D-formable sheet material is provided. The 3D-formable sheet material comprising
The inventors surprisingly found out that the foregoing 3D-formable sheet material according to the present invention provides a good 3D-formability for 3D-formed articles. More precisely, the inventors found that the foregoing 3D-formable sheet material according to the present invention provides sufficient strength and stretchability and that its mass separation is complicated.
It should be understood that for the purposes of the present invention, the following terms have the following meanings:
The term “3D-formable” in the meaning of the present invention refers to a sheet material that can be formed into a 3D-formed article by using 3D-forming processes such that the article retains the 3D form.
The term “3D-formed” article means that the article retains the 3D form into which it has been formed from the 3D-formable sheet material.
The term “dry” with regard to the at least one particulate inorganic filler material is understood to be a material having less than 0.3% by weight of water relative to the weight of the at least one particulate inorganic filler material. The % water is determined according to the Coulometric Karl Fischer measurement method, wherein the at least one particulate inorganic filler material is heated to 220° C., and the water content released as vapour and isolated using a stream of nitrogen gas (at 100 ml/min) is determined in a Coulometric Karl Fischer unit.
The term “dry” with regard to the cellulose material is understood to be a dry cellulose material having <0.5% by weight of water relative to the weight of the cellulose material. The “dry cellulose material” is determined by treating the cellulose material at 103° C. to constant weight in accordance with DIN 52 183.
The term “dry” with regard to the 3D-formable sheet material is understood to be a dry 3D-formable sheet material having <0.5% by weight of water relative to the weight of the 3D-formable sheet material. The “dry 3D-formable sheet material” is determined by treating the 3D-formable sheet material at 103° C. to constant weight in accordance with DIN 52 183.
Where the term “comprising” is used in the present description and claims, it does not exclude other non-specified elements of major or minor functional importance. For the purposes of the present invention, the term “consisting of” is considered to be a preferred embodiment of the term “comprising of”. If hereinafter a group is defined to comprise at least a certain number of embodiments, this is also to be understood to disclose a group, which preferably consists only of these embodiments.
Whenever the terms “including” or “having” are used, these terms are meant to be equivalent to “comprising” as defined above.
Where an indefinite or definite article is used when referring to a singular noun, e.g. “a”, “an” or “the”, this includes a plural of that noun unless something else is specifically stated.
Terms like “obtainable” or “definable” and “obtained” or “defined” are used interchangeably. This e.g. means that, unless the context clearly dictates otherwise, the term “obtained” does not mean to indicate that e.g. an embodiment must be obtained by e.g. the sequence of steps following the term “obtained” even though such a limited understanding is always included by the terms “obtained” or “defined” as a preferred embodiment.
According to another aspect of the present invention, a process for the preparation of a 3D-formed article is provided. The process comprising the steps of:
According to one embodiment of the process, the 3D-formable sheet material has been obtained by
According to another embodiment of the process, the cellulose 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 yet another embodiment of the process, i) the cellulose material is provided in form of an aqueous suspension comprising the cellulose material in a range from 0.2 to 35 wt.-%, more preferably 0.25 to 20 wt.-%, even more preferably 0.5 to 15 wt.-%, most preferably 1 to 10 wt-%, based on the total weight of the aqueous suspension; and/or ii) the at least one particulate inorganic filler material is provided in powder form, or in form of an aqueous suspension comprising the particulate inorganic filler material in an amount from 1 to 80 wt.-%, preferably from 5 to 78 wt.-%, more preferably from. 10 to 78 wt.-% and most preferably from 15 to 78 wt.-%, based on the total weight of the aqueous suspension.
According to one embodiment of the process, the cellulose material is a cellulose material mixture comprising nanofibrillated cellulose and/or microfibrillated cellulose that has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence of fillers and/or pigments, preferably the nanofibrillated cellulose and/or microfibrillated cellulose is in form of an aqueous suspension having a Brookfield viscosity in the range from 1 to 2 000 mPa·s at 25° C., more preferably from 10 to 1 200 mPa·s at 25° C., and most preferably from 100 to 600 mPa·s at 25° C. at a nanofibrillated cellulose and/or microfibrillated cellulose content of 1 wt. %, based on the total weight of the aqueous suspension.
According to another embodiment of the process, the cellulose material is a cellulose material mixture comprising nanofibrillated cellulose and/or microfibrillated cellulose that has been obtained by nanofibrillating and/or microfibrillating cellulose fibre suspension in the presence of fillers and/or pigments, preferably the nanofibrillated cellulose and/or microfibrillated cellulose is in form of an aqueous suspension having a Brookfield viscosity in the range from 1 to 2 000 mPa·s at 25° C., more preferably from 3 to 1 200 mPa·s at 25° C., and most preferably from 10 to 600 mPa·s at 25° C., at a nanofibrillated cellulose and/or microfibrillated cellulose content of 1 wt. %, based on the total weight of the aqueous suspension.
From European patent applications EP 2 386 682 A1, EP 2 386 683 A1, EP 2 236 664 A1, EP 2 236 545 A1, EP 2 808 440 A1, EP 2 529 942 A1 and EP 2 805 986 A1, and from J. Rantanen et al., “Forming and dewatering of a microfibrillated cellulose composite paper”, BioResources 10(2), 2015, pages 3492-3506, nanofibrillated and microfibrillated cellulose and their use in paper are known. However, there is no teaching with respect to their effects in 3D-formable sheet materials.
According to yet another embodiment of the process, the process further comprises a step c) of moisturizing the 3D-formable sheet material provided in step a) to a moisture content of 2 to 30 wt.-%, based on the total dry weight of the 3D-formable sheet material, before and/or during process step b).
According to a further aspect of the present invention, the use of a cellulose material as defined herein and at least one particulate inorganic filler material as defined herein for the preparation of a 3D-formable sheet material is provided. According to a still further aspect of the present invention, the use of a cellulose material as defined herein and at least one particulate inorganic filler material as defined herein for increasing the stretchability of a 3D-formable sheet material is provided, wherein the increase is achieved when the 3D-formable sheet material has a normalized stretch increase per level of moisture content in the range from 0.15 to 0.7% per percent. According to an even further aspect of the present invention, the use of a 3D-formable sheet material as defined herein in 3D-forming processes is provided, preferably in thermoforming, vacuum forming, air-pressure forming, deep-drawing forming, hydroforming, spherical forming, press forming, or vacuum/air-pressure forming. According to another aspect of the present invention, a 3D-formed article, preferably a packaging container, food container, blister pack, food tray, comprising the 3D-formable sheet material, as defined herein, is provided.
According to one embodiment of the present invention, the 3D-formable sheet material comprises a) the cellulose material in an amount from 15 to 55 wt.-%, based on the total dry weight of the 3D-formable sheet material, and b) the at least one particulate inorganic filler material in an amount 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) a normalized stretch increase per level of moisture content in the range from 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) a sheet weight from 50 to 500 g/m2, preferably from 80 to 300 g/m2, and most preferably from 80 to 250 g/m2.
According to yet another embodiment of the present invention, the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence or presence of fillers and/or pigments, preferably the cellulose fibres of the cellulose fibre suspension are such contained in pulps selected from the group comprising 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 fiber material and mixtures thereof.
According to one embodiment of the present invention, the cellulose fibres a) are selected from the group comprising softwood fibres, such as spruce fibres and pine fibres, hardwood fibres, such as eucalyptus fibres, birch fibres, beech fibres, maple fibres, acacia fibres, and other types of fibres, such as hemp fibres, cotton fibres, bagasse or straw fibres, or recycled fiber material and mixtures thereof, and/or b) have a length weighted average fibre length from 500 μm to 3 000 μm, more preferably from 600 μm to 2 000 μm, and most preferably from 700 to 1 000 μm.
According to another embodiment of the present invention, the at least one particulate inorganic filler material is at least one particulate calcium carbonate-containing material, preferably the at least one particulate calcium carbonate-containing material is dolomite and/or at least one ground 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 the aragonitic, vateritic and calcitic mineralogical crystal forms, more preferably the at least one particulate inorganic filler material is at least one precipitated calcium carbonate (PCC).
According to yet another embodiment of the present invention, the at least one particulate inorganic filler material has a) a weight median particle size d50 from 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) a specific surface area of from 0.5 to 200.0 m2/g, more preferably of from 0.5 to 100.0 m2/g and most preferably of from 0.5 to 50.0 m2/g as measured by the BET nitrogen method.
As set out above, the inventive 3D-formable sheet material comprises a cellulose material and at least one particulate inorganic filler material set out in points a) and b). In the following, it is referred to further details of the present invention and especially the foregoing points of the inventive 3D-formable sheet material.
According to the present invention, the 3D-formable sheet material comprises
It is one requirement of the present 3D-formable sheet material that the sum of the amount of the cellulose material and the at least one particulate inorganic filler material is 100.0 wt.-%, based on the total dry weight of the cellulose material and the at least one particulate inorganic filler material.
The 3D-formable sheet material of the present invention comprises the cellulose material in an amount from 5 to 55 wt.-%, based on the total dry weight of the 3D-formable sheet material. Preferably, the 3D-formable sheet material comprises the cellulose material in an amount from 15 to 55 wt.-%, based on the total dry weight of the 3D-formable sheet material. For example, the 3D-formable sheet material comprises the cellulose material in an amount from 20 to 45 wt.-% or from 25 to 35 wt.-%, based on the total dry weight of the 3D-formable sheet material.
Additionally, the 3D-formable sheet material comprises the at least one particulate inorganic filler material in an amount of ≥45 wt.-%, based on the total dry weight of the 3D-formable sheet material. Preferably, the 3D-formable sheet material comprises the at least one particulate inorganic filler material in an amount from 45 to 85 wt.-%, based on the total dry weight of the 3D-formable sheet material. For example, the 3D-formable sheet material comprises the at least one particulate inorganic filler material in an amount from 55 to 80 wt.-% or from 65 to 75 wt.-%, based on the total dry weight of the 3D-formable sheet material.
In one embodiment, the 3D-formable sheet material consists of the cellulose material and the at least one particulate inorganic filler material. That is to say, the 3D-formable sheet material consists of
It is appreciated that the 3D-formable sheet material may comprise additives which are typically used in the field of paper manufacturing and especially 3D-formable sheet materials.
The term “at least one” additive in the meaning of the present invention means that the additive comprises, preferably consists of, one or more additives.
In one embodiment of the present invention, the at least one additive comprises, preferably consists of, one additive. Alternatively, the at least one additive comprises, preferably consists of, two or more additives. For example, the at least one additive comprises, preferably consists of, two or three additives.
For example, the at least one additive is selected from the group consisting of a sizing agent, a paper-strength enhancer, a filler (differing from the at least one particulate inorganic filler material), a retention aid such as Percol®, a binder, a surfactant, a biocide an antistatic agent, a colorant and a flame retardant.
The at least one additive can be present in the 3D-formable sheet material in an amount ranging from 0.01 to 10 wt.-%, based on the total dry weight of the 3D-formable sheet material. For example, the at least one additive can be present in the 3D-formable sheet material in an amount ranging from 0.02 to 8 wt.-%, preferably from 0.04 to 5 wt.-%, based on the total dry weight of the 3D-formable sheet material.
Thus, the 3D-formable sheet material may comprise
In one embodiment, the 3D-formable sheet material consists of
Thus, the 3D-formable sheet material preferably comprises the cellulose material and the at least one particulate inorganic filler material in an amount of ≥90 wt.-%, based on the total dry weight of the 3D-formable sheet material. For example, the 3D-formable sheet material preferably comprises the cellulose material and the at least one particulate inorganic filler material in an amount of 90 to 99.99 wt.-%, based on the total dry weight of the 3D-formable sheet material. Preferably, the 3D-formable sheet material comprises the cellulose material and the at least one particulate inorganic filler material in an amount of 92 to 99.95 wt.-% or in an amount of 95 to 99.9 wt.-%, based on the total dry weight of the 3D-formable sheet material. Alternatively, the 3D-formable sheet material consists of the cellulose material and the at least one particulate inorganic filler material.
One advantage of the 3D-formable sheet material of the present invention is that it features high stretchability as well as high elongation at break such that the 3D-formable sheet material is especially suitable for preparing 3D-formed articles.
The 3D-formable sheet material especially features a high or increased stretchability. In particular, it appreciated that the 3D-formable sheet material has a normalized stretch increase per level of moisture content in the range from 0.15 to 0.7% per percent. For example, the 3D-formable sheet material has a normalized stretch increase per level of moisture content in the range from 0.15 to 0.6% per percent sheet moisture and preferably from 0.2 to 0.6%.
The “normalized stretch increase per level of moisture content” is a material property and is determined by the following formula (I)
wherein d(moisture) defines the moisture content range considered, i.e. the difference between a higher moisture level of interest (e.g. 20%) and a lower moisture level of interest (e.g. 10%);
d(stretch) defines the stretchability range at the moisture content range considered, i.e. the difference between the stretchability at the higher moisture level of interest and the stretchability at the lower moisture level of interest.
It is appreciated that the increased stretchability is dependent on the moisture content of the 3D-formable sheet material.
For example, the 3D-formable sheet material has a stretchability ranging from 4 to 10%, preferably from 5 to 10%, at a moisture content of 10% of the 3D-formable sheet material.
Additionally or alternatively, the 3D-formable sheet material has a stretchability ranging from 6 to 18%, preferably from 7 to 18%, at a moisture content of 20% of the 3D-formable sheet material.
The stretchability at specific moisture content can be determined by the following formula (II)
wherein the “moisture” is defined as (X % moisture−% reference moisture) and the % reference moisture refers to the lower moisture level of interest.
It is appreciated that the 3D-formable sheet material may also feature a high or improved elongation at break. For example, the 3D-formable sheet material has a elongation at break of at least 6%, preferably from 6 to 16% and most preferably from 7 to 15%.
The 3D-formable sheet material preferably has a sheet weight from 50 to 500 g/m2, preferably from 80 to 300 g/m2 and most preferably from 80 to 250 g/m2.
Thus, the 3D-formable sheet material preferably has
For example, the 3D-formable sheet material preferably has
For example, the 3D-formable sheet material preferably has
In one embodiment, the 3D-formable sheet material has
Preferably, the 3D-formable sheet material has
In the following the components of the 3D-formable sheet material are described in more detail.
The cellulose material is a cellulose material mixture comprising
One requirement of the cellulose material mixture is that the sum of the amount of the nanofibrillated cellulose and/or microfibrillated cellulose and the cellulose fibres is 100 wt.-%, based on the total dry weight of the cellulose material mixture.
The use of a nanofibrillated cellulose and/or microfibrillated cellulose has the advantage that the separation of the at least one particulate inorganic filler material and the optional additives there is complicated such that a mass is obtained in which the single components are homogeneously distributed.
In one embodiment, the cellulose material mixture comprises
Alternatively, the cellulose material mixture comprises
Thus, the cellulose material mixture preferably comprises the nanofibrillated cellulose or microfibrillated cellulose, preferably microfibrillated cellulose, in an amount of ≥55 wt.-%, based on the total dry weight of the cellulose material mixture. For example, the cellulose material mixture comprises the nanofibrillated cellulose or microfibrillated cellulose, preferably microfibrillated cellulose, in an amount of 55 to 99 wt.-%, based on the total dry weight of the cellulose material mixture. Preferably, the cellulose material mixture comprises the nanofibrillated cellulose or microfibrillated cellulose, preferably microfibrillated cellulose, in an amount of 60 to 95 wt.-% based on the total dry weight of the cellulose material mixture.
Additionally, the cellulose material mixture comprises the cellulose fibres in an amount of ≤45 wt.-%, based on the total dry weight of the cellulose material mixture. For example, the cellulose material mixture comprises the cellulose fibres in an amount of 1 to 45 wt.-%, based on the total dry weight of the cellulose material mixture. Preferably, the cellulose material mixture comprises the cellulose fibres in an amount of 5 to 40 wt.-%, based on the total dry weight of the cellulose material mixture.
In one embodiment, the weight ratio of nanofibrillated cellulose and/or microfibrillated cellulose to cellulose fibres in the cellulose material mixture on a dry weight basis is from 90:10 to 50:50, more preferably from 90:10 to 60:40 even more preferably from 90:10 to 70:30 and most from 90:10 to 80:20, e.g. about 90:10 or about 85:15.
The terms “nanofibrillated cellulose” and “microfibrillated cellulose” refers to the commonly acknowledged definition, e.g. as defined in H. Sixta (Ed.), Handbook of Pulp, Wiley-VCH.
Cellulose pulp as a raw material is processed out of wood or stems of plants such as hemp, linen and manila. Pulp fibres are built up mainly by cellulose and other organic components (hemicellulose and lignin), The cellulose macromolecules (composed of 1-4 glycosidic linked β-D-Glucose molecules) are linked together by hydrogen bonds to form a so called nanofibril (also designated as primary fibril or micelle) which has crystalline and amorphous domains. Several nanofibrils (around 55) form a so called microfibril. Around 250 of these microfibrils form a fibril.
The fibrils are arranged in different layers (which can contain lignin and/or hemicellulose) to form a fibre. The individual fibres are bound together by lignin as well.
When fibres become refined under applied energy they become fibrillated as the cell walls are broken and torn into attached strips, i.e. into fibrils. If this breakage is continued to separate the fibrils from the body of the fibre, it releases the fibrils. The breakdown of fibres into microfibrils is referred to as “micro fibrillation”. This process may be continued until there are no fibres left and only nanofibrils remain.
If the process goes further and breaks these fibrils down into smaller and smaller fibrils, they eventually become cellulose fragments. The breakdown to nanofibrils may be referred to as “nano-fibrillation”, where there may be a smooth, transition between the two regimes.
The term “nanofibrillated cellulose” in the context of the present invention means fibres, which are at least partially broken down to nanofibrils (also designated as primary fibrils).
The term “microfibrillated cellulose” in the context of the present invention means fibres, which are at least partially broken down to microfibrils. The microfibrillated cellulose preferably has a Brookfield viscosity in the range of from 1 to 2 000 mPa·s at 25° C., more preferably from 10 to 1 200 mPa·s at 25° C., and most preferably from 100 to 600 mPa·s at 25° C., at a nanofibrillated cellulose and/or microfibrillated cellulose content of 1 wt.-%, based on the total weight of the aqueous suspension.
In this respect, fibrillating in the context of the present invention means any process which predominantly breaks down the fibres and fibrils along their long axis resulting in the decrease of the diameter of the fibres and fibrils, respectively. Nanofibrillated and microfibrillated celluloses and their preparation are well known to a person skilled in the art. For example, nanofibrillated and microfibrillated celluloses and their preparation are described in EP 2 386 682 A1, EP 2 386 683 A1, EP 2 236 664 A1 , EP 2 236 545 A1, EP 2 808 440 A1 and EP 2 805 986 A1 which are thus incorporated herewith by references, 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, the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence or presence of fillers and/or pigments.
In one embodiment, the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence of fillers and/or pigments. Thus, the nanofibrillated cellulose and/or microfibrillated cellulose is free of fillers and/or pigments. Accordingly, the 3D-formable sheet material is free of fillers and/or pigments differing from the at least one particulate inorganic filler material in this embodiment.
The nanofibrillated cellulose and/or microfibrillated cellulose that has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence of fillers and/or pigments, is preferably in form of an aqueous suspension. Preferably, the aqueous suspension has a Brookfield viscosity in the range from 1 to 2 000 mPa·s at 25° C., more preferably from 10 to 1 200 mPa·s at 25° C., and most preferably from 100 to 600 mPa·s at 25° C., at a nanofibrillated cellulose and/or microfibrillated cellulose content of 1 wt.-%, based on the total weight of the aqueous suspension.
In an alternative embodiment, the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the presence of fillers and/or pigments.
The fillers and/or pigments are preferably selected from the group comprising precipitated calcium carbonate (PCC); natural ground calcium carbonate (GCC); dolomite; talc; bentonite; clay; magnesite; satin white; sepiolite, huntite, diatomite; silicates; and mixtures thereof. Precipitated calcium carbonate, which may have vateritic, calcitic or aragonitic crystal structure, and/or natural ground calcium carbonate, which may be selected from marble, limestone and/or chalk, are especially preferred.
In a preferred embodiment, the use of natural ground calcium carbonate (GCC) such as marble, limestone and/or chalk as filler and/or pigment may be advantageous.
It is appreciated that the 3D-formable sheet material may thus comprise in addition to the at least one particulate inorganic filler material further fillers and/or pigments. The at least one particulate inorganic filler material and the further fillers and/or pigments may be the same or different. Preferably, the at least one particulate inorganic filler material and the further 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 from 1:10 to 10:1, more preferably 1:6 to 6:1, typically 1:4 to 4:1, especially 1:3 to 3:1, and most preferably 1:2 to 2:1, e.g. 1:1.
The nanofibrillated cellulose and/or microfibrillated cellulose preferably comprises the fillers and/or pigments in amounts ranging from 5 to 90 wt.-%, preferably from 20 to 80 wt.-%, more preferably from 30 to 70 wt.-% and most preferably from 35 to 65 wt.-%, based on the total dry weight of the nanofibrillated cellulose and/or microfibrillated cellulose.
Thus, the cellulose material of the 3D-formable sheet material preferably comprises the fillers and/or pigments in amounts ranging from 2 to 85 wt.-%, preferably from 2 to 70 wt.-%, more preferably from 3 to 50 wt.-% and most preferably from 5 to 40 wt.-%, based on the total dry weight of the cellulose material. it is appreciated that the fillers and/or pigments derive from the nanofibrillating and/or microfibrillating of a cellulose fibre suspension in the presence of fillers and/or pigments.
The nanofibrillated cellulose and/or microfibrillated cellulose that has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the presence of fillers and/or pigments is preferably in form of an aqueous suspension. Preferably, the aqueous suspension has a Brookfield viscosity in the range from 1 to 2 000 mPa·s at 25° C., more preferably from 3 to 1 200 mPa·s at 25° C., and most preferably from 10 to 600 mPa·s at 25° C., at a nanofibrillated cellulose and/or microfibrillated cellulose content of 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 from 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, e.g. 1.6 μm or 3.2 μm.
It is appreciated that the cellulose fibres of the cellulose fibre suspension from which the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained are preferably such contained in pulps selected from the group comprising 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 fiber material, and mixtures thereof.
The nanofibrillated cellulose and/or microfibrillated cellulose is preferably obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the presence of fillers and/or pigments.
The cellulose material mixture further comprises cellulose fibres.
The cellulose fibres present in the cellulose material mixture are preferably selected from the group comprising softwood fibres, such as spruce fibres and pine fibres, hardwood fibres, such as eucalyptus fibres, birch fibres, beech fibres, maple fibres, acacia fibres, and other types of fibres, .such as hemp fibres, cotton fibres, bagasse or straw fibres, or recycled fiber material and mixtures thereof.
It is appreciated that the cellulose fibres present in the cellulose material mixture may originate from the same or different fibres from which the nanofibrillated cellulose and/or microfibrillated cellulose have been obtained. Preferably, the cellulose fibres present in the cellulose material mixture originate from different fibres from which the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained,
In one embodiment, the cellulose fibres present in the cellulose material mixture are eucalyptus fibres.
It is appreciated that the cellulose fibres of the cellulose fibre suspension from which the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained and the cellulose fibres may be the same or different. Preferably, the cellulose fibres of the cellulose fibre suspension from which the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained and the cellulose fibres are different.
Preferably, the cellulose fibres present in the cellulose material mixture have a length weighted average fibre length from 500 μm to 3 000 μm, more preferably from 600 μm to 2 000 μm, and most preferably from 700 to 1 000 μm.
Another essential component of the instant 3D-formable trial is at least one particulate inorganic filler material.
The term “at least one” particulate inorganic filler material in the meaning of the present invention means that the particulate inorganic filler material comprises, preferably consists of, one or more particulate inorganic filler materials.
In one embodiment of the present invention, the at least one particulate inorganic filler material comprises, preferably consists of, one particulate inorganic filler material. Alternatively, the at least one particulate inorganic filler material comprises, preferably consists of, two or more particulate inorganic filler materials. For example, the at least one particulate inorganic filler material comprises, 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.
The term at least one “particulate” inorganic filler material in the meaning of the present invention refers to a solid compound that comprises, preferably consists of, the inorganic filler material.
The at least one particulate inorganic filler material may be a particulate natural, synthetic or blended inorganic filler material such as an alkaline earth metal carbonate (e.g. calcium carbonate or dolomite), metal sulfate (e.g. barite or gypsum) metal silicate, metal oxide (e.g. titania or iron oxide), kaolin, calcined kaolin, talc or mica or any mixture or combination thereof.
Especially good results as regards the stretchability and the elongation at break are obtained in case the at least one particulate inorganic filler material is at least one particulate calcium carbonate-containing material.
The term “calcium carbonate-containing material” refers to a material that comprises at least 50.0 wt.-% calcium carbonate, based on the total clay weight of the calcium carbonate-containing material.
According to one embodiment of the present invention, the at least one particulate calcium carbonate-containing material is selected from dolomite, at least one ground calcium carbonate (GCC), at least one precipitated calcium carbonate (PCC) and mixtures thereof.
“Dolomite” in the meaning of the present invention is a carbonatic calcium-magnesium-mineral having the chemical composition of CaMg(CO3)2 (“CaCO3·MgCO3”). Dolomite mineral contains at least 30.0 wt.-% MgCO3, based on the total weight of dolomite, preferably more than 35.0 wt.-%, more than 40.0 wt.-%, typically from 45.0 to 46.0 wt.-% MgCO3.
“Ground calcium carbonate” (GCC) in the meaning of the present invention is a calcium carbonate Obtained from natural sources, such as limestone, marble or chalk, and processed through a wet and/or dry treatment such as grinding, screening and/or fractionating, for example by a cyclone or classifier.
According to one embodiment, the GCC is obtained by dry grinding. According to another embodiment of the present invention the GCC is obtained by wet grinding and subsequent drying.
In general, the grinding step can be carried out with any conventional grinding device, for example, under conditions such that refinement predominantly results from impacts with a secondary body, i.e. in one or more of: a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled man. In case calcium carbonate-containing material comprises a wet ground calcium carbonate-containing material, the grinding step may be performed under conditions such that autogenous grinding takes place and/or by horizontal ball milling, and/or other such processes known to the skilled man. The wet processed ground calcium carbonate-containing material thus obtained may be washed and dewatered by well known processes, e.g. by flocculation, filtration or forced evaporation prior to drying. The subsequent step of drying may be carried out in a single step such as spray drying, or in at least two steps. It is also common that such a calcium carbonate material undergoes 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 comprising marble, chalk, limestone and mixtures thereof.
“Precipitated calcium carbonate” (PCC) in the meaning of the present invention is a synthesized material, generally obtained by precipitation following reaction of carbon dioxide and lime in an aqueous environment or by precipitation of a calcium and carbonate ion source in water. PCC may be one or more of the aragonitic, vateritic and calcitic mineralogical crystal forms. Preferably, PCC is one of the aragonitic, vateritic and calcitic mineralogical crystal forms.
Aragonite is commonly in the acicular form, whereas vaterite belongs to the hexagonal crystal system. Calcite can form scalenohedral, prismatic, spheral and rhombohedral forms. PCC can be produced in different ways, e.g. by precipitation with carbon dioxide, the lime soda process, or the Solvay process in which PCC is a by-product of ammonia production. The obtained PCC slurry can be mechanically dewatered and dried.
It is preferred that the at least one particulate inorganic filler material is a particulate calcium carbonate-containing material being at least one precipitated calcium carbonate (PCC), preferably at least one precipitated calcium carbonate (PCC) of the aragonitic, vateritic or calcitic mineralogical crystal form.
In addition to calcium carbonate, the at least one particulate calcium carbonate-containing material may comprise further metal oxides such as titanium dioxide and/or aluminium trioxide, metal hydroxides such as aluminium tri-hydroxide, metal salts such as sulfates, silicates such as talc and/or kaolin clay and/or mica, carbonates such as magnesium carbonate and/or gypsum, satin white and mixtures thereof.
According to one embodiment of the present invention, the amount of calcium carbonate in the at least one particulate calcium carbonate-containing material is of ≥50.0 wt.-%, preferably of 90.0 wt.-%, more preferably of ≥95.0 wt.-% and most preferably of ≥97.0 wt.-%, based on the total dry weight of the calcium carbonate-containing material.
It is a preferred that the at least one particulate inorganic filler material, preferably the at least one particulate calcium carbonate-containing material, has a weight median particle size d50 from 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, e.g. 2.7 μm, as measured by the sedimentation method.
Throughout the present document, the “particle size” of a calcium carbonate-comprising filler material or other particulate materials is described by its distribution of particle sizes. The value dx represents the diameter relative to which x % by weight of the particles have diameters less than dx. This means that the d20 value is the particle size at which 20 wt.-% of all particles are smaller, and the d98 value is the particle size at which 98 wt.-% of all particles are smaller. The d98 value is also designated as “top cut”. The d50 value is thus the weight median particle size, i,e. 50 wt.-% of all grains are smaller than this particle size. For the purpose of the present invention the particle size is specified as weight median particle size d50 unless indicated otherwise. For determining the weight median particle size d50 value or the top cut particle size d98 value a Sedigraph™ 5100 or 5120 device from the company Micromeritics, USA, can be used. The method and the instrument are known to the skilled person and are commonly used to determine grain size of fillers and pigments. The measurement is carried out in an aqueous solution of 0.1 wt.-% Na4P2O7. The samples are dispersed using a high speed stirrer and supersonics.
The at least one particulate Moronic filler material, preferably the at least one particulate calcium carbonate-containing material, may have a top cut, for example, of below 40.0 μm. Preferably, the at least one particulate inorganic filler material, preferably the at least one particulate calcium carbonate-containing material, has a top cut of below 30.0 μm and more preferably of 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 from 0.5 to 200.0 m2/g, more preferably of from 0.5 to 100.0 m2/g and most preferably of from 0.5 to 50.0 m2/g as measured by the BET nitrogen method.
The term “specific surface area” (in m2/g) of the at least one particulate calcium carbonate-containing material in the meaning of the present invention is determined using the BET method, which is well known to the skilled man (ISO 9277:1995).
It is appreciated that the 3D-formable sheet material is preferably free of layers/laminates comprising polymeric materials which are suitable for improving the stretchability and the elongation at break of the sheet material. Thus, the 3D-formable sheet material is preferably free of (synthetic) polymeric materials such as PE, PP, EVOH and the like.
According to another aspect of the present invention, a process for the preparation of a 3D-formed article is provided. The process comprising the steps of:
With regard to the definition of the 3D-formable sheet material and preferred embodiments thereof, reference is made to the statements provided above when discussing the technical details of the 3D-formable sheet material of the present invention.
The forming of the 3D-formable sheet material into a 3D-formed article may be undertaken by all the techniques and process lines well known to the man skilled in the art for forming 3D-formed articles. However, it is appreciated that pressure forming processes according to DIN 8583 are typically not suitable for forming the 3D-formable sheet material into a 3D-formed article.
The 3D-formed articles are preferably formed in a tensile compression forming process according to DIN 8584 or a tensile forming process according to DIN 8585.
The forming of the 3D-formable sheet material into a 3D-formed article is preferably carried out by thermoforming, vacuum forming, air-pressure forming, deep-drawing forming, hydroforming, spherical forming, press forming, or vacuum/air-pressure forming. These techniques are well known to the man skilled in the art for forming 3D-formed articles.
It is preferred that the 3D-formable sheet material which is formed into a 3D-formed article should have specific moisture content in order to facilitate the forming process in step b). In particular, it is preferred that the 3D-formable sheet material provided in step a) has a moisture content of ≥2 wt.-%, based on the total dry weight of the 3D-formable sheet material. However, if the moisture content exceeds a specific value, the quality of the resulting 3D-formed article typically deteriorates. Thus, it is preferred that the 3D-formable sheet material provided in step a) has a moisture content of ≤30 wt.-%, based on the total dry weight of the 3D-formable sheet material.
Thus, the 3D-formable sheet material provided in step a) preferably has a moisture content in the range from 2 to 30 wt.-%, based on the total dry weight of the 3D-formable sheet material. For example, the 3D-formable sheet material provided in step a) preferably has a moisture content in the range from 6 to 25 wt.-% or from 10 to 20 wt.-%, based on the total dry weight of the 3D-formable sheet material.
In case 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 may thus be moisturized.
In one embodiment, the process thus further comprises a step c) of moisturizing the 3D-formable sheet material provided in step a) to a moisture content of 2 to 30 wt.-%, based on the total dry weight of the 3D-formable sheet material. Preferably, step c) is carried out such that the 3D-formable sheet material is moisturized to a moisture content of 6 to 25 wt.-% or of 10 to 20 wt.-%, based on the total dry weight of the 3D-formable sheet material.
It is appreciated that the moisture content after moisturizing is determined according to common practice, i.e. the moisture content is preferably not determined immediately after moisturizing. Preferably, the moisture content after moisturizing is determined as soon as a moisture equilibrium in the 3D-formable sheet material is achieved. Methods for obtaining and determining such moisture equilibrium are well known to the person skilled in the art.
For example, the moisture content is determined at least 30 min after moisturizing the 3D-formable sheet material. Preferably, the moisture content is determined 30 min to 24 h, e.g. 1 h to 24 h, after moisturizing the 3D-formable sheet material.
Moisturizing step c) is preferably carried out before and/or during process step b). In one embodiment, moisturizing step c) is carried out before and during process step b). Alternatively, moisturizing step c) is carried out before or during process step b). For example, moisturizing step c) is carried out before process step b).
The moisturizing of the 3D-formable sheet material may be undertaken by all the methods and instruments well known to the man skilled in the art for moisturizing materials. For example, the moisturizing of the 3D-formable sheet material can be carried out by spraying.
It is preferred that the 3D-formable sheet material has been obtained by
If the 3D-formable sheet material comprises additives, the cellulose 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 cellulose-inorganic filler material mixture. It is appreciated that this embodiment preferably applies where the cellulose material does not comprise tiller and/or pigments, If the 3D-formable sheet material comprises additives, the cellulose material is combined with the at least one particulate inorganic filler material and the additives in step i) to form a cellulose-inorganic filler material mixture.
With regard to the definition of the cellulose material, the at least one particulate inorganic filler material, the additives and preferred embodiments thereof, reference is made to the statements provided above when discussing the technical details of the 3D-formable sheet material of the present invention.
The cellulose material is preferably provided in form of an aqueous suspension. For example, an aqueous suspension comprising the cellulose material in a range from 0.2 to 35 wt.-%, more preferably 0.25 to 20 wt.-%, even more preferably 0.5 to 15 wt.-%, most preferably 1 to 10 wt-%, based on the total weight of the aqueous suspension.
In one embodiment, the cellulose material is a nanofibrillated cellulose and/or microfibrillated cellulose that has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence or presence of fillers and/or pigments.
If the cellulose material is a nanofibrillated cellulose and/or microfibrillated cellulose that has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the presence of fillers and/or pigments, the fillers and/or pigments and the at least one particulate inorganic filler material may be the same. That is to say, the fillers and/or pigments are the at least one particulate inorganic filler material. In this embodiment, the cellulose material is thus preferably not further combined with the at least one particulate inorganic filler material.
In another preferred embodiment, the cellulose material is a nanofibrillated cellulose and/or microfibrillated cellulose that has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence or presence of fillers and/or pigments and the cellulose material is further combined with the at least one particulate inorganic filler material.
In any case, the cellulose material provided comprises fillers and/or pigments and/or the cellulose material is combined with the at least one particulate inorganic filler material such that the 3D-formable sheet material comprises the at least one particulate inorganic filler material in an amount of ≥45 wt.-% based on the total dry weight of the 3D-formable sheet material.
If the cellulose material is combined with the at least one particulate inorganic filler material, the at least one particulate inorganic filler material is provided in powder form, i.e. in dry form, or in form of an aqueous suspension.
If the at least one particulate inorganic filler material is provided in form of an aqueous suspension, the aqueous suspension comprises the particulate inorganic filler material preferably in an amount from 1 to 80 wt.-%, more preferably from 5 to 78 wt.-%, even more preferably from 10 to 78 wt.-% and most preferably from 15 to 78 wt.-%, based on the total weight of the aqueous suspension.
In one embodiment, the cellulose material is provided in the form of an aqueous suspension and the at least one particulate inorganic filler material is provided in form of an aqueous suspension.
Alternatively, the cellulose material is provided in the form of an aqueous suspension and the at least one particulate inorganic filler material is provided in powder form.
An aqueous “slurry” or “suspension” in the meaning of the present invention comprises insoluble solids and water and usually may contain large amounts of solids and, thus, can be more viscous and generally of higher density than the liquid from which it is formed.
The term “aqueous” slurry or suspension refers to a system, wherein the liquid phase comprises, preferably consists of, water. However, said term does not exclude that the liquid phase of the aqueous slurry or suspension comprises minor amounts of at least one water-miscible organic solvent selected from the group comprising methanol, ethanol, acetone, acetonitrile, tetrahydrofuran and mixtures thereof. If the aqueous slurry or suspension comprises at least one water-miscible organic solvent, the liquid phase of the aqueous slurry comprises the at least one water-miscible organic solvent in an amount of from 0.1 to 40.0 wt.-% 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 wt.-%, based on the total weight of the liquid phase of the aqueous slurry or suspension. For example, the liquid phase of the aqueous slurry or suspension consists of water. If the liquid phase of the aqueous slurry or suspension consists of water, the water to be used can be any water available such as tap water and/or deionised water.
The cellulose material is combined with the at least one particulate inorganic filler material and the optional additives in any order. Preferably, the at least one particulate inorganic filler material and the optional additives are added to the cellulose material.
The cellulose material is a cellulose material mixture comprising nanofibrillated cellulose and/or microfibrillated cellulose.
Preferably, the cellulose material is a cellulose material mixture comprising nanofibrillated cellulose and/or microfibrillated cellulose that has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence or presence of fillers and/or pigments.
In case the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the absence of fillers and/or pigments, the nanofibrillated cellulose and/or microfibrillated cellulose is preferably in form of an aqueous suspension having a Brookfield viscosity in the range from 1 to 2 000 mPa·s at 25° C., more preferably from 10 to 1 200 mPa·s at 25° C., and most preferably from 100 to 600 mPa·s at 25° C., at a nanofibrillated cellulose and/or microfibrillated cellulose content of 1 wt.-%, based on the total weight of the aqueous suspension.
In case the nanofibrillated cellulose and/or microfibrillated cellulose has been obtained by nanofibrillating and/or microfibrillating a cellulose fibre suspension in the presence of fillers and/or pigments, the nanofibrillated cellulose and/or microfibrillated cellulose is preferably in form of an aqueous suspension having a Brookfield viscosity in the range from 1 to 2 000 mPa·s at 25° C., more preferably from 3 to 1 200 mPa·s at 25° C., and most preferably from 10 to 600 mPa·s at 25° C., at a nanofibrillated cellulose and/or microfibrillated cellulose content of 1 wt.-%, based on the total weight of the aqueous suspension.
The aqueous suspension of the nanofibrillated cellulose and/or microfibrillated cellulose preferably comprises the nanofibrillated cellulose and/or microfibrillated cellulose in an amount from 0.2 to 35 wt.-%, more preferably 0.25 to 20 wt.-%, even more preferably 0.5 to 15 wt.-%, most preferably 1 to 10 wt-%, based on the total weight of the aqueous suspension.
Processes for preparing nanofibrillated and microfibrillated celluloses are well known to a person skilled in the art. For example, processes for preparing nanofibrillated and microfibrillated celluloses are described in EP 2 386 682 A1, EP 2 386 683 A1, EP 2 236 664 A1, EP 2 236 545 A1, EP 2 808 440 A1 and EP 2 805 986 A1 which are thus incorporated herewith by references, 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).
It is appreciated that the term “cellulose-inorganic filler material mixture” refers to a mixture of the cellulose material, the at least one particulate inorganic filler material and the optional additives. Preferably, the cellulose-inorganic filler material mixture is a homogeneous mixture of the cellulose material, the at least one particulate inorganic filler material and the optional additives.
The cellulose-inorganic filler material mixture is preferably an aqueous suspension comprising the cellulose material, the at least one particulate inorganic filler material and the optional additives. In one embodiment, the aqueous suspension of the cellulose-inorganic filler material mixture has solids content in the range from 0.3 to 35 wt.-%, more preferably 0.5 to 30 wt.-%, even more preferably 0.7 to 25 wt.-%, most preferably 0.9 to 20 wt-%, based on the total weight of the aqueous suspension.
According to step ii) of the process, a presheet consisting of the cellulose-inorganic filler material mixture of step i) is formed.
The forming step ii) may be undertaken by all the techniques and methods well known to the man skilled in the art for forming a presheet of the cellulose-inorganic filler material mixture. The forming step ii) may be carried out with any conventional forming machine, for example, under conditions such that a continuous or dicontinuous presheet of the cellulose-inorganic filler material mixture is obtained or other such equipment known to the skilled person. For example, the forming can 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 presheet of the cellulose-inorganic filler material mixture can be subjected to a step of reducing the water content of the presheet, Such stop of reducing the water content can be carried out during or after, preferably after, process step ii). Such step of reducing the water content may be undertaken by all the techniques and methods well known to the man skilled in the art far reducing the water content of a presheet. The step of reducing the water content may be carried out with any conventional method, e.g. by pressure, wet pressing vacuum, force of gravity or suction power such that a presheet having a water content that is reduced compared to the water content before the step of reducing the water content is obtained or other such equipment known to the skilled person.
Unless specified otherwise, the term “reducing the water content” refers to a process according to which only a portion of water is removed from the presheet such that a predried presheet is obtained. Moreover, a “predried” presheet may be further defined by its total moisture content which, unless specified otherwise, is more than or equal to 5 wt.-%, preferably more than or equal to 8 wt.-%, more preferably more than or equal to 10 wt.-%, and most preferably from 20 to 60 wt.-%, based on the total weight of the presheet.
Thus, the process preferably further comprises a step iv1) of dewatering the presheet of step ii).
In one embodiment, the dewatering of step iv1) is carried out under pressure, preferably under pressure in the range from 10 to 150 kPa, more preferably under a pressure in the range from 20 to 100 kPa, and most preferably under a pressure in the range from 30 to 80 kPa.
Alternatively, the process further comprises a step iv2) of wet pressing the presheet of step ii).
In one embodiment, the presheet obtained in step iv1) is further subjected to a step of wet pressing in order to further reduce the water content. In this case, the process further comprises a step iv2) of wet pressing the presheet of step iv1).
Wet pressing step iv2) is preferably carried out under pressure in the range from 100 to 700 kPa, preferably under pressure in the range from 200 to 600 kPa, and most preferably under pressure in the range from 300 to 500 kPa. Additionally or alternatively, wet pressing step iv2) is carried out 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.
Preferably, step iv2) of wet pressing the presheet of step ii) or of step iv1) is carried out under a pressure in the range from 100 to 700 kPa, preferably under a pressure in the range from 200 to 600 kPa, and most preferably under a pressure in the range from 300 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 presheet of step ii) or of step iv1) or of step iv2) is dried into a 3D-formable sheet material.
The term “drying” refers to a process according to which at least a portion of water is removed from the presheet such that a 3D-formable sheet material is obtained. Moreover, a “dried” 3D-formable sheet material may be further defined by its total moisture content which, unless specified otherwise, is less than or equal to 30 wt.-%, preferably less than or equal to 25 wt.-%, more preferably less than or equal to 20 wt.-%, and most preferably less than or equal to 15 wt.-%, based on the total weight of the dried material.
Such step of drying may be undertaken by all the techniques and methods well known to the man skilled in the art for drying a presheet. The step of drying may be carried out with any conventional method, e.g. by pressure, force of gravity or suction power such that a presheet having a water content that is reduced compared to the water content before the drying is obtained or other such equipment known to the skilled person.
In one embodiment, step iii) is carried out by press drying. For example, by press drying under a pressure in the range from 50 to 150 kPa, preferably under a pressure in the range from 60 to 120 kPa, and most preferably under a pressure in the range from 80 to 100 kPa, and/or at a temperature in the range from 80 to 180° C., preferably at a temperature in the range from 90 to 160° C., and more preferably at a temperature in the range from 100 to 150° C.
In one embodiment, step iii) is carried out by press drying under a pressure in the range from 50 to 150 kPa, preferably under a pressure in the range from 60 to 120 kPa, and most preferably under a pressure in the range from. 80 to 100 kPa, and at a temperature in the range from 80 to 180° C., preferably at a temperature in the range from 90 to 160° C., and more preferably at a temperature in the range from 100 to 150° C.
In view of the very good results of the 3D-formable sheet material as defined above, a further aspect of the present invention refers to the use of a cellulose material as defined herein and at least one particulate inorganic filler material as defined herein. for the preparation of a 3D-formable sheet material.
Another aspect of the present invention refers to the use of a cellulose material as defined herein and at least one particulate inorganic filler material as defined herein for increasing the stretchability of a 3D-formable sheet material, wherein the increase is achieved when the 3D-formable sheet material has a normalized stretch increase per level of moisture content in the range from 0.15 to 0.7% per percent. The normalized stretch increase per level of moisture content is preferably determined in accordance with formula (I) defined above.
In one embodiment, the increase is achieved when the 3D-formable sheet material has a normalized stretch increase per level of moisture content in the range from 0.15 to 0.6% per percent and most preferably from 0.2 to 0.6% per percent. The normalized stretch increase per level of moisture content is preferably determined in accordance with formula (I) outlined above.
In one embodiment, the 3D-formable sheet material has a stretchability ranging from 4 to 10%, preferably from 5 to 10%, at a moisture content of 10% of the 3D-formable sheet material. Additionally or alternatively, the 3D-formable sheet material has a stretchability ranging from 6 to 18%, preferably from 7 to 18%, at a moisture content of 20% of the 3D-formable sheet material. The stretchability is preferably determined in accordance with formula (II) outlined above.
A still further aspect of the present invention refers to the use of a 3D-formable sheet material as defined herein in 3D-forming processes. Preferably, the present invention refers to the use of a 3D-formable sheet material as defined herein in thermoforming, vacuum forming, air-pressure forming, deep-drawing forming, hydroforming, spherical forming, press forming, or vacuum/air-pressure forming.
A further aspect of the present invention refers to a 3D-formed article, preferably a packaging container, food container, blister pack, food tray, comprising the 3D-formable sheet material as defined herein.
With regard to the definition of the cellulose material, the at least one particulate inorganic filler material, the 3D-formable sheet material and preferred embodiments thereof, reference is made to the statements provided above when discussing the technical details of the 3D-formable sheet material of the present invention.
The following examples may additionally illustrate the invention but are not meant to restrict the invention to the exemplified embodiments. The examples below show the 3D-formable sheet material and its excellent good mechanical properties such as stretchability and elongation at break according to the present invention:
The following measurement methods are used to evaluate the parameters given in the examples and claims.
Solids Content of Aqueous Suspensions Like Pigment Slurries Cellulose Containing Samples
The suspension solids content (also known as “dry weight”) was determined using a Moisture Analyzer MJ33 from the company Mettler-Toledo, Switzerland, with the following settings: drying temperature of 160° C., automatic switch off if the mass does not change more than 1 mg over a period of 30 s, standard drying of 5 to 20 g of suspension.
Moisture Content
Moisture content (wt. %)=100 (wt. %)−solids content (wt. %)
Particle Size of Mineral Particles
The weight median particle size d50 as used herein, as well as the top cut d98 is determined based on measurements made by using a Sedigraph™ 5120 instrument of Micromeritics Instrument Corporation. The method and the instruments are known to the skilled person and are commonly used to determine grain size of fillers and pigments. The measurement was carried out in an aqueous solution comprising 0.1 wt.-% Na4P2O7. The samples were dispersed using a high speed stirrer and supersonics. For the measurement of dispersed samples, no further dispersing agents were added.
Fiber Length Measurement
A length weighted average fiber length was determined with a Kajaani FS 200 (Kajaani, Electronics Ltd, now Valmet, Finland). The method and the instrument are known to the skilled person and are commonly used to determine fiber morphology parameters. The measurement was carried out solids content of ca. 0.010 wt.-%.
Freeness Tester (Schopper Riegler)
The Schopper-Riegler degree (° SR) was measured according to the Zelleheming Merkblatt V/7/61 and standardized in ISO 5267/1.
Brookfield Viscosity
The Brookfield viscosity of the aqueous suspensions was measured one hour after the production and after one minute of stirring at 25° C.±1° C. at 100 rpm by the use of a Brookfield viscometer type RVT equipped with an appropriate disc spindle, for example spindle 1 to 6.
Light Microscopy to Distinguish Between MFC Types
Micrographs were taken with a light microscope using transmitted light and bright field method.
Film Forming Device: “Scandinavian Type” Laboratory Sheets
An apparatus as described in SCAN-CM64:00 “Preparation of laboratory sheets for physical testing” was used, some modifications (J. Rantanen et al., “Forming and dewatering of a microfibrillated cellulose composite paper”, BioResources 10(2), 2015, pages 3492-3506) were carried out.
Film Forming Device: “Rapid Köthen Type” Laboratory Sheets
An apparatus as described in ISO 5269/2 “Preparation of laboratory sheets for physical testing—Part 2: Rapid Köthen method” was used, some modifications were applied, see the methods section “MFC filler composite films produced with “Rapid Köthen Type” laboratory sheet former” for more details.
Tensile Tester
A L&W Tensile Strength Tester (Lorentzen & Wettre, Sweden) was used for determination of the elongation at break according to procedures described in ISO 1924-2.
3D Forming Equipment and Procedure
A Laboratory Platen Press Type P 300 (Dr. Collins, Germany) was used for forming. Pressure, temperature, and pressing time were adjusted accordingly. Two aluminum dies were used. A first form with outer dimensions of 16 cm×16 cm×2.5 cm and a female die part representing a circular segment with a diameter of 10 cm and a depth of 1 cm representing linear stretch levels of ca. 3%. A second form with outer dimensions of 16 cm×16 cm×3.5 cm and a female die part representing a circular segment with a diameter of 10 cm and a depth of 2 cm, representing linear stretch levels of ca. 10%.
Flexible rubber plates with the dimensions 20 cm×20 cm×1 cm made of EPDM (ethylene propylene diene monomer rubber)
Compound of Microfibrillated Cellulose (MFC) and Filler
A compound of microfibrillated cellulose (MFC) and filler was obtained by treatment of 40 wt. % enzymatically (Buckman Maximyze 2535) and mechanically (disk refiner, to a freeness of >60° SR) pre-treated dissolving pulp together with 60 wt. % GCC filler (Hydrocarb® 60) at a solids content of 55% in a co-rotating twin screw extruder. The quality of the micro fibrillation is characterized with the microscopic image in
Microfibrillated Cellulose (MFC) Without Filler
A microfibrillated cellulose (MFC) as characterized with the microscopic image in
Hardwood Pulp
Once dried market eucalyptus pulp with a length weighted average fiber length of 0.81 mm.
Softwood Pulp
Once dried softwood pulp (pine) with a length weighted average fiber length of 2.39 mm.
GCC, Hydrocarb® 60 (Available from Omya International AG, Switzerland)
A dispersed ground calcium carbonate (GCC) pigment slurry with 78 wt. % solids content and a weight median particle size d50 of 1.6 μm was used.
PCC, Syncarb® F0474 (Available from Omya International AG, Switzerland)
A non-dispersed precipitated calcium carbonate (PCC) pigment slurry with 15 wt. % solids content and a weight median particle size d50 e of 2.7 μm was used.
Percol® 1540, BASF (Germany)
Preparing Microscopy Samples of Microfibrillated Cellulose (MFC) Produced in the Presence of Filler
A small sample (0.1 g) of wet (ca. 55 wt. %) MFC-filler-compound (described in the material section) was placed into a glass beaker, and 500 ml of deionized water were added. A kitchen blender was used to assist in separating fibres and calcium carbonate particles. 2 ml of 10 wt. % hydrochloric acid were then added to dissolve the calcium carbonate, then the resulting mixture was mixes with the kitchen blender for 2 minutes. A few drops of this suspension was given on a glass microscope slide and dried in an oven at 120° C.
Preparing Microscopy Samples of MFC
Approximately 1 g of microfibrillated cellulose (MFC) without filler as described above in the material section (solids content of 3.8 wt.-%) was placed into a glass beaker, and 500 ml deionized water were added. A kitchen blender was used for 2 minutes to separate the fiber material. A few drops of this suspension were given on a glass microscope slide and dried in an oven at 120° C.
Preparation of Hardwood Pulp
Once dried eucalyptusus pulp was disintegrated according to ISO 5263-1 and diluted to a solids content of 1.5 wt.-%. No refining was applied.
Preparation of Refined Hardwood Pulp
Once dried eucalyptus pulp was disintegrated according to ISO 5263-1 and diluted to a solids content of 3 wt.-%. A laboratory disk refiner (Escher Wyss, now Voith, Germany) was used to prepare eucalyptusus pulp with a freeness of 30° SR.
Preparation of Softwood Pulp
Once dried softwood pulp was disintegrated according to ISO 5263-1 and diluted to a solids content of 1.5 wt.-%. No refining was applied.
Preparation of Refined Softwood Pulp
Once dried softwood pulp was disintegrated according to ISO 5263-1 and diluted to a solids content of 1.5 wt.-%. A laboratory disk refiner (Escher Wyss, now Voith, Germany) was used to prepare softwood pulp with a freeness of 25° SR.
Preparing Furnish for Film Forming Without MFC
According to the formulations based on dry weight, hardwood pulp or hardwood. pulp or softwood pulp or refined softwood pulp, eventual GCC and/or PCC particles as well as deionized water to obtain a final solids content of 1 wt. % wore prepared in high shear conditions (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) with a mixing time of 15 minutes.
Preparation of Liquid Suspension of the MFC Filler Compound
Deionized water was added to the compound with a solids content of 55 wt. % in a quantity to obtain 10 wt. % solids content. High shear mixing (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) was applied for 15 minutes to disperse the compound, followed by further dilution with lionized water to a desired solid content level (5 wt.-%, 4 wt.-%, 2.5 wt.-%, 1 wt.-%) again with a 15 minutes high shear mixing step (Pendraulik, 2000 rpm).
Preparation of Furnish for Film Forming with MFC Filler Compound
According to the formulations based on dry Weight, mixtures of the MFC filler compound suspension with 1 wt.-%, solids content, hardwood pulp or softwood pulp and deionized water to obtain a final solids content of 1 wt.-% were prepared in high shear conditions (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) with a mixing time of 15 minutes.
Preparation of MFC Suspension Without Filler
Deionized water was added to the MFC, suspension in order to obtain desired solid content levels (2 wt.-%, 1 wt.-%), high shear mixing (Pendraulik, LD 50 Labordissolver, Pendraulik, Germany) was applied for 15 minutes to ensure proper mixing.
Preparation of Furnish for Film Forming with MFC Without Filler
According to the formulations based on dry weight, mixtures containing MFC, PCC and/or GCC, eucalyptus pulp or softwood pulp as well as deionized water to obtain a final solids content of 1% were prepared in high shear conditions (Pendraulik, LD 50 Labordissolver, Pendraulik., Germany) with a mixing time of 15 minutes.
MFC Filler Composite Films Produced with “Scandinavian Type” Laboratory Sheet Former
A modified “Scandinavian Type” laboratory sheet former was used to produce films. An according quantity of the prepared furnish to obtain a film weight of usually 200 g/m2 was filled into the upper section which was tightly connected to a membrane as top part of a lower section. The top section was closed with a hood and an overpressure of 0.5 bar was applied to accelerate dewatering through the membrane. No agitation or further dilution was used. After forming the sheets were prepared as known in the art between two blotting papers and then pressed for 260 seconds at 420 kPa. A further hot press step with four sheets placed between two blotting papers and a temperature of 130° C. as well as a pressure of 95 kPa was used to dry the sheets. For physical testing, the sheets were placed in a conditioned room, for forming a wetting procedure was applied.
MFC Filler Composite Films Produced with “Rapid Köthen Type” Laboratory Sheet Former
A sheet forming procedure according to ISO 5269/2 “Preparation of laboratory sheets for physical testing—Part 2: Rapid Köthen method” was used with the following modifications: a wire with a mesh width of 50 μm was used.. No water for dilution was added. No air for mixing was used. 5 seconds after filling the dewatering valve was opened and vacuum was applied for 25 seconds The sheets were pressed with Sheet Press (PTI, Austria) and then dried between blotting papers at 115 ° C. for 8 minutes.
Re-Wetting Sheets for Forming Trials
Based on the present moisture content (100—solids content in wt. %), a desired amount of deionized water to obtain 6.25 wt.-%, 8 wt.-%, 10 wt.-%, 15 wt.-% or 20 wt.-% moisture content was sprayed at the MFC filler composite films by using an aerosol can. MFC filler composite films of the same composition and the same moisture level were stored for 24 hours in a closed plastic bag to ensure homogeneous distribution of humidity.
3D Forming
For 3D forming a stack has to be prepared, from bottom to top: at first there is the bottom part of the platen press, followed by the aluminum die with the mold facing up, the sheet/film/material to be formed, a pile of rubber plates (3-4 for the 1 cm deep form, 5-6 for the 2 cm deep form) and finally the top part of the platen press. In the press used, the bottom part was moving and could be heated to a desired temperature. Before starting forming trials, the according die was placed in the heated press to get the desired temperature. Pressure, process dynamics (speed and time), temperature have to be adjusted accordingly.
a) Viscosities of MFC Suspensions
b) MFC Filler Composite Sheet Material Properties at Different Moisture Levels
The properties of the obtained sheet materials are also shown in
[1]m.c.: moisture content
c) 3D Forming Experiments
(1) 3D Forming Parameters
“Scandinavian type” laboratory sheets. Lower pressure in forming beneficial.
[1] m.c.: moisture content
(2) Reference Samples
“Rapid Köthen type” laboratory sheets.
[1] m.c.: moisture content
(3) Compound Series 1, Basic Conditions
“Scandinavian type” laboratory sheets.
[1] m.c.: moisture content
(4) Compound Series 2, Forced Conditions and 15 wt. % Moisture Content
“Scandinavian type” laboratory sheets.
[1] m.c.: moisture content
(5) Compound series 3, Forced Conditions and 20 wt. % Moisture Content
“Scandinavian type”laboratory sheets.
[1] m.c.: moisture content
(6) Compound Series 4, Forced Conditions, Different Compositions at 10 wt. % Moisture Content
“Scandinavian type” laboratory sheets.
[1] m.c.: moisture content
(7) Compound Series 5, Forced Conditions, Different Compositions at 20 wt. % Moisture Content
“Scandinavian type” laboratory sheets.
[1] m.c.: moisture content
| Number | Date | Country | Kind |
|---|---|---|---|
| 15189863 | Oct 2015 | EP | regional |
| 16166349 | Apr 2016 | EP | regional |
This application is a continuation of U.S. application Ser. No. 16/736,262, filed Jan. 7, 2020, now U.S. Pat. No. 11,384,210, issued Jul. 12, 2022, which claims the benefit of U.S. application Ser. No. 15/292,491, filed Oct. 13, 2016, now U.S. Pat. No. 10,577,469, issued Mar. 3, 2020, which claims the benefit of European Patent Application No. 15189863.2, filed Oct. 14, 2015 and European Patent application No. 16166349.7, filed Apr. 21, 2016, the entire contents of which is incorporated herein by reference.
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| Number | Date | Country | |
|---|---|---|---|
| 20230130544 A1 | Apr 2023 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16736262 | Jan 2020 | US |
| Child | 17834086 | US | |
| Parent | 15292491 | Oct 2016 | US |
| Child | 16736262 | US |
