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    • 专利摘要:
    process for making coated substrates, coated substrate, and, use of a substrate. the present invention relates to a process for making coated substrates providing a substrate, providing at least one mineral material, providing a polysaccharide material comprising one or more polysaccharide (s), coating the substrate with at least one mineral material, and coating the resulting pre-coating layer of mineral material with the gel comprising one or more polysaccharide (s), as well as the coated substrate obtained by this process and its use.
    公开号:BR112013030697B1
    申请号:R112013030697-1
    申请日:2012-05-21
    公开日:2020-10-06
    发明作者:Patrick A. C. Gane；Catherine Jean Ridgway；Michel Schenker
    申请人:Omya International Ag；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for making coated substrates, as well as the coated substrates obtained by this process and its use.
    [0002] It is an ongoing goal to improve the properties of certain substrates, for example, in papermaking to provide papers with better surface properties, for example, in terms of smoothness and surface uniformity, as well as structural stability.
    [0003] Advantage of significant rigidity, for example, can be obtained by using polysaccharides, be they fillers or coatings. For example, nano or microfibrillary cellulose is well known in papermaking as a coating material, as well as in wet finish application, but is hampered by high cost and potentially wasteful use in typical wet finish applications.
    [0004] The use of nano or microfibrillar cellulose in the wet end of paper / cardboard manufacturing strongly prevents membrane dehydration, increasing extra cost in both drying and slowing down the paper machine and, if used as a surface treatment agent, it shows little lining retention.
    [0005] The solubility and fineness of the material makes it inefficient to be retained and, when retained, is generally inefficiently applied to the spatial distribution of the paper fiber matrix.
    [0006] Loss of expensive material such as nano cellulose or microfibrillary in the void matrix of a paper or cardboard fiber, therefore, needs to be avoided, and maximum structural integrity of the surface needs to be maintained.
    [0007] Thus, the objective of the present invention is a method for producing coated substrates with good surface properties, for example, in terms of smoothness and surface uniformity, as well as structural stability, avoiding any undesirable material loss during production.
    [0008] It has been surprisingly observed that coating substrates with polysaccharide material in combination with a pre-coating of mineral material, which is able to absorb such polysaccharide material, significantly increases the efficiency of the use of such material, as well as the quality of the substrate, for example, in terms of smoothness and surface uniformity, surface resistance and rigidity in folding, where permeability can be easily controlled by the pre-coating and polysaccharide material ratio.
    [0009] Pre-coatings of mineral material are generally known, for example, by unpublished European patent application No. 10 168 352.2, but no indication can be observed in the prior art of combining such pre-coatings of mineral material with layers polysaccharide material, providing the aforementioned best characteristics of the resulting paper.
    [00010] It was observed that, using a pre-coating of mineral material, the polysaccharides of the polysaccharide material do not pass through the surface of the substrate and can integrate themselves into the porous structure of the pre-coating of mineral material, providing excellent retention and continuity of thin layer essential in the development of an efficient concentration of the polysaccharide on the surface of the substrate, which can be especially advantageous, for example, in the case of nanofibrillar cellulose, where the cellulosic material is kept on the surface of the substrate absorbing the nanofine fraction of the nanofibrillar cellulose , forming a mixed layer in situ.
    [00011] Thus, the above problem is solved by a process for making coated substrates, which is characterized by the following steps: - providing a substrate, - providing at least one mineral material, - providing a polysaccharide material comprising one or more polysaccharides (s ), - coating the substrate with at least one mineral material to obtain a pre-coating layer of mineral material, - coating the pre-coating layer of mineral material with the polysaccharide material comprising one or more polysaccharide (s).
    [00012] The observed effects appear to be linked to the well-known I-beam concept, in which the beam in this case consists of a substrate, such as a sheet of paper or cardboard, experiencing high stresses along the axial fibers that are further away from the neutral axis (not tensioned) under folding.
    [00013] According to the I-beam concept, which is normally used in construction, relatively little material is needed in the area close to the neutral axis for rigidity in bending, although it is certainly necessary to have sufficient z-direction resistance to resist delamination in the printing, folding and gluing processes.
    [00014] Contrary to this concept, being a homogeneous material, beam I can be considered representing the distribution of the density of the sheet; the neutral axis is arranged along the center of the membrane, which can be of relatively low density material and, above all, high density, is concentrated on the outer planar surfaces.
    [00015] The concept of beam I applies to nano and microfibrillar cellulosic material, as well as to other polysaccharides, such as starch, etc., used in the present invention, that is, the more structurally dense the material, the larger it will need to be the density differentiation between the distribution of external strength and bulky internal structure layers for the stiffening effect to be maximized, while when the overall density is low (for example, in uncalendered paper), the paper-type construction can be used for maximum benefit, and the outer layers can be kept at low density.
    [00016] Suitable substrates according to the present invention can be paper or cardboard, for example, calendered or uncalendered paper or cardboard, and can be selected from the group comprising standard coated and uncoated paper, which can be woodless or wood comprising (e.g. PlanoJet; Papyrus AB, Sweden).
    [00017] Substrates that can preferably be used in the present invention are selected from the group comprising printing papers, writing papers, copy papers, publication papers, synthetic papers, non-woven products, cardboard and packaging materials, construction materials such as decorative papers and cardboard and surface finishes.
    [00018] The mineral material that is used as a pre-coating on the substrate is preferably selected from the group comprising pigments and mineral fillers.
    [00019] Especially preferable, the mineral material is selected from the group comprising precipitated calcium carbonate (PCC), which can have a crystalline structure, calcitic argonitic; natural ground calcium carbonate (GCC), which can be selected from marble, limestone and / or chalk; calcium carbonate with modified surface; dolomite; baby powder; bentonite; clay; magnesite; satin white; sepiolite, huntite, diatomite; silicates; titanium dioxide; and mixtures thereof.
    [00020] In an especially preferred embodiment, said mineral material is selected from the group comprising calcium carbonates with modified surface, more preferably, calcium carbonates with reacted surface being a reaction product of natural calcium carbonate with carbon dioxide and a or more acid (s), in which carbon dioxide is formed in situ by treatment with acid and / or is supplied by an external source.
    [00021] Preferably, the natural calcium carbonate used for this reaction is selected from the group comprising marble, chalk, calcite, dolomite, limestone and mixtures thereof. In a preferred embodiment, the natural calcium carbonate is ground before treatment with an acid and carbon dioxide. The grinding step can be carried out with any conventional grinding device such as a mill known to those skilled in the art.
    [00022] Preferably, the surface-reacted natural calcium carbonate for use in the present invention is prepared as an aqueous suspension with a pH measured at 20 ° C, greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5.
    [00023] In a preferred process for the preparation of the aqueous suspension, the natural calcium carbonate, both finely divided, such as by grinding, or not, is suspended in water. Preferably, the slurry has a natural calcium carbonate content in the range of 1% by weight to 80% by weight, more preferably 3% by weight to 60% by weight, and even more preferably 5% by weight to 40% by weight. weight, based on the weight of the slurry.
    [00024] In a next step, an acid is added to the aqueous suspension containing the natural calcium carbonate. Preferably, the acid has a pKa at 25 ° C of 2.5 or less. If the pKa at 25 ° C is 0 or less, the acid is preferably selected from sulfuric acid, hydrochloric acid, or mixtures thereof. If the pKa at 25 ° C is 0 to 2.5, the acid is preferably selected from H2SO3, H2SO4, H3PO4, oxalic acid or mixtures thereof. One or more acid (s) can be added to the suspension as a concentrated solution or a more diluted solution. Preferably, the molar ratio of the acid to the natural calcium carbonate is 0.05 to 4, more preferably 0.1 to 2.
    [00025] As an alternative, it is also possible to add the acid to the water before the natural calcium carbonate is suspended.
    [00026] In a next step, natural calcium carbonate is treated with carbon dioxide. If a strong acid such as sulfuric acid or hydrochloric acid is used for treatment with natural calcium carbonate acid, carbon dioxide is automatically formed. Alternatively, or in addition, carbon dioxide can be supplied by an external source.
    [00027] Acid treatment and carbon dioxide treatment can be carried out simultaneously which is the case when a strong acid is used. It is also possible to perform treatment with acid first, for example, with a medium strong acid with a pKa in the range of 0 to 2.5, followed by treatment with carbon dioxide supplied by an external source.
    [00028] Preferably, the concentration of carbon dioxide gas in the suspension is, in terms of volume, such that the ratio (volume of suspension) :( volume of CO2 gas) is from 1: 0.05 to 1:20 , even more preferably 1: 0.05 to 1: 5.
    [00029] In a preferred embodiment, the acid treatment step and / or the carbon dioxide treatment step are repeated at least once, more preferably several times.
    [00030] Subsequent to the acid treatment and carbon dioxide treatment, the pH of the aqueous suspension, measured at 20 ° C, naturally reaches a value greater than 6.0, preferably greater than 6.5, more preferably greater than 7, 0, even more preferably greater than 7.5, thereby preparing the surface-reacted natural calcium carbonate as an aqueous suspension with a pH greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0 , even more preferably greater than 7.5. If the aqueous suspension naturally reaches equilibrium, the pH is greater than 7. A pH greater than 6.0 can be adjusted without the addition of a base while stirring the aqueous suspension continues for a sufficient period of time, preferably 1 hour at 10 hours, more preferably 1 to 5 hours.
    [00031] Alternatively, before reaching the equilibrium that occurs at a pH greater than 7, the pH of the aqueous suspension can be increased to a value greater than 6 by adding a base subsequent to the carbon dioxide treatment. Any conventional base such as sodium hydroxide or potassium hydroxide can be used.
    [00032] Additional details regarding the preparation of natural calcium carbonate with reacted surface are disclosed in WO 00/39222 and US 2004/0020410 A1, content of these references being included in the present application.
    [00033] In a preferred embodiment of the preparation of natural calcium carbonate with reacted surface, the natural calcium carbonate is reacted with the acid and / or carbon dioxide in the presence of at least one compound selected from the group consisting of silicate, silica, aluminum hydroxide, alkaline earth aluminate such as sodium or potassium aluminate, magnesium oxide, or mixtures thereof. Preferably, at least one silicate is selected from an aluminum silicate, a calcium silicate, or an alkaline earth metal silicate. These components can be added to an aqueous suspension comprising natural calcium carbonate before adding the acid and / or carbon dioxide.
    [00034] Alternatively, the silicate and / or silica and / or aluminum hydroxide and / or alkaline earth aluminate and / or magnesium oxide component (s) may be added to the aqueous suspension of natural calcium carbonate while the reaction of natural calcium carbonate with an acid and carbon dioxide has already started. Additional details regarding the preparation of natural calcium carbonate with surface reacted in the presence of at least one component (s) of silicate and / or silica and / or aluminum hydroxide and / or alkaline earth aluminate are disclosed in WO 2004/083316 , the content of these references being included in this application.
    [00035] It is also possible to use precipitated calcium carbonate with reacted surface, which is preferably produced according to a process described in EP application No. 2 070 991, namely, by placing a pigment comprising PCC in contact with H3O ions and with at least one anion capable of forming water-insoluble calcium salts, said anion being solubilized in an aqueous medium to form a pigment slurry comprising reacted surface PCC, wherein said reacted surface PCC comprises an insoluble calcium salt at least partially crystalline of said anion formed on the surface of at least part of the PCC, and an excess of solubilized calcium ions is provided.
    [00036] In a preferred embodiment, the mineral material has a specific surface area of 1 m2 / g to 200 nr / g, more preferably 20 m2 / g to 120 m2 / g and even more preferably 30 m2 / g to 115 m2 / g, especially of preferably 46 m2 / g to 100 m2 / g, above all preferably 50 m2 / g to 80 m2 / g, eg 55 m2 / g measured using nitrogen and the BET method according to ISO 9277.
    [00037] Furthermore, it is preferred that the mineral material has a median particle size (I / SO) from 0.01 to 50 pm, more preferably from 0.05 to 25 pm, even more preferably 0.1 to 10 pm pm, especially preferably from 0.2 to 5 pm, for example, 2.7 pm, particularly from 0.5 to 1.5 pm, for example, 0.8 pm measured according to the method mentioned below .
    [00038] For particles with a dso greater than 0.5 pm, the median particle size in weight t / so was determined using a Sedigraph 5100 device from Micromeritics, USA. The measurement was performed in an aqueous solution of 0.1% by weight of Na4P2θ . The samples were dispersed using a high speed shaker and ultrasound. For particles with a / 50 <500 nm, the median particle size by volume was determined using a Malvern Zetasizer Nano ZS from Malvern, UK. The measurement was performed in an aqueous solution of 0.1% by weight of Na4P2θ . The samples were dispersed using a high speed shaker and ultrasound.
    [00039] In a preferred embodiment, the mineral material is a natural calcium carbonate with reacted surface with a specific surface area in the range of 15 to 200 m2 / g and a median particle size by weight in the range of 0.1 to 50 p , m. More preferably, the specific surface area is in the range of 20 to 80 m2 / g and the median particle size by weight is in the range of 0.5 to 25 pm. Even more preferably, the specific surface area is in the range of 30 to 60 m2 / g and the median particle size by weight is in the range of 0.7 to 7 pm.
    [00040] The mineral material can be provided in the form of a powder, although it is preferably applied in the form of a suspension, such as an aqueous suspension. In this case, the solids content of the mineral material of the suspension is preferably from 10 to 80% by weight, more preferably from 20 to 75% by weight, still more preferably from 30 to 60% by weight, above all it is preferably from 40 to 55% by weight, for example, 50% by weight.
    [00041] It is possible to combine the mineral material with binders such as, for example, styrene acrylate latex binders, such as Acronal S360D (BASF, Ludwigshafen, Germany) in order to improve the bonding of the mineral material pre-coating to the substrate .
    [00042] Additional binders, which can be advantageously used in combination with the mineral material are, for example, selected from the group comprising starch, proteins, styrene butadiene latex, polyvinyl alcohol, poly (vinyl acetate), and mixtures thereof.
    [00043] The binders can be used in an amount of 1 to 30% by weight, preferably 4 to 20% by weight, more preferably 5 to 15% by weight, above all preferably 7 to 10% by weight based on weight dry mineral material.
    [00044] The polysaccharide material used in the present invention comprises one or more polysaccharides (s), which are preferably selected from the group comprising linear and branched polysaccharides such as cellulose, starch, chitin, chitosan, pectin, xanthan gum and dextran, and derivatives of the same.
    [00045] Polysaccharide materials comprising one or more polysaccharide (s) according to the present invention, can be used in the dry state or in the form of suspensions, solutions, dispersions or emulsions, or as gels, especially nanogels, in which the liquid medium it can be water or organic solvents.
    [00046] They preferably have a solids content of 0.01% by weight to 50% by weight, preferably from 1 to 15% by weight, more preferably from 3 to 12% by weight, above all preferably from 4 to 10 % by weight. Generally, the solids content can be as high as up to the saturation concentration depending on the viscosity of the polysaccharide.
    [00047] Especially preferred are nanogels, that is, the polysaccharide particles comprised in the gel have a diameter in the nanometric range, that is, less than or equal to 1 pm, for example, from 1 to 200 nm, preferably from 10 to 100 nm , more preferably from 15 to 80 nm, even more preferably from 20 to 50 nm, above all preferably from 25 to 40 nm, for example, 30 nm.
    [00048] It has been found that the combination of such a polysaccharide material, especially nanogels, as a top coat application in a pre-coat of absorbent mineral material has numerous positive effects. For example, the retention of such layers on the substrates is considerably greater, and the substrates are provided with a smoother surface, as well as greater folding rigidity compared to uncoated substrates, or substrates directly coated with such a polysaccharide material without a pre- mineral material coating.
    [00049] Even materials, such as starch, which are well known and commonly used as a reinforcing agent, for example, in papermaking, either applied directly to the wet finish or as an ironing agent on the substrate surface, can be used much more effectively by combining with the pre-coating of absorbent mineral material, for example, in terms of stiffening the leaf, which is not generally related to internal or surface resistance per se, which is the main property normally conferred by starch, which is due to the fact that the polysaccharide material is at least partially absorbed in the pre-coating layer of mineral material.
    [00050] In this regard, starches that can be used in accordance with the present invention can be any one commonly known in coating applications, such as corn starch, tapioca, wheat and potato starch in its native or chemical form or thermally modified, as well as cationic starches. Examples for starches that are used in the present invention are modified starches such as those available from Cerestar Cargill (Krefeld, Germany) with the trademarks C Film TCF 07302, C Film TCF 07311, C Film TCF 07312, C Film TCF 07324, as well as cationic starches such as C Film HS 05978, any of which can be made into colloidal starch solutions, which are especially used in the present invention, by dispersing the powdered starch in water at a certain solids content, for example, up to 45% by weight and heating the dispersion, as is known to those skilled in the art. In accordance with the present invention, starches can also generally be used in the form of solutions and dispersions.
    [00051] The aforementioned effect of combining the polysaccharide material with a pre-coating of mineral material, can be even greater by the use of nanofibrillar cellulose gels forming a superficial nanocomposite in situ. This increase is due to the nanofibrillar structural improvement properties in terms development of resistance integrity of longer duration compared to soluble binding agents.
    [00052] Thus, in an especially preferred embodiment, the polysaccharide material is a nanofibrillar cellulose gel.
    [00053] Cellulose is the structural component of the primary cell wall of green plants and is the most common organic compound on Earth. It is of high interest in many applications and industries.
    [00054] Cellulose pulp as a raw material is processed from wood or plant stems such as hemp, flax and manila. Pulp fibers are mainly made up of cellulose and other organic components (hemicellulose and lignin). Cellulose macromolecules (composed of β-D-Glucose molecules linked to 1-4 glycosides) are linked together by hydrogen bonds to form a so-called primary fibril (mycelium) that has crystalline and amorphous domains. Several primary fibrils (around 55) form a so-called microfibril. Around 250 of these microfibrils form a fibril.
    [00055] Fibrils are arranged in different layers (which may contain lignin and / or hemicellulose) to form a fiber. The individual fibers are also linked together by lignin.
    [00056] When fibers are refined under applied energy they become fibrillated as the cell walls are broken and become attached strips, that is, in fibrils. If this break continues to separate the fibrils from the fiber body, it will release the fibrils. The breakdown of fibers in microfibrils is referred to as “microfibrillation”. This process can continue until there are no more fibers left and only nanosize (thickness) fibrils remain.
    [00057] If the process continues further and breaks these fibrils into ever smaller fibrils, they eventually become fragments of cellulose or nanofibrillar gels. Depending on how long the latter lasts, some nanofibrils may remain between the nanofibrillary gels. The break in primary fibrils can be referred to as “nanofibrillation”, where there can be a smooth transition between the two regimes. Primary fibrils form a gel (metastable network of primary fibrils) in an aqueous environment that can be referred to as a “nanofibrillar gel”. It can be considered that gel formed from nanofibrils contains nanocellulose.
    [00058] Thus, nanofibrillar cellulose in the context of the present invention means fibers, which are at least partially broken down into primary fibrils, and nanofibrillar gel means a gel, which is formed from these primary fibrils in an aqueous environment (stable primary network of primary fibrils) considered at the limit of fineness to be essentially nanocellulose), in which there is a smooth transition between nanofibers and nanofibrillar gel, comprising nanofibrillar gels containing a wide range of nanofibrils, all of which are understood by the term nanofibrillar cellulose gels according to the present invention .
    [00059] Nanofibrillary gels are desirable, as they normally contain very thin fibrils, which are considered to be partly made of nanocellulose, showing a stronger bonding potential for themselves, or with any other material present, than for fibrils that are not that thin or do not exhibit nanocellulosic structure.
    [00060] Such nanofibrillary gels are commercially available. For example, under the trademark AVOCEL® MF 40-10 (J. Rettenmaier & Sõhne GmbH & Co KG, Rosenberg, Germany).
    [00061] In general, nanofibrillary gels used in the present invention can be produced by fibrillation. In this regard, fibrillation means any process that predominantly breaks fibers and fibrils along its long axis resulting in a decrease in the diameter of fibers and fibrils, respectively.
    [00062] The size of the cellulose fibers before fibrillation is in principle not critical. Generally any commercially available and processable fiber is used in the device used for its fibrillation. Depending on their origin, cellulose fibers can have a length of 50 mm at 0.1 pm. Such fibers, as well as those with a length of preferably 20 mm to 0.5 pm, more preferably 10 mm to 1 mm, and typically 2 to 5 mm, can be advantageously used, where also larger and smaller fibers can be used. used.
    [00063] It is advantageous that the cellulose fibers are supplied in the form of a suspension, especially an aqueous suspension. Preferably, such suspensions have a solids content of 0.2 to 35% by weight, more preferably 0.25 to 10% by weight, even more preferably 0.5 to 5% by weight, especially 1 to 4% by weight, above all preferably preferably 1.3 to 3% by weight, for example, 1.5% by weight.
    [00064] Cellulose fibers that can be used in the production of such gels can be such contained in natural, chemical, mechanical, chemiomechanical, thermomechanical pulps. Especially used are pulps selected from the group comprising eucalyptus pulp, spruce pulp, pine cone pulp, beech pulp, hemp pulp, cotton pulp, bamboo pulp, bagasse and mixtures thereof. In one embodiment, all or part of this cellulose fiber can be produced from a step of recycling a material comprising cellulose fibers. Thus, the pulp can also be recycled and / or deinked pulp.
    [00065] In a special embodiment, cellulose fibers can be fibrillated in the presence of at least one filler and / or pigment providing a preferred nanofibrillar cellulose gel. Fibrillation is performed until the gel is formed, where the formation of the gel is verified by monitoring the viscosity depending on the shear rate. By increasing the shear rate in stages, a certain curve reflecting a decrease in viscosity is obtained. If, subsequently, the shear rate is reduced in steps, the viscosity increases again, but the corresponding values in at least part of the range of the shear rate as the shear approaches zero are lower when increasing the shear rate. shear, graphically expressed by a hysteresis manifestation when the viscosity is plotted against the shear rate. As soon as this behavior is observed, a nanofibrillar cellulose gel used in the present invention is formed.
    [00066] At least one filler and / or pigment used in the fibrillation of cellulose fibers is preferably selected from the group comprising precipitated calcium carbonate (PCC); natural ground calcium carbonate (GCC); calcium carbonate with modified surface; dolomite; baby powder; bentonite; clay; magnesite; white satin mica; sepiolite, huntite, diatomite; silicates; and mixtures thereof. Precipitated calcium carbonate, which may have a distinct crystalline structure, aragonitic calcite, and / or natural ground calcium carbonate, which can be selected from marble, limestone and / or chalk, are especially preferred.
    [00067] In a special modality, the use of precipitated calcium carbonate scalenohedral or rhombohedral, prismatic ultrafine discrete can be advantageous.
    [00068] The filler (s) and / or pigment (s) may be provided in the form of a powder, although they are preferably added in the form of a suspension, such as an aqueous suspension. In this case, the solids content of the suspension is not critical, as long as it is a pumpable liquid.
    [00069] In a preferred embodiment, the filler and / or pigment particles used in the fibrillation of cellulose fibers have a median particle size of 0.01 to 15 pm, preferably 0.1 to 10 pm, more preferably 0.3 at 5 pm, especially from 0.5 to 4 pm and above all preferably 0.7 to 3.2 pm, for example, 2 pm, where, as previously mentioned, for particles with a median particle size dso greater than 0.5. pm, the median particle size by weight was determined using a Sedigraph 5100 device, and for particles with a median particle size i / 50 <500 nm, the median particle size by volume was determined using a Malvern Zetasizer Nano ZS.
    [00070] During the fibrillation process, the size of the charge (s) and / or pigment (s) as well as the size of the fibers can change.
    [00071] Thus, fibrillated fibers, also called fibrils, which include aggregates of cellulose molecules, can have a diameter of 1 to 200 nm, preferably from 10 to 100 nm, more preferably from 15 to 80 nm, even more preferably from 20 to 50 nm, above all preferably from 25 to 40 nm, for example, 30 nm, determined as the volume median particle size using a Malvern Zetasizer Nano ZS.
    [00072] The length of such fibrils, which can vary greatly depending on the pulp source and the production method, can typically be from 1 to 5,000 pm, preferably from 10 to 2,000 pm, more preferably from 50 to 1,000 pm, above all preferably from 100 to 500 pm and was determined by SEM images, where the length was measured by comparison with the scale bar.
    [00073] The combination of fibers and at least one filler and / or pigment can be accomplished by adding the filler and / or pigment to the fibers in one or several steps. Likewise, the fibers can be added to the filler and / or pigment in one or several steps. The filler (s) and / or pigment (s) as well as the fibers can be added completely or in portions before or during the fibrillation step. However, addition before fibrillation is preferred.
    [00074] Preferably, the weight ratio of fibers for filler (s) and / or pigment (s) based on dry weight is 1:33 to 10: 1, more preferably 1:10 to 7: 1, even more preferably 1: 5 to 5: 1, typically 1: 3 to 3: 1, especially 1: 2 to 2: 1 and above all preferably 1: 1.5 to 1.5: 1, for example, 1: 1.
    [00075] The dosage of filler and / or pigment can be critical. If there is too much of the filler and / or pigment, this can influence the formation of the gel. Thus, if no gel formation is observed in a specific combination, it may be necessary to reduce the amount of filler and / or pigment.
    [00076] Furthermore, in one embodiment, the combination is stored for 2 to 12 hours, preferably 3 to 10 hours, more preferably 4 to 8 hours, for example, 6 hours, before its fibrillation, since this ideally results swelling of the fibers facilitating fibrillation.
    [00077] Fiber swelling can be facilitated by storage at a higher pH, as well as by adding cellulose solvents such as copper (II) ethylenediamine, iron and sodium tartrate or lithium chlorine / dimethylacetamine, or any other method known in the art.
    [00078] Fibrillation is performed using any device used for this purpose. Preferably, the device is a homogenizer. It can also be an ultrathin friction crusher such as a Supermasscolloider from Masuko Sangyo Co. Ltd, Japan, or one described in US 6,214,163 or US 6,183,596.
    [00079] Any commercially available homogenizer is suitable for fibrillation, especially high pressure homogenizers, in which suspensions are pressed under high pressure through a restricted opening, which may comprise a valve, and are discharged into the high pressure restricted opening against a hard impact surface directly in front of the restricted opening, thus reducing the particle size. Pressure can be generated by a pump, such as a piston pump, and the impact surface can comprise an impact ring that extends around the opening of the annular valve. An example of a homogenizer that can be used in the present invention is Ariete NS2006L by GEA Niro Soavi. However, inter alia, homogenizers such as APV Gaulin Series, HST HL Series or Alfa Laval SHL Series can also be used.
    [00080] In addition, devices such as ultrathin friction crushers, for example, a Supermasscolloider, can be advantageously used in the present invention.
    [00081] Additional details regarding the production of the nanofibrillar cellulose gel, in the presence of at least one filler and / or pigment, can be taken from the European patent application No. 2 236 545.
    [00082] It is furthermore advantageous to combine such gels that are produced in the presence of fillers and / or pigments with even more additional non-fibrillated fibers and / or at least one additional filler and / or pigment after gel formation.
    [00083] In this regard, additional non-fibrillated fibers are preferably selected from cellulose fibers as previously defined. However, also another fiber material can be advantageously used as additional non-fibrillated fibers in the process of the present invention.
    [00084] At least one additional filler and / or pigment can be selected from the group comprising precipitated calcium carbonate (PCC); natural ground calcium carbonate (GCC); calcium carbonate with modified surface; dolomite; baby powder; bentonite; clay; magnesite; white satin mica; sepiolite, huntite, diatomite; silicates; and mixtures thereof. Precipitated calcium carbonate, which may have a distinct crystalline structure, argonitic calcite, and / or natural ground calcium carbonate, which can be selected from marble, limestone and / or chalk, are especially preferred.
    [00085] In a special modality, the use of precipitated calcium carbonate, scalenohedral or ultra-thin prismatic rhombohedral may be advantageous.
    [00086] This charge (s) and / or additional pigment (s) may also be provided in the form of a powder, although it is preferably added in the form suspension, such as an aqueous suspension. In this case, the solids content of the suspension is not critical, as long as it is a pumpable liquid.
    [00087] However, it is especially advantageous if at least one additional filler and / or pigment is a very fine product in terms of particle size, and especially preferably, it comprises at least a fraction of particles with an average diameter / / 50 in the nanometric range, contrary to the pigment (s) and / or filler (s) used in the formation of gel, which are very coarse.
    [00088] Thus, it is furthermore preferable that at least one additional charge and / or pigment particle has a median particle size of 0.01 to 5 pm, preferably 0.05 to 1.5 pm, more preferably 0.1 at 0.8 pm and above all preferably 0.2 to 0.5 pm, for example, 0.3 pm, where, as previously mentioned, for particles with a median particle size 1/50 greater than 0.5 pm, the median particle size by weight was determined using a Sedigraph 5100 device and, for particles with a median particle size 1/50 <500 nm, the median particle size by volume was determined using a Malvern Zetasizer Nano ZS.
    [00089] Additional details regarding the nanofibrillar cellulose gel combined with additional non-fibrillated fibers and / or additional fillers and / or pigments after the formation of such a gel can be taken from unpublished European patent applications No. 10 161 166.3 and 10,161 173.9.
    [00090] The mineral material, as well as any of the fillers and / or pigments used in nanofibrillar cellulose gels, can be associated with dispersing agents such as those selected from the group comprising homopolymers or copolymers of polycarboxylic acids and / or their salts or derivatives such as esters based on, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, for example, acrylamide or acrylic esters such as methyl methacrylate, or mixtures thereof; alkaline polyphosphates, phosphonic, citric and tartaric acid and their salts or esters; or mixtures thereof.
    [00091] The mineral material as well as the polysaccharide material can be coated on the substrate, or on the pre-coating of mineral material, respectively, by means of any well-known equipment for coating substrates, for example, by countertop coating, curtain, spatula coating, blade coating and the like known in the art.
    [00092] Especially preferred, especially on a laboratory scale, are benchtop coaters such as those available from Erichsen GmbH & Co. KG, Hemer, Germany, in which different rods, such as different round wire rods, can be used depending on the desired coating weights.
    [00093] In order to obtain optimum coating coverage, it may be advantageous to load a large quantity of the product in front of the stem before being extracted. This ensures that there is enough of the product to be coated, and in the case of remaining product, such as fibers, if nanofibrillar gels are used, it can be extracted with the rod.
    [00094] This later feature can also serve as a means of recycling the fiber retains fraction while distributing the soluble and nanofine fraction in the coating structure. A filtration process like this can be used to reduce manufacturing energy, if nanofibrillar cellulose gels are used by adopting selective filtration and reuse of the fiber fraction to produce additional cellulose gel, thus additionally preventing viscosity from increasing in production and its associated energy loss, processing equally efficient if necessary and consequently providing a potential cost reduction in the production of nano and general microfibrillar cellulose.
    [00095] Thus, the application of pre-coating of absorbent mineral material can also be used to promote a filtration process to absorb the less well-refined fibrillar cellulosic liquid reinforcement phase.
    [00096] Such a procedure can also provide better efficiency in a nanofibrillar production process in place, and thus provide a semicontinuous extraction of the important nanogel in an effective circuit process, returning the excess microfiber retention generated during the coating process.
    [00097] Opportunities to save substrate material are clearly identifiable, for example, the costs of refining papermaking can be reduced and / or greater load loading applied, or more recycled fiber can be employed. The improved surface properties also increase the permeability control for both better printability and the production of cost effective barrier layers.
    [00098] If the coarser fraction is also applied as a surface treatment, however, the application considered would require both a non-contact method and a size press application avoiding the exclusion of size in shear elements. Also, the use of air blade elements can be made by blowing off the excess coating.
    [00099] Non-cellulosic polysaccharide material such as, for example, starch-based polysaccharide material would not have these problems, and could be applied directly using an extraction rod.
    [000100] The mineral material as well as the polysaccharide material can be independently coated from each other on the substrate and / or the pre-coating of mineral material, respectively, in one or several layers.
    [000101] The total coating weight of the pre-coating of mineral material can be from 2 gm-2 to 50 gm-2, preferably from 5 gm-2 to 40 gm-2, more preferably from 7 gm-2a to 30 gm 2 above all preferably 8 gm-2a25 gm-2.
    [000102] The total coating weight of polysaccharide material can be from 0.5 gm-2 to 20 gm'2, preferably from 1 gm-2 to 15 gm-2, more preferably from 2 gnr2 all gm-2, above all preferably from 3 gnr2 to 5 gnr2.
    [000103] It is a further aspect of the present invention to provide a coated substrate obtained by the above-described process in detail.
    [000104] Thus, an additional aspect of the present invention is a coated substrate comprising a pre-coating of mineral material, and a coating comprising a polysaccharide material comprising one or more polysaccharide (s), wherein, depending on the polysaccharide used, the material Polysaccharide can be partially or completely absorbed by the pre-coating of mineral material. It is also possible that a part of the polysaccharide material, such as, for example, cellulose fibers, is covering the mineral material while the rest of the polysaccharide material is absorbed in the pre-coating of mineral material.
    [000105] In a preferred embodiment the coated substrate is a coated paper as defined above.
    [000106] Another aspect of the present invention is finally the use of the coated substrates according to the invention as packaging material, composites, barrier layers, printing surfaces, reinforcement aids and / or binders.
    [000107] The figures described below, and the examples and experiments, serve to illustrate the present invention and should not restrict it in any way. Description of figures:
    [000108] SEM images described below were obtained by fixing the sample in a probe holder, coating this sample with gold in order to make it electrically conductive, subsequently placing the sample in the high vacuum chamber of the SEM (scanning electron microscope) ) (vacuum: approximately 2 - 3 x 10'5 mbar (2-3 mPa), room temperature, voltage: 30 kV, working distance: 10 mm) and starting the image formation. It is indicated where a previous sample preparation was carried out.
    [000109] Figure 1 shows a SEM image of natural ground calcium carbonate with reacted surface. The sample was prepared by spraying it with a sprinkler on filter paper. Then, the filter paper with the sample layer was dried at room temperature.
    [000110] Figures 2 (a) and (b) show SEM images of commercial nanodispersed cellulose gel in different magnifications after lyophilization. Samples with a solids content of 10% by weight of the material in water, were frozen with shock with liquid nitrogen, followed by freeze-drying of the frozen sample with vacuum shock (approximately 0.080 mbar (8 Pa), approximate temperature -55 ° C ).
    [000111] Figure 3 shows SEM images of nanofibrillated cellulose gel formed in the presence of calcium carbonate (a) after lyophilization, (b) as a suspension sprinkled on filter paper and then dried. The sample (a) with a solids content of 0.5% by weight of the material in water was frozen with shock with liquid nitrogen, followed by lyophilization, the sample was frozen with vacuum shock (approximately 0.080 mbar (8 Pa), approximate temperature -55 ° C). Sample (b) with a solids content of 0.5% by weight of the material in water was sprayed with a sprinkler on filter paper. The filter paper with the sample layer was dried at room temperature.
    [000112] Figure 4 shows the coating weights (uptake) of different polysaccharide materials on substrates of mineral and uncoated material, respectively, depending on the measured applied volume.
    [000113] Figure 5 shows SEM images of a non-calendered base paper only (figure 5a) and coated with a commercial cellulose gel (applied three times) (figure 5b).
    [000114] Figure 6 shows SEM images of an uncalendered base paper coated with a mineral material only (figure 6a) and coated with a triple layer of a commercial cellulose gel on top of the mineral material layer (figure 6b).
    [000115] Figure 7 shows SEM images of base paper pre-coated with mineral material and subsequently coated with a nanofibrillated cellulose gel formed in the presence of calcium carbonate (figure 7a) and a starch material (figure 7b).
    [000116] Figure 8 is a cross-sectional SEM image of fiber kept out of a commercial cellulose gel in the layer of pre-coated absorbent mineral material on an uncalendered base paper.
    [000117] Figure 9 is a cross-sectional SEM image of a starch material absorbed on the surface of the pre-coated mineral material layer on a non-calendered base paper.
    [000118] Figure 10 is an illustration of the roughness values of selected coated samples.
    [000119] Figure 11 is an illustration of the rigidity in folding uncalendered and calendered papers pre-coated with increasing amounts of mineral material and coated with increasing amounts of commercial cellulose gel, cellulose gel comprising filler and starch material.
    [000120] Figures 12 a) to e) are more detailed illustrations of the rigidity in folding uncalendered and calendered papers pre-coated with increasing amounts of mineral material and coated with increasing amounts of commercial cellulose gel, cellulose gel comprising filler and starch material showing the benefits of the present invention.
    [000121] Figure 13 is an illustration of the permeability of uncalendered and calendered papers pre-coated with increasing amounts of mineral material and coated with increasing amounts of commercial cellulose gel, cellulose gel comprising filler and starch material. EXAMPLES 1. Materials Substrate: Standard non-coated 80 gm2 copy paper (PlanoJet; Papyrus AB, Sweden). Mineral Material: Natural ground calcium carbonate with reacted surface (Omyajet B6606; Omya AG, Oftringen, Switzerland; see figure 1); weight median particle diameter µ / 50 = 2.70 pm (Sedigraph 5100); specific surface area = 56 nr / g; in the form of an aqueous slurry with a solids content of 50% by weight with respect to the mineral material.
    [000122] The mineral material was mixed with 10% by weight based on the amount of mineral material of a styrene acrylate latex binder (Acronal S360D; BASF, Ludwigshafen, Germany) and diluted to obtain a total solids content of 40% in weight. Polysaccharide Material:
    [000123] PM 1: ARBOCEL MF 40-10 (J. Rettenmeyer und Sõhne GmbH & Co. KG, Rosenberg, Germany), a nanodisperse cellulose with a solids content of 10% by weight, a median (fibrous) particle diameter < 1 pm, and a wet sieve residue at 25 pm <0.2% by weight (see figure 2).
    [000124] PM 2: Nanofibrillary cellulose gel formed in the presence of calcium carbonate using a dissolving disc and then fibrillated using a Supermasscolloider (cf. figure 3).
    [000125] 180 g of dried eucalyptus pulp, 5,820 g of tap water and 18 g of Omyacarb 1 AV (available from Omya AG; fine calcium carbonate powder, manufactured from a high purity, white marble; particle size median in weight i / 50 is 1.7 pm as measured by Malvern Mastersize X) (load pulp 10: 1, dry / dry) were mixed using a Pendraulik stirrer at 2,000 rpm with a mounted dissolving disc (d = 70 mm) for at least 10 minutes. This mixture was processed with the Supermasscolloider as described below.
    [000126] The previous composition was processed with an ultrafine friction crusher (Supermasscolloider from Masuko Sangyo Co. Ltd, Japan (Model MKCA 6-2) with silicon carbide stones assembled with a granulation class of 46 (granulation size 297 - 420 pm) The clearance between the stones was adjusted to “-50” pm (dynamic 0 point, as described in the manual distributed by the supplier). The speed of the rotary crusher was adjusted to 2,500 rpm for passes 1-5, 2,000 rpm for passes 6 and 7, 1,500 rpm for passes 8 and 9, 1,000 rpm for passes 10 and 11, 750 rpm for passes 12 and 13 and 500 rpm for passes 14 and 15.
    [000127] PM 3: Cationic starch solution (C-FILM 05978; Cargill International S.a, 1206 Geneva, Switzerland), produced at 12% by weight of solids concentration. Comparative Examples:
    [000128] For comparative purposes, the aforementioned polysaccharide materials were coated directly on the substrate, that is, without a pre-coating of mineral material using the equipment described below. Inventive Examples:
    [000129] In order to illustrate the benefits of combining the polysaccharide material with a pre-coating of mineral material according to the invention, and thus preventing polysaccharides, especially cellulose fiber material, from passing through the surface, a discreetly bimodal porous coating layer (ie, with intraparticle pores and interparticle pores) consisting of the mineral material was first applied directly to the base paper.
    [000130] The mineral material coating formulation was applied to the base paper using a range of different round wire rods on a bench topper (Erichsen GmbH & Co. KG, Hemer, Germany) to obtain a range of different coating weights (see table below).
    [000131] These sheets were then coated with the polysaccharide materials described above PM 1, PM 2 and PM 3, respectively, which were also each coated with three different coating weights. 2.Methods
    [000132] The thinnest rod available for the bench topcoat was used only to the extent that a light coating was required.
    [000133] Due to the high water content of the polysaccharide materials, a curl resulting from the paper was a problem, especially if larger amounts were applied. This problem was addressed by keeping the paper as flat as possible during drying, and, in the case of higher application weights, between multiple application layers.
    [000134] It was also observed that, in order to obtain the ideal covering coverage, a large quantity of the product must be loaded in front of the rod before being stretched. This ensures that there is enough of the thin fibrillar gel to be coated, and remaining fibers can be extracted with the rod.
    [000135] From the table below, the coating weights achieved when using the different rods for the pre-coatings of the mineral-latex material and also for the gel layers coated both on the base paper itself and on the pre-coat mineral-latex material can be taken.
    stem 0 (white): wet film thickness: 4 pm stem 1 (yellow): wet film thickness: 6 pm stem 2 (red): wet film thickness: 12 pm stem 3 (green): wet film thickness: 24 pm rod 4 (black): wet film thickness: 40 pm
    [000136] For each pre-coated substrate there is generally a decrease in the uptake of polysaccharide material as the coating weight of the applied pre-coating layers increases. This is a clear indication that the uptake of polysaccharide material in an uncoated paper is defined by the porosity of the paper fiber matrix, that is, the retention in uncoated paper is very poor, and only when a pigmented coating layer is applied, capturing the polysaccharide material on the surface improves retention. The capture of the material, therefore, is related to the permeation roughness or, when coated, inversely in the coating coverage.
    [000137] The papers were subsequently calendered at 90 ° C at a load of 40 bar (4 MPa) adopting 4 passes through a single passage opening between rollers using a Voith calender - HB THERM Series 3. 3.Features 3.1.Retention
    [000138] Retention was essentially assessed visually using SEM images using a secondary electronic detector SEM LEO 435 VPi.
    [000139] For this purpose, the samples were mounted with tape on a standard aluminum sample holder and pre-coated with 50 nm gold.
    [000140] Figure 5 shows SEM images of a non-calendered base paper only (figure 5a) and coated with PM 1, that is, commercial cellulose gel (applied three times), without a pre-coating of mineral material ( figure 5b).
    [000141] As can be seen from figure 5b, although there is relatively good coverage per PM 1 (x3), there is still a clear definition of the underlying fiber and some penetration into the sheet by the gel.
    [000142] As can be seen from figure 6 showing SEM images of a non-calendered base paper coated with mineral material (rod 4) only (figure 6a) and coated with a triple layer of PM 1 on top of the material layer mineral (stem 4) (figure 6b), base paper fibers can no longer be identified, although cellulose fibril residues are clearly observed.
    [000143] Since the base paper is coated with the mineral material, it is no longer possible to see the individual base paper fibers and the coating of this with PM 1 shows complete retention.
    [000144] This clearly shows that the pre-coating of mineral material provides better coverage with the cellulose gel.
    [000145] The samples pre-coated with the mineral material layer (stem 4) and subsequently coated with PM 2 (x3) show some light and dark pieces in the SEM image (Figure 7a). The samples subsequently coated with PM 3 (x3) show a comparable result, but a more uniform coating (Figure 7b).
    [000146] In addition, cross-sectional images were taken (cf. figure 8), which showed that part of the fibrillar portion of PM 1 (3x) is kept out on top of the pre-coating layer (stem 4). The largest fraction of the fibers is kept on the surface while the nanogel components will be filtered in the mineral material coating structure and will be retained in it, thus forming a layered composite providing especially good resistance according to the beam I principle.
    [000147] As can be seen from figure 9, PM 3 (3x) on the other hand is absorbed directly in the absorptive layer, thus forming a nanocomposite in situ, equally. 3.2.Roughness
    [000148] Roughness of the coated surfaces was determined by surface profilometry using confocal laser scanning microscopy (CLSM or LSCM) using a Zeiss LSM 5 PASCAL, which is a technique for acquiring high resolution optical images at different depths . These depths in defined measured positions can be converted into a roughness value. CLSM analysis allows a comparison of the surface roughness of the samples to be made.
    [000149] CLSM roughness values are shown in figure 10. Each point is an average of 10 3D measurements calculated from the formula (the depth profile is measured at 10 different locations on the sheet, so the average of these 10 points is calculated ):
    where Rq is the mean square deviation. The double sum over Nx and Ny describes the number of pixels in the x- or y- direction, z is the surface height value and <z> is the average surface height value.
    [000150] It can be seen from figure 10 that the samples of the base paper have the roughest surfaces, that calendering gives a smoothing effect, in which the values for the applications of pre-coating of mineral material are all seen on the left of the figure 10, above the “base” label. Coating the base with mineral material gives a lower roughness value, and, again, calendering significantly decreases this value.
    [000151] Coating with a layer of PM 1 reduces the roughness when coated on the paper itself, as well as on the layer of the lightest pre-coated mineral material. Applying three layers of PM 1 (PM 1 x 3) has a greater effect, but here we also observe the greater effect of a pre-coating of heavier mineral material (triangular points). 3.3. Folding rigidity
    [000152] Samples were measured for bending stiffness using the beam method (Lorentzen & Wettre Bending Tester) in both uncalendered and calendered samples. Eight samples per sheet were measured. These were cut in the direction of the machine and four were measured at the top and four at the rear. The average of these eight measurements is reported.
    [000153] The stiffness in folding the samples of uncalendered and calendered papers pre-coated with increasing amounts of mineral material and coated with increasing amounts of PM 1, PM 2 and PM 3 was measured, the results of which are shown in figure 11.
    [000154] The folding stiffness values tend to the measured coating weights for the samples. Values also decrease with calendering, as would be expected. For the greatest improvement in rigidity, a higher pre-coating weight was required. This supports the need for better retention of the stiffening agent.
    [000155] Figures 12 a) to e) show very clearly the benefits of the present invention. The dashed lines form a reference in relation to the substrate, indicating the benefits of applying pre-coatings of the polysaccharide material. Pre-coating rod and paper 1 show more benefit for uncalendered samples. Pre-coating rod 2 and rod 3 show more benefit for calendered samples. 3.4. Permeability
    [000156] A stack of paper samples (approximately 70 cut into 1.5 x 1.5 cm2 sheets) is placed under a light overpressure, applied by an appropriate light weight to ensure that the sheets are laid flat, in a mold of PTFE with an internal diameter of 30 mm (available from Prüfmaschinen AG, Dietikon, Switzerland) and used to form cylindrical inlays. Subsequently, resin (Technovit 4000; Heraeus Kulzer GmbH, Wehrheim / Ts, Germany) is poured around it in order to embed the paper.
    [000157] The rapidly increasing viscosity of the chosen curing resin results in a penetration of approximately 1 mm locally at the outer limits of the sample. This depth of penetration is clearly visible due to the change in opacity at the edge of the sample and can therefore be calibrated. The open area of the porous sample, that is, that without resin, is evaluated so that the permeable cross sectional area can be established. The sample discs are placed on a disc containing the probe liquid in order to saturate the sample void network before placing it in the instrument. Hexadecane is used in experiments with density, p = 773 kgm-3 and viscosity, η = 0.0034 kgm 's1. The sample disc is then placed in a specially constructed pressure cell. The use of resin to embed samples allows rigid tightening and sealing of the sample in the pressure cell chamber. Gas overpressure is supplied by a bottle of nitrogen. The pressure cell is fixed on a microbalance and a PC samples the continuous flow in the balance data using specially developed software (available from Dr. C. J. Ridgway, Omya Development AG, CH 4665 Oftringen, Switzerland). Details of this measurement technique can be found in Ridgway et al. [Ridgway et al., 2003].
    [000158] The continuous flow can be expressed in terms of the Darcy permeability constant, k, as

    [000159] where áV (t) / at is defined as the volumetric flow or flow per unitary cross sectional area, A, ΔP is the pressure difference applied across the sample, ηc the viscosity of the liquid and Z is the length of the sample, in this case calculated as the number of sheets multiplied by the sheet thickness.
    [000160] The permeability of samples calendered with the highest pre-coating weights and gels 1 to 3 coated once or three times was measured. The results are shown in figure 13, and it can be seen that coating with PM 1 reduced the permeability considerably by closing the surface of the absorption pre-coating layer, forming a liquid (oil) barrier layer. PM 2 also reduced permeability. The application of PM 3 gives an almost sealing effect to the pre-coated layer resulting in a very low permeability value.
    权利要求:
    Claims (23)
    [0001]
    1. Process for making coated substrates, characterized by the fact that it comprises the steps of: - providing a substrate, - providing at least one mineral material, - providing a polysaccharide material comprising one or more polysaccharide (s), in which the polysaccharide material is in the form of a nanogel, - coating the substrate with at least one mineral material to obtain a pre-coating layer of mineral material, - coating the pre-coating layer of mineral material with the polysaccharide material comprising one or more polysaccharides ( s).
    [0002]
    2. Process according to claim 1, characterized by the fact that the substrate is selected from the group comprising papers and cardboard, such as calendered and uncalendered, coated and uncoated papers and cardboard; synthetic papers; non-woven products; packaging material; construction materials such as decorative paper and cardboard; and surface finishes.
    [0003]
    Process according to claim 1 or 2, characterized by the fact that said mineral material is selected from the group comprising pigments and / or mineral fillers, preferably from the group comprising precipitated calcium carbonate (PCC); natural ground calcium carbonate (GCC); calcium carbonate with modified surface; dolomite; baby powder; bentonite; clay; magnesite; white satin mica; sepiolite, huntite, diatomite; silicates; titanium dioxide; and mixtures thereof.
    [0004]
    4. Process according to claim 3, characterized by the fact that said mineral material is selected from calcium carbonates with modified surface, being a reaction product of natural calcium carbonate with carbon dioxide and one or more acid (s ), in which carbon dioxide is formed in situ by the acid treatment and / or is supplied by an external source.
    [0005]
    5. Process according to claim 3, characterized by the fact that said mineral material is selected from calcium carbonates with modified surface, being a reaction product of a pigment comprising PCC with H3O + ions and with at least one anion capable of forming water-insoluble calcium salts, said anion being solubilized in an aqueous medium to form a pigment slurry comprising reacted surface PCC, wherein said reacted surface PCC comprises an insoluble calcium salt at least partially crystalline from said anion formed on the surface of at least part of the PCC, and an excess of solubilized calcium ions is provided.
    [0006]
    Process according to any one of claims 1 to 5, characterized in that said mineral material has a median particle size of 0.01 to 50 pm, more preferably from 0.05 to 25 pm, even more preferably 0.1 to 10 pm, especially preferably from 0.2 to 5 pm, for example, 2.7 pm, particularly from 0.5 to 1.5 pm, for example, 0.8 pm.
    [0007]
    Process according to any one of claims 1 to 6, characterized in that said mineral material is supplied in the form of an aqueous suspension with a solids content is 10 to 80% by weight, is more preferably 20 to 75% by weight, even more preferably from 30 to 60% by weight, above all preferably from 40 to 55% by weight, for example, 50% by weight.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that said mineral material is supplied in combination with a binder, which is preferably selected from the group comprising styrene acrylate latex starch, proteins, butadiene latex styrene, polyvinyl alcohol, poly (vinyl acetate), and mixtures thereof.
    [0009]
    Process according to any one of claims 1 to 8, characterized by the fact that said one or more polysaccharide (s) comprised in said polysaccharide material is selected from the group comprising linear and branched polysaccharides such as cellulose, starch, chitin, chitosan , pectin, xanthan gum and dextran, and derivatives thereof.
    [0010]
    A process according to any one of claims 1 to 9, characterized by the fact that said polysaccharide material comprising one or more polysaccharide (s) is a nanofibrillar cellulose gel.
    [0011]
    Process according to claim 10, characterized in that said nanofibrillar cellulose gel is produced by fibrillating cellulose fibers in the presence of at least one filler and / or pigment until a gel is formed.
    [0012]
    12. Process according to either claim 10 or 11, characterized by the fact that said cellulose fibers are selected from those contained in pulps selected from the group comprising eucalyptus pulp, spruce pulp, pine cone pulp, beech pulp, pulp of hemp, cotton pulp, bamboo pulp, bagasse, as well as recycled and / or deinked pulp, and mixtures thereof.
    [0013]
    Process according to claim 11 or 12, characterized by the fact that said charge and / or pigment is selected from the group comprising precipitated calcium carbonate (PCC), natural ground calcium carbonate (GCC), calcium carbonate with surface modified; dolomite; baby powder; bentonite; clay; magnesite; white satin mica; sepiolite, huntite, diatomite; silicates; and mixtures thereof; and is preferably selected from the group of precipitated calcium carbonate with crystalline crystalline, argonitic calcitic structure, especially scalenehedral or rhombohedral precipitated calcium carbonate, ultra-thin discrete prismatic; natural ground calcium carbonate being selected from marble, limestone and / or chalk; and mixtures thereof, and preferably has a median particle size of 0.01 to 15 pm, preferably 0.1 to 10 pm, more preferably 0.3 to 5 pm, especially from 0.5 to 4 pm and above all preferably 0.7 to 3.2 pm, for example, 2 pm.
    [0014]
    Process according to any one of claims 10 to 13, characterized by the fact that said nanofibrillar cellulose gels are additionally combined with additional non-fibrillated fibers and / or at least one additional filler and / or pigment.
    [0015]
    Process according to claim 14, characterized in that said at least one additional charge and / or pigment has a median particle size of 0.01 to 5 pm, preferably 0.05 to 1.5 pm, more preferably 0.1 to 0.8 pm and above all preferably 0.2 to 0.5 pm, for example, 0.3 pm.
    [0016]
    16. Process according to any one of claims 1 to 15, characterized by the fact that the mineral material, as well as the polysaccharide material comprising one or more polysaccharide (s), is (are) coated, independently of each other, on the substrate and / or pre-coating of mineral material, respectively, in one or several layers.
    [0017]
    17. Process according to any one of claims 1 to 16, characterized by the fact that the total coating weight of the pre-coating of mineral material is from 2 grn2 to 50 gm-2, preferably from 5 grn2 to 40 gm-2, more preferably from 7 gm-2a to 30 gm-2, above all preferably from 8 gm-2a to 25 gm-2.
    [0018]
    18. Process according to any one of claims 1 to 17, characterized in that the total coating weight of the polysaccharide material is 0.5 gm-2a 20 gm-2, preferably 1 gm'2a 15 gm-2, more preferably 2 grn2all grn2, above all preferably 3 gm-2 to 5 gm-2.
    [0019]
    19. Coated substrate, characterized by the fact that it is obtained by the process as defined in any one of claims 1 to 18.
    [0020]
    20. Coated substrate according to claim 19, characterized in that the polysaccharide material can be partially or completely absorbed by the pre-coating of mineral material.
    [0021]
    21. Coated substrate according to claim 19 or 20, characterized in that a part of the polysaccharide material covers the mineral material, while the rest of the polysaccharide material is absorbed in the pre-coating of mineral material.
    [0022]
    22. Coated substrate according to any one of claims 19 to 21, characterized in that it is coated paper.
    [0023]
    23. Use of a substrate as defined in any of claims 19 to 22, characterized by the fact that it is in the form of packaging material, composites, barrier layers, printing surfaces, reinforcement aids and / or binders.
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    同族专利:
    公开号 | 公开日
    EP2529942A1|2012-12-05|
    TWI579429B|2017-04-21|
    RU2560349C2|2015-08-20|
    ES2712823T3|2019-05-14|
    PL2529942T3|2016-07-29|
    HRP20160193T1|2016-03-25|
    RU2013158317A|2015-07-20|
    EP2714415B1|2018-12-12|
    SI2714415T1|2019-04-30|
    TR201902476T4|2019-03-21|
    KR101706418B1|2017-02-13|
    WO2012163711A1|2012-12-06|
    CN103608185A|2014-02-26|
    CA2837912C|2017-01-03|
    US20140302337A1|2014-10-09|
    CA2837912A1|2012-12-06|
    UY34108A|2013-01-03|
    HUE028506T2|2016-12-28|
    EP2714415A1|2014-04-09|
    TW201250083A|2012-12-16|
    US9175442B2|2015-11-03|
    ES2563732T3|2016-03-16|
    KR20140017664A|2014-02-11|
    SI2529942T1|2016-03-31|
    BR112013030697A2|2016-12-06|
    CN103608185B|2016-08-31|
    EP2529942B1|2016-01-13|
    JP2014515439A|2014-06-30|
    DK2529942T3|2016-04-18|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-05-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11168651.5A|EP2529942B1|2011-06-03|2011-06-03|Process for manufacturing coated substrates|
    EP11168651.5|2011-06-03|
    US201161495453P| true| 2011-06-10|2011-06-10|
    US61/495453|2011-06-10|
    PCT/EP2012/059374|WO2012163711A1|2011-06-03|2012-05-21|Process for manufacturing coated substrates|
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