 process to manufacture structured material, use of nanofibrillar cellulose gels
专利摘要:
PROCESS FOR MANUFACTURING STRUCTURED MATERIAL, USE OF NANOFIBRILLARY CELLULOSE GELS, AND, STRUCTURED MATERIAL A process for manufacturing structured material by providing cellulose fibers and at least one filler and / or pigment, combining cellulose fibers and at least one filler and / or pigment, fibrillar the cellulose fibers in the presence of at least one filler and / or pigment until a gel is formed, subsequently providing additional non-fibrillated fibers and combining the gel with the additional non-fibrillated fibers. 公开号:BR112012027635B1 申请号:R112012027635-2 申请日:2011-04-26 公开日:2020-12-08 发明作者:Patrick A. C. Gane；Michel Schenker；Ramjee Subramanian；Joachim Schoelkopf 申请人:Omya International Ag； IPC主号:
专利说明:
The present invention concerns a process for the production of structured materials as well as the structured materials obtained by this process. In many technical fields, mixtures of materials are used to control or improve certain properties of a product. Such mixtures of materials can be, for example, in the form of undefined mixtures, or in the form of composite structures. A composite material is basically a combination of two or more materials, each of which retains its own distinctive properties. The resulting material has characteristics that are not characteristic of the components in isolation. Most commonly, composite materials have a volume phase, which is continuous, called the matrix; and a dispersed, non-continuous phase called reinforcement. Some other examples of basic composites include concrete (cement mixed with sand and aggregate), reinforced concrete (steel rebar in concrete) and fiberglass (glass fibers in a resin matrix) ). The following are some of the reasons why composites are selected for certain applications: -High strength to weight ratio (high tensile strength of low density) -Resistance to high lowering -High tensile strength at high temperatures -High hardness Typically, reinforced materials are strong, while the matrix is usually a flexible or resistant material. If the composite is designed and manufactured correctly, it combines with the strength of the reinforcement with the hardness of the matrix to achieve a combination of desirable properties not available in any conventional simple material. For example: polymer / ceramic composites have a larger modulus than the polymer component, but are not as fragile as ceramics. Since the reinforcement material is of primary importance in the strengthening mechanism of a composite, it is convenient to classify the composites according to the characteristics of the reinforcement. The following three categories are commonly used: a) “fiber reinforced”, where the fiber is the component that carries the primary load. b) “reinforced particle”, in which the charge is formed by the matrix and the particles. c) “strengthened dispersion”, in which the matrix is the component that carries the largest load. d) “structural composites”, in which the properties depend on the constituents and the geometric design. Generally, the strength of the composite depends mainly on the amount, combination and type of fiber (or particle) reinforced in the resin. In addition, the composite is often formulated with fillers and additives that change processing and performance parameters. Thus, in the prior art, it is generally known to combine different materials in order to obtain materials having modified properties or being able to control certain properties of a material in which they are applied and there is a continuing need for such materials allowed for control under measurement of the characteristics of the materials, as well as in relation to their cost efficiency and environmental compliance. An important field in this regard is the production of structured material and its properties. An example of structured materials is paper, in the manufacture in which a number of different materials are combined, each of which can positively or negatively influence the properties of other components, or the final paper. One of the most common groups of additives in the field of paper making and finishing are fillers having several advantageous functions on paper. For example, fillers are used for reasons of opacity or to provide a smooth surface to fill the voids between the fibers. There are, however, limitations regarding the amount of fillers, which can be added to the paper, as increasing the quantities filled in conventional paper leads to an inverse connection between strength and optical properties. In this way, conventional paper can contain a certain amount of fillers, but if the content of the filler is much greater, the mechanical properties of the paper will significantly decrease. Several methods have been proposed to improve its relationship and to produce a highly filled paper having good optics as well as mechanical properties, but there is still a need for the processes for making the paper allowing the contents of the larger filler as commonly used without essentially impairing the paper strength. The search for methods to control the properties of structured materials or products containing such structured materials, it was observed that special nanofibrillary cellulosic gels comprising calcium carbonate can be useful. Cellulose is a structural component of the primary cell wall of green plants and is the most common organic compound on earth. And of great interest in many applications and industries. Cellulose pulp as a raw material is processed out of wood or plant stems such as hemp, flax and manila. Pulp fibers are built mainly from cellulose and other components organic (hemicellulose and lignin). The cellulose macromolecules (1-4 glycosidic compounds linked by the fl-D-Glucose molecules) are linked together by the hydrogen bond to form a so-called primary fibril (micelle) that has crystalline and amorphous domains. of 55) form a so-called microfibril. Around 250 of these microfibrils form a fibril. The fibrils are arranged in different layers (which may contain lignin and / or hemicellulose) to form a fiber. Individual fibers are linked together by lignin as well. When the fibers become refined under applied energy they become fibrillated as the cell walls are broken and removed in the linked bands, that is, in the fibrils. If this break is continued, separating the fibrils from the fiber body, it releases the fibrils. The breakdown of fibers in microfibrils is referred to as “microfibrillation”. This process can be continued until there are no left fibers and only the nanosize (thickness) fibrils remain. If the process continues and breaks these fibrils into smaller fibrils, they eventually become cellulose fragments or nanofibrillar gels. Depending on when this last step is taken, some nanofibrils may remain between the nanofibrillar gels. The breakdown of primary fibrils can be referred to as “nanofibrillation”, where a smooth transition between the two regimes can occur. The primary fibrils form a gel in a watery environment (stable target network of primary fibrils) that can be referred to as a “nanofibrillar gel”. The gel called from nanofibril as can be considered to contain nanocellulose. Nanofibrillary gels are desirable when they usually contain many thin fibrils, considered to be made up partly of nanocellulose, showing a stronger bonding potential alone, or in any other material present, than fibrils that are not of this modofin or not exhibit the nanocellulosic structure. From unpublished European Patent Application No. 09 156 703.2, nanofibrillar cellulose gels are known. However, there is no knowledge as to their effects on structured materials. It was observed that such nanofibrillar cellulose gels can be useful in the production and control, especially of the mechanical properties, of structured materials. In this way, the above problem is solved by a process for the manufacture of structured materials, which is characterized by the following steps: a) supplying cellulose fibers; b) provide at least one filler and / or pigment; c) combining cellulose fibers from step a) and at least one filler and / or pigment from step b); d) fibrillar the cellulose fibers in the presence of at least one filler and / or pigment until a gel is formed; e) provide additional non-fibrillated fibers; f) combining the gel from step d) with the fibers from step e). Nanofibrillary cellulose in the context of the present invention means fibers, which are at least partially breaking primary fibrils. If these primary fibrils are in an aqueous environment, a gel (target stable network of primary fibrils considered at the limit of clarity to be essentially nanocellulose) is formed, which is indicated as a “nanofibrillar gel”, in which it is a smooth transition between nano fibers and nanofibrillary gel, which comprises nanofibrillary gels containing a variation in the length of nanofibrils, all of which are comprised of the term nanofibrillary cellulose gels according to the present invention. In this regard, fibrillar in the context of the present invention means any process that predominantly breaks the fibers and fibrils along its long axis resulting in a decrease in the diameter of the fibers and fibrils, respectively. According to the process of the present invention, fibrillation of cellulose fibers in the presence of at least one filler and / or pigment provides a nanofibrillar cellulose gel. Fibrillation is performed until the gel is formed, in which the formation of the gel is verified by monitoring the viscosity depending on the cut rate. In the step-by-step increase in the cut rate a certain curve reflects a decrease in viscosity is obtained. If, subsequently, the cut rate is reduced step by step, the viscosity increases again, but the corresponding values in at least part of the cut rate range as zero cut methods are lower than when the increase in the cut rate cut, graphically expressed by hysteresis manifests when viscosity is plotted against a cut rate. As soon as this behavior is observed, a nanofibrillar cellulose gel according to the present invention is formed. Further details regarding the production of the nanofibrillar cellulose gel can be taken from unpublished European Patent Application No. 09 156 703. The cellulose fibers, which can be used in the process of the present invention can be such contained in the thermomechanical, chemiomechanical, mechanical, chemical and natural pulps. Especially useful are the pulps selected from the group comprising eucalyptus pulp, spruce pulp, pine 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 emitted from the step of recycling the material comprising cellulose fibers. In this way, the pulp can also be recycled and / or depigmented pulp. The size of the cellulose fibers is not critical at first. In general, any commercially available and processed fibers in the device used for their fibrillation are useful in the present invention. Depending on their origin, cellulose fibers can have a length of 50 mm at 0.1 pm. Such fibers, as well as having 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 in the present invention, where also shorter and longer fibers long ones can be useful. It is advantageous for use in the present invention that the cellulose fibers from step a) 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 from 0.25 to 10% by weight, even more preferably from 0.5 to 5% by weight, especially from 1 to 4% by weight, more preferably 1.3 to 3% by weight, for example, 1.5% by weight. The additional non-fibrillated fibers from step e) are preferably selected from the cellulose fibers as defined above, too. However, other non-fibrillated fibers can also be advantageously used in the process of the present invention. At least one filler and / or pigment is selected from the group comprising precipitated calcium carbonate (PCC); natural ground calcium carbonate (GCC); surface modified calcium carbonate; dolomite; baby powder; bentonite; clay; magnesite; white satin, sepiolite, huntite, diatomite; silicates and mixtures thereof. Precipitated calcium carbonate, which may have a valeritic, calcified or aragonitic crystal structure and / or natural crushed calcium carbonate, which can be selected from marble, limestone and / or chalk, are especially preferred. In a specially designed form, the use of precipitated rhombohedral, scalenohedral or prismatic ultrafine calcium carbonate may be advantageous. Fillers and / or pigments can be supplied in the form of a powder, although these 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 they are a pumpable liquid. In a preferred embodiment, filler and / or pigment particles from step b) have an average 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 more preferably from 0.7 to 3.2 pm, for example, 2 pm. For determining the weight of the average particle size d5o, for particles having a d50 greater than 0.5 pm, a Sedigraph 5100 device from Micromeritics, USA was used. The measurement was performed in an aqueous solution of 0.1% by weight of Na4P2O7. The samples were dispersed using a high speed shaker and ultrasound. For the determination of the average particle size volume for particles having a d50 <500 nm, a Malvem Zetasizer Nano ZS from the company Malvern, UK was used. The measurement was performed in an aqueous solution of 0.1% by weight Na4P2O7. The samples were dispersed using a high speed shaker and ultrasound. In view of the advantageous effect of the addition of nanofibrillar cellulosic gels in relation to the properties of mechanical paper still in the filler and / or high pigment contents, in an especially preferred embodiment, before, during or after the addition of additional fibers in step e ), but after step d) and before step f), at least one additional filler and / or pigment are added. This at least one additional filler and / or pigment may be the same or a different filler and / or pigment from step b) selected from the group comprising precipitated calcium carbonate (PCC); natural ground calcium carbonate (GCC); surface modified calcium carbonate; dolomite; baby powder; bentonite; clay; magnesite; satin white, sepiolite, huntite, diatomite; silicates and mixtures thereof. Precipitated calcium carbonate, which may have a valeritic, calcitic or aragonitic crystal structure and / or natural crushed calcium carbonate, which can be selected from marble, limestone and / or chalk, are especially preferred. In a special embodiment, the use of precipitated rhombohedral, scalenohedral or prismatic ultrafine discrete calcium carbonate can be advantageous. These additional fillers and / or pigments can also be supplied in the form of a powder, although these 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 they are a pumpable liquid. It has, however, been shown to be particularly advantageous if at least one additional filler and / or pigment is a product preferably thin in terms of particle size and especially preferably comprises at least a fraction of particles having an average diameter d50 in the nanometer range, contrary to pigments and / or fillers used in forming the gel, which are otherwise thick. Thus, it is still preferred that at least one additional filler and / or pigment particle has an average particle size of 0.01 to 5 pm, preferably 0.05 to 1.5 pm, more preferably 0.1 to 0.8 pm and more preferably 0.2 to 0.5 pm, for example, 0.3 pm, where a particle size is determined as mentioned above. Any of the fillers and / or pigments used in the present invention 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 ethers based on, for example, acid acrylic, methacrylic acid, maleic acid, fumaric acid, itaconic acid, for example, acrylamide or acrylic esters such as methyl methacrylate or mixtures thereof; alkyl polyphosphates, phosphonic, citric and tartaric acids or their salts or esters; or mixtures of these. The combination of fibers and at least one filler and / or pigment from step b) can be accomplished by adding the filler and / or pigment to the fibers in one or several steps. Also, the fibers can be added to the filler and / or pigment in one or several steps. The fillers and / or pigments from step b) as well as the fibers from step a) can be added completely or in portions before or during the fibrillar step. However, addition before fibrillation is preferred. During the fibrillation process, the size of fillers 10 and / or pigments as well as the size of the fibers can change. Preferably, the weight ratio of fibers to fillers and / or pigments from step b) on a dry weight basis is 1:33 to 10: 1, more preferably 1:10 to 7: 1, even more preferably 1 : 5 to 5: 1, typically from 1: 3 to 3: 1, especially from 1: 2 to 2: 1 and more preferably from 151: 1.5 to 1.5: 1, for example, 1: 1. The dosage of the filler and / or pigment in step b) can be critical. If there is not much of the filler and / or pigment, it can influence the formation of the gel. Thus, if no gel formation is observed in the specific combination, it must be necessary to reduce the amount of the filler and / or pigment. In addition, 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 fibrillar, as this ideally results in the expansion of the fibers facilitating fibrillation. The expansion of the fiber can be facilitated by storage at the increased pH, as well as by the addition of similar cellulose solvents, for example, copper (II) ethylenediamine, sodium-iron tartrate or lithium-chlorine / dimethylacetamine, or by any other method known in the art. Fibrillar is carried out using any useful device, therefore. Preferably the device is a homogenizer. This can also be an ultrathin friction crusher such as a Supermasscolloider from Masuko Sangyo Co. Ltd, Japan or one as described in U.S. 6,214,163 or U.S. 6,183,596. Suitable for use in the present invention are any commercially available homogenizers, especially high pressure homogenizers, in which suspensions are compressed under high pressure through a restricted opening, which may comprise a valve and are discharged from the pressure restricted opening. high against a hard impact surface directly in front of the restricted opening, thereby 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 extending around the annular valve opening. An example for a homogenizer, which can be used in the present invention is Ariete NS2006L by GEA Niro Soavi. However, inter alia, such homogenizers such as APV Gaulin series, HST HL series or Alfa Laval SHL series can be used. In addition, devices such as ultrathin friction crushers, for example, a Supermasscolloider, can be advantageously used in the present invention. The structured material can be produced by mixing the nanofibrillary cellulosic gel and additional non-fibrillated fibers, as well as, optionally, additional filler and / or pigment and subsequently remove water from the combination to form a base structure such as, for example, a foil. base paper. In this regard, generally any commonly used method of removing water known to that person skilled in the art can be used, such as, for example, heat drying, pressure drying, vacuum drying, freeze drying, or drying under the supercritical conditions. The dewatering step can be carried out on known devices such as at a filter pressure, for example, as described in the Examples. Generally, other methods that are well known in the field of molding aqueous systems can be applied to obtain the inventive composites. In a special embodiment, additional non-fibrillated fibers can be supplied in the form of a fiber structure made such as a fiber net and to combine this structure with the gel, as well as, optionally, with filler and / or additional pigment , resulting in at least 10 partial coating of the fiber structure by the gel. Generally, the structured material, as well as any layers of the fiber structure, for example, fiber net and gel, in this respect can vary in thickness. For varying the thickness of structured materials and, optionally, the different layers of the resulting structured material, allowing control of the material properties as well as the product in which the material is applied. Thus, the material structured according to the present invention can be as thin as a film, can have a thickness that is typically seen in conventional papers, but can also be as thick as sheets and can still be in the form of compact blocks , inter alia depending on the fiber and gel ratio. For example, in the production of paper, it is advantageous that the structured material and the layers thereof, respectively, are instead thin. Thus, it is preferred that a layer of fiber has a thickness of 0.02 mm to 0.23 mm and one or more layers of gel have a thickness of 0.005 mm to 0.15 mm, where the total thickness of the structured material is 0.05 mm to 0.25 mm. Regarding the applications of the paper, it was observed that the combination of the cellulosic nanofibrillar gel with the fibers for the formation of the paper has a considerable influence on the properties of the paper with respect to the filler load. Thus, it is an especially preferred embodiment that the structured material is paper. In this regard, adding only a minimal amount of nanofibrillar cellulosic gel is necessary. The amounts of the nanofibrillary cellulosic gel in paper applications expressed by the cellulosic content of the gel in relation to the additional non-fibrillated fibers (dry / dry weight basis) can be about 0.5 to 20% by weight, preferably 1 to 15% by weight, 2 to 10% by weight, 3 to 6% by weight, for example, 5% by weight. In this way, it is possible to form a sheet of paper that comprises the gel on the base paper and / or on a layer coating of the fiber net resulting in the layer structures of the paper-forming fibers and gels. Papers that can be manufactured and improved with respect to increasing filler quantities by the process of the present invention are papers, which are preferably selected from, but not limited to, printing and writing paper, as well as newspapers. In addition, by the process of the present invention it is still possible to introduce the filler into the tissue paper. Thus, by the process of the present invention more efficient use of low grade fibers is achieved. By adding nanofibrillary cellulosic gel to base suppliers containing fibers deficient in granting strength to the product based on the final fiber, the strength of the paper can be improved. With respect to the total content of filler and / or pigment in the paper, it is especially preferred that the filler and / or pigments are present in an amount of 1% by weight to 60% by weight, preferably from 5% by weight to 50% in weight, more preferably from 10 to 45% by weight, even more preferably from 25% by weight to 40% by weight, especially from 30 to 35% by weight on a dry weight basis of the structured material. The use of nanofibrillary cellulose gels as defined above for the production of structured material is an additional aspect of the invention, in which the gel is combined with the additional non-fibrillated fibers and the resulting combination is devoid of water. Another aspect of the present invention is the structured material obtained by the process according to the invention, or by the use of nanofibrillar cellulose gels for the production of structured material as mentioned. Due to their mechanical strength properties, nanofibrillar cellulose gels can be advantageously used in applications such as composites of materials, plastics, paints, rubbers, concrete, ceramics, panels, supports, plates and films, coatings and extrusion profiles, adhesives , food or wound healing applications. The figures described below and the examples and experiments, serve to illustrate the present invention and should not be restricted in any way. Description of figures: Figure 1 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to rupture extensions. Figure 2 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to the extent of the break. Figure 3 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to the tensile index. Figure 4 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to the elasticity modules. Figure 5 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to the extent of cut development. Figure 6 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to the internal connection. Figure 7 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to opacity. Figure 8 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to dispersion. Figure 9 shows a comparison of the prior art paper samples and according to the invention containing GCC as a filler with respect to absorbance. Figure 10 shows a comparison of prior art paper samples and according to the invention containing GCC as a filler with respect to air resistance. Figure 11 shows a comparison of the paper samples of the prior art and according to the invention containing PCC as a filler with respect to rupture extensions. Figure 12 shows a comparison of the prior art paper samples and according to the invention containing PCC as a filler with respect to the extent of the break. Figure 13 shows a comparison of the prior art paper samples and according to the invention containing PCC as a filler with respect to the tensile index. Figure 14 shows a comparison of the prior art paper samples and according to the invention containing PCC as a filler with respect to cutting development work. Figure 15 shows a comparison of the prior art paper samples and according to the invention containing PCC as a filler with respect to the extent of internal bonding. Figure 16 shows a comparison of the prior art paper samples and according to the invention containing PCC as a filler with respect to opacity. Figure 17 shows a comparison of the prior art paper samples and according to the invention containing PCC as a filler with respect to light scattering. Figure 18 shows a comparison of the prior art paper samples and according to the invention containing PCC as a filler with respect to air permeability. Figure 19 shows a comparison of the prior art paper samples and according to the invention containing PCC as a filler with respect to Bendtsen's roughness. EXAMPLES In the context of the present invention the following terms are used: -solid content [% by weight] means total solids, ie any non-volatile material (essentially pulp / cellulose and filler) -cellulosic solid content [% by weight] means the fraction of cellulosic material only in the total mass, ie pulp before fibrillation, or nanocellulose after fibrillation. The valve can be calculated using total solids content and the reason for filling the pulp. The levels of addition (ratios) of the gels in the compositions (for example, paper samples): any percentage to be understood as% by weight of the dry cellulosic content (see above) in the total mass of the composition (the paper sample is 100% in Weight). Density, thickness and volume were determined in accordance with ISO 534, the weight was determined in accordance with ISO 536, Climate control was carried out in accordance with ISO 187: 1997. 1. Nanofibrillary cellulosic gel with standard GCC fillers Material Filler (gel): -Omyacarb® 1 AV (OC 1 AV) (dry powder) -Omyacarb * 10 AV (OC 10 AV) (dry powder) Both available from Omya AG; Fine calcium carbonate powder, manufactured from high purity, white marble; The weight of the average particle size is 1.7 or 10 pm, respectively, measured by Malvern Mastersizer X. -Hydrocarb® 60 AV (HC 60 AV) (dispersed product) Available from Omya AG: Natural crushed calcium carbonate (marble) , selected, rhombohedral particle shape, microcrystalline of high clarity in the form of a pre-dispersed paste. The weight of the d4 average particle size is 1.6 pm, measured by Sedigraph 5100. Suspension solids = 78% by weight. Pulp (gel): Dry pine surfaces, gloss: 88.19%, TCF bleached Dry eucalyptus, gloss: 88.77%, TCF bleached Pine not dry, gloss: 88.00% Filler (paper samples): -Hydrocarb ® HO - ME (dispersed product) Available from Omya AG; Naturally crushed calcium carbonate (marble), selected, rhombohedral particle shape, microcrystalline of high clarity in the form of a pre-dispersed paste (62% solids content by weight); The weight of the average particle size d50 is 0.8 pm as measured by Sedigraph 5100. Pulp (paper samples): -80% by weight of short fiber (birch) / 20% by weight of long fiber (pine), freedom: 23 ° SR (Brightness: 88.53%) 5 Retention aid: Polyimin 1530 (available from BASF) Gel formation The gels were processed with an ultra-friction crusher (Supermasscolloider from Masuko Sangyo Co. Ltd, Japan (Model MKCA 6-2) with mounted silicon carbide stones having a grain class of 46 (grain size 297 - 420 pm) The dynamic 0 point was adjusted as described in the manual released by the supplier (the zero point is defined as the touch point of the stones, so that the gap between the stones is 0 mm). 1500 rpm. The suspensions to be fibrillated were prepared as follows: 80 g of the dry surface pulp was cut into 40 x 40 mm pieces and 3920 g of tap water were added. In the case where the wet pulp was used, 800 g of pulp (solids content: 10% by weight) was mixed with 3200 g of tap water. Each of the suspensions was agitated in a 10 dm3 bucket at 2000 rpm using a 70 mm diameter disk. The suspensions were stirred for at least 10 minutes at 2000 rpm. First, the pulp was disintegrated by passing it twice through the crusher with an open stone slit (0 pm). Subsequently, the stone slit was narrowed to -200 pm to fibrillate the pulp in two passes. The filler (according to table 1) was added to this fibrillated pulp suspension and this mixture was crushed by circulating it three times with a stone slit from -300 to -400 pm. Table 1: Paper sample formation 60 g dry weight of a wood fiber paste made of 80% by weight of birch and 20% by weight of pine, with an SR value of 23 ° and the amount according to the nanocellulosic gel (see 5 table 2 ) is diluted in 10 dm3 of tap water. The filler (Hydrocarb®HO-ME) is added in an amount so as to obtain the desired total filler content based on the final paper weight (see table 2). After 15 minutes of stirring and following the addition of 0.06% dry weight, relative to the dry weight of the paper, of a polyacrylamide retention aid, 10 a blade with a weight of 80 g / m2 is formed using a former sample paper type Rapid-Köthen. Each slide was dried using the Rapid-Köthen dryer. The filler content is determined by the combustion of a dry sample of four in a silencing furnace heated to 570 ° C. After combustion is completed, the residue is transferred in a desiccator to cool. When the ambient temperature is reached, the weight of the waste is measured and the mass is reported to the initially measured weight of the four dry paper samples. Table 2: Paper sample testing Usually, the addition of fillers, while improving the optical properties, preferably has a destabilizing effect on the mechanical properties of a paper blade. However, as can be taken from the following experiments, the mechanical properties of a gel containing papers are comparable or better than those of paper samples not containing the gel according to the invention, even in the larger filling contents and in the same or better optical properties . In addition, paper samples have significantly higher air resistance, which is an advantage over ink and printing penetration. The paper samples were tested and characterized as follows: 1..Mechanical properties The mechanical properties of the paper samples according to the invention were characterized by their rupture extension, rupture stress, tensile index, E module, cutting development work and internal bonding. The extent of rupture, stress at break, tensile index and modulus E (modulus of elasticity) of the paper samples were determined by the tensile test according to ISO 1924-2. Cutting development work was determined according to DIN 53115. The internal connection was determined according to SCAN-P80: 98 / TAPPI T 541 om. As can be seen from Figures 1, 2, 3, 4, 5 and 6, rupture extension, rupture tension, tensile index, E module and internal bond values of the comparative paper samples N °. 1 and 2 decrease with increasing filler content. Looking at the inventive paper samples, it can be seen that any of the paper samples No. 3, 4, 6, 8 and 9 containing 30% by weight filler, plus the additional gel, has better rupture extensions, rupture stress, tensile index, module E, cutting development work and internal bonding properties than comparative paper sample no. two. Still, the paper samples N °. 5 and 7 containing filler in an amount as high as 50% by weight and gel according to the invention has better or comparable breaking length, breaking stress, tensile index, E module, cutting development work and internal bonding properties than comparative paper samples having a much lower filler content. 2.Optical properties The optical properties of the paper samples according to the invention were characterized by their opacity, light scattering and light absorption. The opacity of the paper samples was determined according to DIN 53146. The dispersion and absorbance were determined according to DIN 54500. As can be seen from Figures 7, 8 and 9, opacity (determined as opacity reduced by weight), light scattering and light absorbance of comparative paper samples No. 1 and 2 increases with increasing filler content. Looking at the inventive paper samples, it can be seen that any of the paper samples No. 3, 4, 6, 8 and 9 containing 30% filler weight, plus the additional gel, have better opacity or comparable, light scattering and light absorbing properties than the comparative paper sample No. two. Paper samples No. 5 and 7 containing filler in an amount as high as 50% by weight and gel according to the invention has better opacity, light scattering and light absorbing properties than comparative paper samples having a lower filler content. 3.Air resistance Air resistance was determined in accordance with ISO 5636-1 / -3. As can be seen from Figure 10, air resistance of comparative paper samples No. 1 and 2 are around or slightly increased with increasing filler content. Looking at the inventive paper samples, it can be seen that any of the paper samples No. 3, 4, 6, 8 and 9 containing 30% filler weight, plus the additional gel, has significantly greater air resistance than comparative paper samples N °. 2. In this regard, paper samples No. 5 and 7 containing filler in an amount as high as 50% by weight and gel according to the invention has the greatest air resistance. 2. Nanofibrillar cellulosic gel with standard PCC fillers Material Filler (gel): -Hydrocarb® 60 AV (HC 60 AV) (dispersed product) Available from Omya AG: Natural crushed calcium carbonate (marble), selected, rhomboid particle shape, high clarity microcrystalline in the form of a pre-dispersed paste. The weight of the average particle size d50 is 1.6 pm, measured by Sedigraph 5100. Suspension solids = 78%. Pulp (gel): Dry pine surfaces, brightness: 88.19%; TCF targeted Dry, shiny eucalyptus; 88.77%; Targeted TCF Filler (paper samples): -PCC (precipitated calcium carbonate) Available from Omya AG; scalenohedral particle shape with a d5o of 2.4 pm measured by Sedigraph 5100. Specific surface area: 3.2 m2 / g; Suspension solids: 20% by weight; pH: 8. Pulp (paper samples): -100% refined eucalyptus at 30 ° SR (TCF bleaching sequence; Brightness = 88.7%) Retention aid: Polyimin 1530 (available from BASF) Gel formation The gels were processed with an ultrathin friction crusher (Supermasscolloider from Masuko Sangyo Co. Ltd, Japan (Model MKCA 6-2) with silicon carbide stones assembled having a grain class of 46 (grain size 297 - 420 pm) The dynamic 0 point was adjusted as described in the manual released by the supplier (the zero point is defined as the touch point of the stones, so that the gap between the stones is 0 mm). 1500 rpm. The suspensions to be fibrillated were prepared as follows: 80 g of the dry surface pulp was cut into 40 x 40 mm pieces and 3920 g tap water were added. The pulp surfaces were wetted overnight in water. The next day, the suspensions were stirred in a 10 dm1 bucket at 2000 rpm using a 70 mm diameter dissolving disc. The suspensions were stirred for at least 10 minutes at 2000 rpm. First, the pulp was disintegrated by passing it twice through the crusher with an open stone slit (0 pm). Subsequently, the stone slit was narrowed to -200 pm to fibrillate the pulp in two passes. The filler (according to table 3) was added to this fibrillated pulp suspension and this mixture was crushed by circulating three times with a stone slit from -300 to -400 pm.Table 3: Paper sample formation 60 g dry eucalyptus pulp with an SR value of 30 ° and the amount according to the nanocellulosic gel (see table 4) is diluted in 10 dm3 of tap water. The filler (PCC FS 270 ET) is added in an amount so as to obtain the desired total filler content based on the final paper weight (see table 4). After 15 minutes of stirring and following the addition of 0.06% dry weight, relative to the dry weight of the paper, of a polyacrylamide retention aid, a slide with a weight of 80 g / m2 is formed using sample of Rapid- Kõthen type paper. Each slide was compressed wet for 1 minute at 0.42 bar (42 kPa) and dried using the Rapid-Kõthen dryer. The filler content is determined by the combustion of a dry paper sample four in a silencing furnace heated to 570 ° C. After the combustion is finished, the residue is transferred in a desiccator to cool. When the ambient temperature is reached, the weight of the residue is measured and the mass is reported to the initially measured weight of the four dry paper sample. Table 4: Paper sample testing As in the case of paper samples, combining nanofibrillar cellulosic gel with standard GCC fillers, comparable effects on mechanical, optical and penetration and printing properties were observed when the filler added to the paper samples was standard PCC run filler. Thus, the mechanical properties as well as penetration and printing properties (expressed by the air permeability of the respective paper samples) must be significantly improved in the comparable optical properties. The paper samples were tested and characterized as follows: 1. Mechanical properties The mechanical properties of the paper samples according to the invention were characterized by their rupture extent, tear strength, tensile index, cutting development work and internal bonding. The extent of rupture, stress at break and tensile index of the paper samples were determined by the tensile test according to ISO 1924-2. The cutting development work was determined according to DIN 53115. The internal connection was determined according to SCAN-P80: 98 / TAPPIT 541 om. As can be seen from Figures 11, 12, 13, 14 and 15, rupture extension, rupture tension, tensile index, cut development work and internal connection values of the comparative paper samples N °. 10-13 essentially decreases with increasing filler content. Looking at the inventive paper samples, it can be seen that any of the paper samples No. 14 to 20 containing corresponding amounts of the filler, plus the additional gel, have better breaking lengths, breaking strength, tensile index, cutting development work and internal bonding properties than the corresponding comparative paper samples. 2.Optical properties The optical properties of the paper samples according to the invention were characterized by their opacity and light scattering. The opacity of the paper samples was determined according to DIN 53146. The light scattering was determined according to DIN 54500. As can be seen from Figures 16 and 17, the opacity and light scattering of comparative paper samples No. 10—13 increases with increasing filler content. Looking at the inventive paper samples, it can be seen that any of the paper samples No. 14-20 containing corresponding amounts of the filler, plus the additional gel, has better opacity or comparability and light scattering properties than the corresponding comparative paper samples. 3.Air permeability Air permeability was determined according to ISO 5636-1 /-3. As can be seen from Figure 18, air permeability of comparative paper samples N °. 10-13 is around it or slightly increased with increasing filler content. Looking at the inventive paper samples, it can be seen that any of the paper samples No. 14-20 containing corresponding amounts of the filler, plus the additional gel, has significantly less air permeability than the corresponding comparative paper samples. 4. Bendtsen's roughness Bendtsen's roughness was determined in accordance with ISO 8791-2. A lower surface roughness is an advantage for the calendering properties. A lower surface roughness means that less pressure has been applied for calendering. As can be seen from Figure 18, Bendtsen's roughness of the comparative paper samples No. 10 - 13 decreases with increasing filler content. However, looking at the inventive paper samples, it can be seen that any of the paper samples N °. 14-20 containing corresponding amounts of the filler, plus the additional gel, have a comparable or lesser Bendtsen roughness than the corresponding comparative paper sample and thus provides a lower surface roughness.
权利要求:
Claims (18) [0001] 1. Process to manufacture structured material, characterized by the fact that it is distinguished by the steps of: (a) supplying cellulose fibers; (b) provide at least one filler and / or pigment; (c) combining the cellulose fibers from step a) and at least one filler and / or pigment from step b); (d) fibrillar the cellulose fibers in the presence of at least one filler and / or a pigment until there are no fibers and a nanofibrillar gel of only primary fibrils is formed in an aqueous environment, and that the formation of the gel is verified by monitoring the mixture viscosity depending on the shear rate, where the decrease in the viscosity of the mixture by step by step increase in the shear rate is stronger than the corresponding increase in viscosity by the subsequent step by step decrease in the shear rate during at least part of the cut rate range when the cut approaches zero (e) provide additional non-fibrillated fibers; (f) combining the gel from step d) with the fibers from step e). [0002] 2. Process according to claim 1, characterized by the fact that the combination of step f) is dewatered in dewatering step g). [0003] 3. Process according to claim 1 or 2, characterized by the fact that the cellulose fibers of steps a) and / or e) are independently selected from those contained in pulps selected from the group comprising eucalyptus pulp, spruce pulp , pine pulp, beech pulp, hemp pulp, cotton pulp, bamboo pulp, bagasse, as well as recycled and / or depigmented pulp and mixtures thereof. [0004] Process according to any one of claims 1 to 3, characterized in that the cellulose fibers of step a) are supplied in the form of a suspension, preferably having a solids content of 0.2 to 35% by weight , more preferably from 0.25 to 10% by weight, even more preferably from 0.5 to 5% by weight, especially from 1 to 4% by weight, more preferably from 1.3 to 3% by weight, for example, 1.5% by weight. [0005] Process according to any one of claims 1 to 4, characterized in that the filler and / or pigment of step b) is selected from the group comprising precipitated calcium carbonate (PCC), natural crushed calcium carbonate (GCC ), surface-modified calcium carbonate; dolomite; baby powder; bentonite; clay; magnesite; SATIN WHITE; sepiolite, huntite, diatomite; silicates and mixtures thereof, and is selected from the group of precipitated calcium carbonate having a valeritic, calcitic or aragonitic crystalline structure, especially prismatic, scalenoed or rhombohedral precipitated calcium carbonate, distinct from the ultrafine; natural crushed calcium carbonate being selected from marble, limestone and / or chalk and mixtures of these. [0006] Process according to any one of claims 1 to 5, characterized in that the filler and / or pigment particles of step b) have a median particle size of 0.01 to 15 gm, preferably 0.1 to 10 gm, more preferably from 0.3 to 5 gm, especially from 0.5 to 4 gm and more preferably from 0.7 to 3.2 gm, for example, 2 µm. [0007] Process according to any one of claims 1 to 6, characterized by the fact that before, during or after the addition of additional fibers in step e), but after step d) and before step f), at least one additional filler and / or pigment are added, which are selected from the group comprising precipitated calcium carbonate; natural crushed calcium carbonate; surface modified calcium carbonate; dolomite; baby powder; bentonite; clay; magnesite; SATIN WHITE; sepiolite, huntite, diatomite; silicates and mixtures thereof and is selected from the group of precipitated calcium carbonate having a valeritic, calcitic or aragonitic crystalline structure, especially prismatic, scalenoed or rhombohedral precipitated calcium carbonate, distinct from ultrafine; natural crushed calcium carbonate being selected from marble, limestone and / or chalk and mixtures of these. [0008] Process according to claim 7, characterized in that the at least one additional filler and / or pigment particle has an average particle size of 0.01 to 5 µm, preferably 0.05 to 1.5 µm. one, more preferably from 0.1 to 0.8 µm and more preferably from 0.2 to 0.5 gm, for example, 0.3 gm. [0009] Process according to any one of claims 1 to 8, characterized in that the filler and / or pigment from step b) and / or at least one additional filler and / or pigment are associated with dispersing agents selected from the group which comprises homopolymers or copolymers of polycarboxylic acids and / or their salts or derivatives, such as ethers based on acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid; acrylamide or acrylic esters, methyl methacrylate or mixtures thereof; alkyl polyphosphates, phosphonic, citric and tartaric acids or their salts or esters or mixture thereof. [0010] Process according to any one of claims 1 to 9, characterized in that the combination of fibers and at least one filler and / or pigment from step b) is carried out by adding the filler and / or pigment to the fibers or the fibers to the filler and / or pigment in one or several stages. [0011] Process according to any one of claims 1 to 10, characterized in that the filler and / or pigment from step b) and / or the fibers from step a) are added entirely or in portions before or during the fibrillar step (d), preferably before the fibrillation step (d). [0012] Process according to any one of claims 1 to 11, characterized in that the weight ratio of fibers to filler and / or pigment from step b) on a dry weight basis is from 1:33 to 10: 1 , more preferably from 1:10 to 7: 1, even more preferably from 1: 5 to 5: 1, typically from 1: 3 to 3: 1, especially from 1: 2 to 2: 1 and most preferably from 1: 1 , 5 to 1.5: 1, for example, 1: 1. [0013] 13. Process according to any one of claims 1 to 12, characterized by the fact that fibrillation is carried out by means of a homogenizer or an ultrathin friction crusher. [0014] Process according to any of claims 1 to 13, characterized in that the additional non-fibrillated fibers of step e) are in the form of a fiber network. [0015] 15. Process according to any one of claims 1 to 14, characterized by the fact that the structured material is a paper. [0016] 16. Process according to claim 15, characterized by the fact that the amount of gel expressed by the cellulosic content of the gel in relation to the additional non-fibrillated fibers (dry / dry weight basis) can be from 0.5 to 20% in weight, preferably 1 to 15% by weight, 2 to 10% by weight, 3 to 6% by weight, for example, 5% by weight. [0017] 17. Process according to claim 15 or 16, characterized in that the total content of filler and / or pigment on a dry weight basis of the structured material is from 1% by weight to 60% by weight, preferably 5 % by weight to 50% by weight, more preferably from 10 to 45% by weight, even more preferably from 25% by weight to 40% by weight, especially from 30 to 35% by weight. [0018] 18. Use of nanofibrillary cellulose gels as defined in any of claims 1 to 17, characterized by the fact that it is for the production of structured material by combining the gel with additional fibers and subsequently pouring the combination.
类似技术:
公开号 | 公开日 | 专利标题 BR112012027635B1|2020-12-08|process to manufacture structured material, use of nanofibrillar cellulose gels ES2717327T3|2019-06-20|Process for the production of gel-based composites KR101790353B1|2017-10-25|Process for the production of nano-fibrillar cellulose gels KR20180125048A|2018-11-21|Process for the production of nano-fibrillar cellulose suspensions AU2014227494B2|2016-02-04|Process for the manufacture of structured materials using nano-fibrillar cellulose gels JP7033105B2|2022-03-09|Methods for Making Structured Materials Using Nanofibril Cellulose Gel
同族专利:
公开号 | 公开日 ES2668812T3|2018-05-22| KR101737664B1|2017-05-18| SI2386682T1|2014-07-31| HRP20140549T1|2014-07-18| US10053817B2|2018-08-21| AU2011246522A1|2012-11-01| RU2012150422A|2014-06-10| DK2563966T3|2018-04-30| WO2011134939A1|2011-11-03| CA2796135A1|2011-11-03| KR20130064073A|2013-06-17| US10633796B2|2020-04-28| US10100467B2|2018-10-16| JP6224176B2|2017-11-01| US20130126112A1|2013-05-23| TWI586869B|2017-06-11| RU2570472C2|2015-12-10| NZ603759A|2013-12-20| JP6968646B2|2021-11-17| CL2012002985A1|2013-11-04| TW201142107A|2011-12-01| EP2386682A1|2011-11-16| DK2386682T3|2014-06-23| MX2012012450A|2012-11-21| JP2019196580A|2019-11-14| JP2016216884A|2016-12-22| EP3336247A1|2018-06-20| JP2013527333A|2013-06-27| AU2011246522B2|2014-06-26| UY33356A|2011-12-01| JP2018031105A|2018-03-01| JP5961606B2|2016-08-02| CN102869832A|2013-01-09| EP2563966B1|2018-01-24| US20180327971A1|2018-11-15| PL2563966T3|2018-08-31| HK1256662A1|2019-09-27| CN102869832B|2015-12-02| CO6620035A2|2013-02-15| BR112012027635A2|2016-08-09| EP2563966A1|2013-03-06| ES2467694T3|2014-06-12| EP2386682B1|2014-03-19| PL2386682T3|2014-08-29| PT2386682E|2014-05-27| CA2796135C|2017-08-15| NO2563966T3|2018-06-23| US20150330024A1|2015-11-19| JP2022000550A|2022-01-04|
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法律状态:
2017-11-28| B25D| Requested change of name of applicant approved|Owner name: OMYA INTERNATIONAL AG (CH) | 2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]| 2019-02-26| B06T| Formal requirements before examination [chapter 6.20 patent gazette]| 2020-01-14| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]| 2020-08-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2020-12-08| 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 26/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |
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申请号 | 申请日 | 专利标题 EP10161166.3A|EP2386682B1|2010-04-27|2010-04-27|Process for the manufacture of structured materials using nano-fibrillar cellulose gels| EP10161166.3|2010-04-27| US34377510P| true| 2010-05-04|2010-05-04| US61/343775|2010-05-04| PCT/EP2011/056542|WO2011134939A1|2010-04-27|2011-04-26|Process for the manufacture of structured materials using nano-fibrillar cellulose gels| 相关专利
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