Compositions

专利摘要:

公开号:ES2641064T9
申请号:ES11791031.5T
申请日:2011-11-09
公开日:2017-12-11
发明作者:John Claude Husband；Per Svending；David Robert Skuse
申请人:FiberLean Technologies Ltd；
IPC主号:

专利说明:

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DESCRIPTION
Compositions Field of the invention
The present invention relates to compositions, such as loaded and coated papers, comprising microfibrillated cellulose and particulate inorganic material.
Background of the invention
Inorganic particulate materials, for example an alkaline earth metal carbonate (eg, calcium carbonate) or caolm, are widely used in a number of applications. These include the production of compositions containing minerals that can be used in papermaking, paper coating or polymeric composite production. In paper and polymer products, such charges are typically added to replace a part of other more expensive components of the paper or polymer product. Loads can also be added in order to modify the physical, mechanical and / or optical requirements of paper and polymer products. Clearly, the greater the amount of cargo that can be included, the greater the potential for cost savings. However, the amount of load added and the associated cost savings must be balanced against the physical, mechanical and optical requirements of the final paper or polymer product. Therefore, there is a continuing need for the development of loads for paper or polymers that can be used with a high load level, without adversely affecting the physical, mechanical and / or optical requirements of final paper or polymer products . Therefore, the development of loads for paper or polymers that can be used with a high load level without adversely affecting the physical, mechanical and / or optical requirements of paper products is continually needed. It also requires the development of methods for preparing these charges economically.
The present invention seeks to provide alternative and / or improved loads for paper or polymer products that can be incorporated into the paper or polymer product at relatively high load levels while maintaining, or even improving, the physical, mechanical and / or physical properties. or optics of the paper or polymer product. The present invention also seeks to provide an economical method for preparing such loads. Thus, the authors of the present invention have surprisingly found that a charge comprising microfibrillated cellulose and an inorganic particulate material can be prepared by economic methods and can be loaded into paper or polymeric products at relatively high levels while being maintain or even improve the physical, mechanical and / or optical properties of the final paper or polymer product.
In addition, the present invention seeks to address the problem of preparing microfibrillated cellulose economically on an industrial scale. Current microfibrillation methods of cellulosic material require relatively high amounts of energy due in part to the relatively high viscosity of the starting material and the microfibrillated product, and until now it has proved difficult to achieve a commercially viable process for preparing microfibrillated cellulose on an industrial scale .
In the prior art document EP2236664A1, the manufacture of nanofibrillar cellulose is described, which is prepared by breaking cellulose fibers into primary fibrils.
Summary of the invention
In accordance with a first aspect, the present invention is directed to an article comprising a paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material and one or more functional coatings on the paper product, wherein the cellulose Microfibrillated has a fiber bias of 20 to 50.
The prior art document mentioned above EP2236664A1 does not describe, nor does it even refer to the preparation of a coprocessed microfibrillated cellulose, not to mention microfibrillated cellulose having a fiber bias of 20 to 50.
According to a second aspect, the present invention is directed to a paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, wherein the paper product has: i) a first tensile strength greater than a second tensile strength of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; ii) a first tear strength greater than a second tear resistance of the paper product devoid of the composition of coprocessed microfibrillated cellulose and particulate inorganic material; and / or iii) a first burst resistance greater than a second burst resistance of the paper product devoid of the composition of coprocessed microfibrillated cellulose and particulate inorganic material; and / or iv) a first sheet light scattering coefficient greater than a second sheet light scattering coefficient of the paper product devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material; and / or v) a first porosity less than a second porosity of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; and / or vi) a first resistance in the z direction (internal link) than a second resistance in the z direction (internal link) of the
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paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; wherein microfibrillated cellulose has a fiber bias of 20 to 50.
According to a third aspect, the present invention is directed to a coated paper product, wherein the coating comprises a composition of coprocessed microfibrillated cellulose and inorganic particulate material, and wherein the coated paper product has:
i. a first gloss greater than a second gloss of the coated paper product comprising a coating composition devoid of the coprocessed microfibrillated cellulose composition and inorganic particulate material; and / or ii. a first stiffness that is greater than a stiffness of the coated paper product comprising a coating composition devoid of the composition of coprocessed microfibrillated cellulose and particulate inorganic material; and / or iii. a first barrier property that is better compared to a second barrier property of the coated paper product comprising a coating composition devoid of the co-processed microfibrillated cellulose composition and particulate inorganic material, wherein the microfibrillated cellulose has a bias of the 20 to 50 fiber.
According to a fourth aspect, the present invention is directed to a polymer composition comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, wherein the microfibrillated cellulose has a fiber bias of 20 to 50.
According to a fifth aspect, the present invention is directed to a papermaking composition comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, wherein the papermaking composition has a first cationic demand less than a second cationic demand of the composition for the manufacture of paper devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material, wherein the microfibrillated cellulose has a fiber bias of 20 to 50.
According to a sixth aspect, the present invention is directed to a papermaking composition comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, wherein the papermaking composition is substantially devoid of retention aids. , and where microfibrillated cellulose has a fiber bias of 20 to 50.
According to a seventh aspect, the present invention is directed to a paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, wherein the paper product has a first formation index smaller than a second training index. of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material, and wherein the microfibrillated cellulose has a fiber bias of 20 to 50.
Detailed description of the invention
As used herein, "coprocessed microfibrillated cellulose composition and inorganic particulate material" refers to compositions produced by the processes for microfibrillation of fibrous substrates comprising cellulose in the presence of an inorganic particulate material as described in the present memory
Unless otherwise stated, "functional coating" refers to a coating or coatings applied to the surface of a paper product to modify, enhance, improve and / or optimize one or more non-graphic properties of said paper product (ie that is, properties not related mainly to the graphic properties of the paper). In embodiments, the functional coating is not one that comprises a composition of coprocessed microfibrillated cellulose and inorganic particulate material. For example, the functional coating may be a polymer, a metal, an aqueous composition, a liquid barrier layer or a printed electronic layer.
Paper products
In some embodiments, the paper products comprise a coprocessed microfibrillated cellulose composition and inorganic particulate material incorporated in the paper pulp (eg, in the paper base as a loading composition). For example, paper products may comprise at least about 0.5% by weight, at least about 5% by weight, at least about 10% by weight, at least about 15% by weight, at least about 20% by weight , at least about 25% by weight, at least about 30% by weight, or at least about 35% by weight of a composition of coprocessed microfibrillated cellulose and inorganic particulate material, based on the total weight of the paper product. In general, paper products will comprise at most about 50% by weight, for example, at most about 45% by weight, or at most about 40% by weight of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. In a particular embodiment, the paper product comprises from about 25% to about 35% by weight of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. The fiber content of the co-processed microfibrillated cellulose composition and inorganic particulate material may be at least
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about 2% by weight, at least about 3% by weight, at least about 4% by weight, at least about 5% by weight, at least about 6% by weight, at least about 7% by weight, at least about 8 % by weight, at least about 10% by weight, at least about 11% by weight, at least about 12% by weight, at least about 13% by weight, at least about 14% by weight or at least about 15% by weight weight. In general, the fiber content of the coprocessed microfibrillated cellulose composition and inorganic particulate material will be less than about 25%, for example, less than about 20% by weight.
After coprocessing to form the composition of coprocessed microfibrillated cellulose and inorganic particulate material, additional inorganic material may be added (e.g., by combination or mixing) to reduce the content of the coprocessed microfibrillated cellulose composition and inorganic material in particles.
In particular embodiments, paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material have a lower porosity compared to paper products without (i.e., devoid of) the composition of coprocessed microfibrillated cellulose and inorganic particulate material. . For example, the porosity of paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have an approximately 10% less porous, approximately 20% less porous, approximately 30% less porous, approximately 40% less porous or about 50% less porous than a porosity of paper products devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material. Such a reduction in porosity can provide a better coating resistance for coated paper products comprising coprocessed microfibrillated cellulose and particulate inorganic material. Such a reduction in porosity may allow a reduction in the weight of the coating for coated paper products comprising coprocessed microfibrillated cellulose and inorganic particulate material, without compromising the physical and / or mechanical properties of the coated paper product.
In one embodiment the porosity is determined using the Bendtsen Model 5 porosity meter in accordance with SCAN P21, SCAN P60, BS 4420 and Tappi UM 535.
In other embodiments, paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material have a tensile strength approximately 2% greater, approximately 5% greater, approximately 10% greater, approximately 15% greater, approximately 20% greater, or approximately 25% greater than the tensile strength of paper products devoid of a co-processed microfibrillated cellulose composition and inorganic particulate material (i.e., the paper product has the same amount of charge).
In further embodiments, paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material have a tear strength approximately 2% greater, approximately 5% greater, approximately 10% greater, approximately 15% greater, approximately 20% greater , or about 25% greater than the tear strength of paper products devoid of a composition of co-processed microfibrillated cellulose and inorganic particulate material (e.g., the paper product has the same amount of charge). Such strong low porosity paper products may comprise functional papers such as gaskets, grease-proof papers, plasterboard board, fireproof paper, wallpapers, laminates or other functional paper products.
In one embodiment, tensile strength is determined using the Testometrics tensile tester in accordance with SCAN P16.
In further embodiments, paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material have a resistance in the z-direction (internal bond) about 2% higher, about 5% higher, about 10% higher, about 15% greater, approximately 20% greater, or approximately 25% greater than the resistance in the z direction (internal bond) of paper products devoid of a composition of coprocessed microfibrillated cellulose and inorganic particulate material (e.g., the product of paper has the same amount of load).
In one embodiment, the resistance in the z direction (internal link) is determined using a Scott junction meter in accordance with TAPPI T569.
In some embodiments, paper products comprising a coprocessed microfibrillated cellulose composition and inorganic particulate material can be coated. Particular embodiments of the coated paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, may have a higher brightness compared to the coated paper product devoid of the coprocessed microfibrillated cellulose composition and inorganic particulate material. For example, coated paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a brightness of approximately 5% greater, approximately 10% greater, or approximately 20% greater, than coated paper products devoid of cellulose composition
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coprocessed microfibrillated and inorganic particulate material.
In one embodiment, the brightness is determined according to the TAPPI T 480 om-05 method (specular gloss of the paper and cardboard at 75 degrees).
In other embodiments, coated paper products comprising a cellulose composition
Coprocessed microfibrillated and inorganic particulate material may have better printing properties such as print brightness, breakage, print density, repel speed or percentage of lost points.
In other embodiments, coated paper products comprising a cellulose composition
Coprocessed microfibrillated and inorganic particulate material may have a lower humid vapor transmission rate (MVTR, tested according to a modified version of TAPPI T448 using silica gel as the desiccant and a relative humidity of 50%) compared to the product of Coated paper devoid of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. For example, coated paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have an MVTR of approximately 2% less, approximately 4% less, approximately 6% less, approximately 8% less, approximately 10% less, approximately 12% less, approximately 15% less, or approximately 20% than coated paper products devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material (e.g., the paper product has the same amount of charge) .
In some embodiments, paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may serve as a basis for functional coatings such as liquid packaging coatings, barrier coatings and coatings for printed electronics. Paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material provide a smooth surface for applying functional coatings thereon. For example, paper products may include a barrier coating comprising a polymer, a metal, an aqueous composition (eg, a water-based barrier layer), or a combination thereof.
The aqueous composition may comprise one or more inorganic particulate materials described herein. For example, the aqueous composition may comprise caolm, such as laminated caolm or hyperlaminated caolm. By "rolled" caolm is meant a caolm product that has a high form factor. A laminated caolm has a form factor of about 20 to less than about 60. A hyperlaminated caolm has a form factor of about 60 to 100 or even greater than 100. The "form factor," as used herein. , is a measure of the ratio of the diameter of the particle to the thickness of the particle for a population of particles of variable size and shape when measured using methods, apparatus and equations of electrical conductivity, described in US Pat. No. 5,576,617. As the technique for determining the form factor in patent 617 is described in more detail, the electrical conductivity of a composition of an aqueous suspension of oriented particles that is tested is measured when the composition flows through a container. Electrical conductivity measurements are taken along one direction of the container and along another direction of the container transverse to the first direction. Using the difference between the two conductivity measurements, the form factor of the particulate material being tested is determined.
In some embodiments, paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material provide a low permeability surface for the application of the functional coating on the paper product. Therefore, finer functional coatings, less quantity and / or non-polymeric can be used to achieve a desired function (eg, barrier function). In some embodiments, coated paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have better oil resistance (measured using an oil-based solution of Sudan Red IV in dibutyl phthalate using a printing unit IGT) compared to the coated paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material. For example, coated paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have an oil resistance that is about 2% higher, about 4% higher, about 6% higher, about 8% higher, or approximately 10% higher than the coated paper products devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material (e.g., the coated paper product has the same amount of filler).
Improved paper and sheet manufacturing properties
In some embodiments, paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material allow for improved processing for the manufacture of said paper products. For example, by including a composition of coprocessed microfibrillated cellulose and inorganic particulate material in the paper pulp, the final wet processing of the paper base may not require pretreatment (eg, addition of cationic polymers). In addition, compared to a paper pulp that includes microfibrillated cellulose, a paper pulp that includes a microfibrillated cellulose composition
coprocessed and inorganic material in particles has less change or does not change the cationic demand, has improved retention and improved formation. In some embodiments, in which retention is improved by the composition of coprocessed microfibrillated cellulose and inorganic particulate material used in the paper product, the use of retention aids can be reduced or eliminated and product damage can be avoided. of 5 paper resulting from retention aids.
The cationic demand of a paper pulp sample for papermaking is indicated by the amount of highly charged cationic polymer needed to neutralize its surface. A flowing current test can be used to determine the cationic demand, based on the amount of cationic titration agent (eg, poly-DADMAC) necessary to reach a zero signal. Another way to determine the end point is to evaluate the zeta potential after each incremental addition of titration agent. Another strategy to determine the cationic demand is to mix the sample with a known excess of cationic titration agent, filter to separate the solids, and then re-titrate to a final color point (colloidal titration). In embodiments, the cationic demand of a paper pulp for the manufacture of paper comprising the composition of coprocessed microfibrillated cellulose and inorganic material in particles composition of coprocessed microfibrillated cellulose and inorganic material in particles, is comparable to or less than the cationic demand of a paper pulp for papermaking devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material (e.g., the pulp has the same amount of charge).
In one embodiment, the cationic demand (also called "anionic charge") is measured using the Mutek PCD 03 Titrator device according to the method described later in the "Examples".
20 Retention is a general term for the process of keeping fine particles and fine fibers within the paper web when it is being formed. The retention to the first step gives a practical indication of the effectiveness by which these fine materials are retained in the paper web when it is being formed. In some embodiments, the retention at the first step of a paper pulp comprising the composition of coprocessed microfibrillated cellulose and inorganic particulate material is greater, for example, about 2% higher, about 5% higher, or about 10% higher that a paper pulp devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material (e.g., the paper pulp has the same amount of charge).
In one embodiment, the retention to the first step is determined based on the measurement of solids in the input box (HB) and the white water tray (WW) and is calculated according to the following formula:
30 Retention = [(HBs6lids-WWs6lids) / HBs6lids] x 100
The retention of ashes (determined by incineration) during paper formation can be improved in paper products formed from paper pulp comprising the composition of coprocessed microfibrillated cellulose and inorganic particulate material, compared to a paper pulp devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material (e.g., the pulp has the same amount of charge). In embodiments, the retention during the formation of paper formed from a paper pulp comprising the composition of coprocessed microfibrillated cellulose and inorganic particulate material, is at least about 5%, at least about 10%, at least about 15% , at least about 20%, or at least about 25% higher, than a paper pulp devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material (e.g., paper pulp 40 has the same amount of charge ).
In one embodiment, the retention of ashes is determined following the same principles as the retention at the first step, but based on the weight of the ash component in the input box (HB) and the white water tray (WW), and It is calculated according to the following formula:
Ash Retention = [(HBcenizas-WWcenizas) / HBcenizas] x 100
45 Paper formation is the resulting non-uniform distribution of fibers, fiber fragments, mineral fillers and chemical additives in the web that forms the paper. The formation can be characterized by the variation of the small scale base weight in the plane of the paper sheet. Another way to describe the formation is the variability of the base weight of the paper. The non-uniform structure of the paper can be seen with the naked eye on length scales ranging from fractions of a millimeter to a few centimeters. In some embodiments, the formation index (PTS) of a paper pulp 50 comprising the composition of coprocessed microfibrillated cellulose and inorganic particulate material is at least about 5% less, about 10% less, about 15% less, about 20 %, or about 25% less than a paper pulp devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material (e.g., the paper pulp has the same amount of charge).
In one embodiment, the training index (PTS) is determined using the DOMAS software developed by PTS in accordance with the measurement method described in section 10-1 of its manual. "'DOMAS 2.4 User Guide".
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In other embodiments, a cardboard product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have better folding and / or cracking resistance.
Paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may also have a combination of improved sheet properties. For example, sheets of paper products comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material have better strength properties and better formation. Without being limited by a particular theone, such a combination is surprising because it is believed that additional refining or fibrillation undesirably damages the formation of the paper due to the reduced stability that leads to a propensity to flocculate, but may increase the strength of the sheet. of paper.
In other embodiments, the paper product sheets comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, have better tensile strength, tear strength and resistance in the z direction (internal bond). This is surprising because normally in the refining of the paste, increasing the tensile strength will decrease the tear strength and / or the resistance in the z direction. For example, sheets of paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a tensile strength that is at least about 2% higher, at least about 3% higher, at least about 4 % higher, at least about 5% higher, at least about 6% higher, at least about 7% higher, at least about 8% higher, at least about 9%, at least about 10% higher, at least about 12% higher , at least about 15% higher, or at least about 20% higher than the paper product sheets devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material (e.g., the paper product sheet has the same load quantity). In other embodiments, sheets of paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a tear strength that is at least about 5% higher, at least about 10% higher, at least about 15 % higher, at least about 20% higher, or at least about 25% higher than paper product sheets devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material (e.g., the paper product sheet has the same amount of cargo). In other embodiments, the paper product sheets comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, have a combination of better tensile strength and better tear strength. For example, paper product sheets comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a tensile strength that is about 2% to about 10% greater than paper product sheets devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material, and a tear strength of about 5% to about 25% greater than sheets of paper product devoid of the coprocessed microfibrillated cellulose composition and inorganic particulate material.
In one embodiment, the tear strength is determined according to the TAPPI method T414 om-04 (Internal tear resistance of the paper (Elmendorf type method)).
In other embodiments, the paper product sheets comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, have better tensile strength and better dispersion (i.e., optical) properties, e.g. eg, scattering of leaf light and absorbing leaf light. Again this is surprising, since normally increasing tensile strength decreases the light scattering of the sheet. In some embodiments, sheets of paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a coefficient of light scattering of the sheet (in m2.kg "1, measured using filters 8 and 10 ) which is at least about 2% higher, at least about 3% higher, at least about 4% higher, at least about 5% higher, at least about 6% higher, at least about 7% higher, at least about 8% higher, at least about 9% higher, or at least about 10% higher than the paper product sheets devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material (e.g., the paper product sheet has the same amount of loading.) In other embodiments, the paper product sheets comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material have a combination of better tensile strength and / or better tear resistance, and better light scattering. For example, paper product sheets comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a tensile strength that is about 2% to about 10% greater than paper product sheets devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material, and / or a tear strength of about 5% to about 25% greater than sheets of paper product devoid of the coprocessed microfibrillated cellulose composition and inorganic particulate material, and a coefficient of light scattering of the sheet (in m2.kg "1, measured using filters 8 and 10) that is about 2% to about 10% higher, for example, about 2% to about 5% greater than paper product sheets devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material (e.g., product sheet d e paper has the same amount of charge).
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In one embodiment, the scattering and light absorption coefficients of the sheet are measured using the reflectance data of an Elrepho instrument: R inf = reflectance of a stack of 10 sheets, Ro = reflectance of 1 sheet on a black cup, and these values and the substance (gm-2) of the sheet are introduced into the Kubelka - Munk equation described in "Paper Optics" by Nils Pauler, (published by Lorentzen and Wettre, ISBN 91-971-765-6-7 ), P. 29-36.
Burst resistance is widely used as a measure of tear strength on many types of paper. In some embodiments, sheets of paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a burst resistance that is at least about 5% higher, at least about 10% higher, at least about 15 % higher, at least about 20% higher, or at least about 25% higher than paper product sheets devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material (e.g., the paper product sheet has the same amount of cargo).
In one embodiment, burst resistance is determined using the Messemer Buchnel burst tester according to SCAN P24.
In some embodiments, said improved properties of the paper product sheets can be achieved in paper product sheets comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, which includes microfibrillated cellulose having a dso in the range of approximately 25 pm to about 250 pm, more preferably from about 30 pm to about 150 pm, even more preferably from about 50 pm to about 140 pm, still more preferably from about 70 pm to about 130 pm, and most preferably from about 50 pm at about 120 pm. In particular embodiments, the microfibrillated cellulose of the coprocessed microfibrillated cellulose composition and inorganic particulate material has a high bias (as defined below) directed towards a desired d50. In one embodiment, a skewed particle size distribution of microfibrillated cellulose can be produced by microfibrillation of the fibrous substrate comprising cellulose in the presence of an inorganic particulate material in a discontinuous process in which the composition of coprocessed microfibrillated cellulose and inorganic material in particles having the inclination of the desired microfibrillated cellulose can be dragged by washing the microfibrillation apparatus with water or any other liquid.
In some embodiments, the microfibrillated cellulose of the composition of coprocessed microfibrillated cellulose and inorganic particulate material has a size distribution of single mode particles. In other embodiments, the microfibrillated cellulose of the composition of coprocessed microfibrillated cellulose and inorganic particulate material has a size distribution of multimodal particles produced, for example, by minor or partial microfibrillation of the fibrous substrate comprising cellulose in the presence of inorganic particulate material.
Coatings
In some embodiments, the coatings may comprise a composition of coprocessed microfibrillated cellulose and inorganic particulate material. Coatings comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may also be used as functional paper such as that used for liquid packaging, barrier coatings or printed electronic applications. For example, the functional coating may be a barrier layer, e.g. eg, a liquid barrier layer, or the functional coating may be a printed electronic layer.
The coating comprising a composition of coprocessed microfibrillated cellulose and particulate inorganic material can be applied to a paper product to produce a paper or paper product coating having higher strength properties (e.g., tensile strength , tear resistance and stiffness), higher brightness and / or better printing properties (e.g., print brightness, breakage, print density, or percentage of lost points). For example, the paper product coated with a coating comprising a composition of coprocessed microfibrillated cellulose and particulate inorganic material may have a tensile strength approximately 5% greater, approximately 10% greater, or approximately 20% greater than the resistance to the traction of a paper product coated with a coating devoid of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. In some embodiments, the paper product coated with a coating comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a tear strength approximately 5% greater, approximately 10% greater, or approximately 20% greater than the resistance to tearing of a paper product coated with a coating devoid of a composition of coprocessed microfibrillated cellulose and particulate inorganic material. In some embodiments, the paper product coated with a coating comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a stiffness approximately 5% greater, approximately 10% greater, or approximately 20% greater than a product stiffness paper coated with a coating devoid of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. In some embodiments, the paper product coated with a coating comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a brightness of approximately 5% greater, approximately 10% greater, or approximately 20% greater than the brightness of a product of paper coated with a coating devoid of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. In some
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embodiments, the paper product coated with a coating comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may have a barrier property that is better than the barrier property of the paper product coated with a coating devoid of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. The barrier property can be selected from the rate at which one or more of oxygen, moisture, fat and aromas pass (ie, are transmitted) through the coated paper product. The coating comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material may, therefore, slow down or improve (i.e. decrease) the rate at which one or more of oxygen, moisture, fat and aromas pass through coated paper product.
In some embodiments, tensile strength, tear strength and gloss are determined according to the methods described above.
In embodiments, the stiffness (ie, the elastic modulus) is determined according to the stiffness measurement method described in J.C. Husband, L.F. Gate, N. Norouzi, and D. Blair, "The Influence of Kaolin Shape Factor on the Stiffness of Coated Papers," TAPPI Journal, June 2009, p. 12-17 (see in particular the section entitled "Experimental methods"); and J.C. Husband, J.S. Preston, L.F. Gate, A. Storer, and P. Creaton, "The Influence of Pigment Particle Shape on the ln-Plane tensile Strength Properties of Kaolin-based Coating Layers", TAPPI Journal, December 2006, p. 3-8 (see in particular the section entitled "Experimental methods").
In one embodiment, the inorganic particulate material is caolm. Advantageously, the caolm is a laminated caolm or a hyperlaminated caolm.
Dispersible compositions
In some embodiments, the composition of coprocessed microfibrillated cellulose and inorganic particulate material may be in the form of a dry or substantially dry redispersible composition, produced by the methods described herein or by any other drying process known in the art (p e.g. lyophilized). The composition of coprocessed microfibrillated cellulose and dried inorganic particulate material can be easily dispersed in an aqueous or non-aqueous medium (eg, polymers).
Therefore, in accordance with a third aspect of the present invention, a polymer composition is provided comprising the composition of coprocessed microfibrillated cellulose and inorganic particulate material described herein.
The polymer composition may comprise at least about 0.5% by weight, at least about 5% by weight, at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, or at least about 35% by weight of a co-processed microfibrillated cellulose composition and inorganic particulate material, based on the total weight of the polymer composition. In general, the polymer will comprise at most about 50% by weight, for example, at most about 45% by weight, or at most about 40% by weight of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. In a particular embodiment, the polymer composition comprises from about 25% to about 35% of a composition of coprocessed microfibrillated cellulose and inorganic particulate material. The fiber content of the co-processed microfibrillated cellulose composition and inorganic particulate material may be at least about 2% by weight, at least about 3% by weight, at least about 4% by weight, at least about 5% by weight, at least about 6% by weight, at least about 7% by weight, at least about 8% by weight, at least about 10% by weight, at least about 11% by weight, at least about 12% by weight, at least about 13% by weight, at least about 14% by weight or at least about 15% by weight. In general, the fiber content of the co-processed microfibrillated cellulose composition and inorganic particulate material will be less than about 25% by weight, for example, less than about 20% by weight.
The polymer may comprise any natural or synthetic polymer or a mixture thereof. The polymer can be, for example, thermoplastic or thermosetting. The term "polymer" used herein includes homopolymers and / or copolymers, as well as crosslinked and / or entangled polymers.
Polymers, which include homopolymers and / or copolymers, comprised in the polymer composition of the present invention can be prepared from one or more of the following monomers: acrylic acid, methacrylic acid, methyl methacrylate and alkyl acrylates having 1-18 carbon atoms in the group alkyl, styrene, substituted styrenes, divinylbenzene, diallyl phthalate, butadiene, vinyl acetate, acrylonitrile, methacrylonitrile, maleic anhydride, esters of maleic acid or smoking acid, tetrahydrophthalic acid or anhydride, itaconic anhydride, and esters of itaconic acid, with or without a dimer, crosslinking tetramer or tetramer, crotonic acid, neopentyl glycol, propylene glycol, butanediols, ethylene glycol, diethylene glycol, dipropylene glycol, glycerol, cyclohexyanodimethanedimethanedimethanedimethanedimethanedimethanedimethanedimethanedimethanedimethane phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic anhydride, adipic acid or succmic acids, azela acid ico and dfimer fatty acids,
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toluene diisocyanate and diphenylmethane diisocyanate. CopoUmmers comprising methyl methacrylate and styrene monomers are preferred.
The polymer can be selected from one or more of poly (methyl methacrylate) (PMMA), polyacetal, polycarbonate, polyacrylonitrile, polybutadiene, polystyrene, polyacrylate, polypropylene, epoxy polymers, unsaturated polyester, polyurethanes, polycyclopentadiene and co-polymers. Suitable polymers also include liquid rubbers, such as silicones.
The preparation of polymer compositions of the present invention can be carried out by any suitable mixing method known in the art, as will be readily apparent to one skilled in the art.
Such methods include the combination of the individual components or their precursors and subsequent processing in a conventional manner. Some of the ingredients can, if desired, be pre-mixed before adding to the composition mixture.
In the case of thermoplastic polymer compositions, said processing may comprise the melt mixture, either directly in an extruder to make an article from the composition, or the premix in a separate mixing apparatus. Dry blends of the individual components, alternatively, can be injection molded directly without melt premixing.
The polymer composition can be prepared by mixing the components thereof intimately with each other. Said composition of coprocessed microfibrillated cellulose and inorganic particulate material can then be suitably mixed with the polymer and any desired additional components, before processing as described above.
For the preparation of crosslinked or cured polymer compositions, the mixture of the uncured components or their precursors, and, if desired, the composition of coprocessed microfibrillated cellulose and inorganic particulate material and any desired non-perlite component or components, shall be placed. in contact under suitable conditions of heat, pressure and / or light, with an effective amount of any crosslinking agent or curing system, in accordance with the nature and quantity of the polymer used, in order to crosslink and / or cure the polymer.
For the preparation of the polymer compositions where the composition of coprocessed microfibrillated cellulose and inorganic particulate material and any other or other desired components at the time of polymerization, the combination of the monomers and any other precursors of Desired polymer, the composition of coprocessed microfibrillated cellulose and inorganic particulate material and any other or other desired components, will be brought into contact under the appropriate conditions of heat, pressure and / or light, according to the nature and quantity of the or used monomers, in order to polymerize the monomers or monomers with the perlite and any other or other components in situ.
The fibrous substrate comprising cellulose
The fibrous substrate comprising cellulose can be obtained from any suitable source such as wood, herbs (e.g., sugar cane, bamboo) or rags (e.g., textile waste, cotton, hemp or linen). The fibrous substrate comprising cellulose may be in the form of a paste (i.e., a suspension of cellulose fibers in water), which can be prepared by any suitable chemical or mechanical treatment, or combination thereof. For example, the pulp may be a chemical pulp, or a chemothemomechanical pulp, or a mechanical pulp or a recycled pulp, or a waste of wastebasket, or a waste stream of wastebasket, or waste from a wastebasket or a combination thereof. The cellulose pulp can be beaten (for example, in a Valley blender) and / or refined in another way (for example, by processing in a conical or plate refiner) to any predetermined degree of refining, described in the art as the Canadian refining grade (CSF) in cm3. The CSF means a value for the refining or drainage rate of the paste measured by the speed at which a pulp suspension can be drained. For example, cellulose pulp may have a Canadian refining degree of approximately 10 cm3 or greater before being microfibrillated. The cellulose pulp may have a CSF of about 700 cm3 or less, for example, equal to or less than about 650 cm3, or equal to or less than about 600 cm3, or equal to or less than about 550 cm3, or equal to or less than about 500 cm3, or equal to or less than about 450 cm3, or equal to or less than about 400 cm3, or equal to or less than about 350 cm3, or equal to or less than about 300 cm3, or equal to or less than about 250 cm3, or equal or less than about 200 cm3, or equal to or less than about 150 cm3, or equal to or less than about 100 cm3, or equal to or less than about 50 cm3. The water can then be removed from the cellulose pulp by methods well known in the art, for example, the pulp can be filtered through a sieve in order to obtain a wet sheet comprising at least about 10% solids, for example, at least about 15% solids, or at least about 20% solids, or at least about 30% solids, or at least about 40% solids. The paste can be used in an unrefined state, that is, without beating or removing the water, or otherwise refined.
The fibrous substrate comprising cellulose can be added to a crushing vessel or homogenizer in a dry state. For example, a waste of dry litter can be added directly to the shredder container. The aqueous environment in the shredder bowl will then facilitate the formation of a paste.
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The inorganic particulate material
The inorganic particulate material may be, for example, an alkaline earth metal carbonate or sulfate, such as calcium carbonate, magnesium carbonate, dolomite, gypsum, a hydrated kandite clay such as caolm, haloisite or ball clay, a Kandite clay anhydrous (calcined) such as metacaolm or fully calcined caolm, talc, mica, huntite, hydromagnesite, crushed glass, perlite or diatomaceous earth, or magnesium hydroxide or aluminum trihydrate, or combinations thereof.
A preferred inorganic particulate material for use in the method according to the first aspect of the present invention is calcium carbonate. Hereinafter, the invention will tend to be described in terms of calcium carbonate, and in relation to aspects where calcium carbonate is processed and / or treated. The invention should not be considered to be limited by such embodiments.
The particulate calcium carbonate used in the present invention can be obtained from a natural source by crushing. Crushed calcium carbonate (GCC) is typically obtained by breaking and then crushing a mineral source such as gypsum, marble or limestone, which can be followed by a classification stage by particle size, in order to obtain a product that has the desired degree of fineness. Other techniques such as bleaching, flotation and magnetic separation can also be used to obtain a product that has the desired degree of fineness and / or color. The particulate solid material can be autogenously crushed, that is, by wear between the particles of the solid material itself, or, alternatively, in the presence of a particle crushing medium comprising particles of a material other than calcium carbonate which It is going to crush. These procedures can be carried out with or without the presence of a dispersant and biocides, which can be added at any stage of the process.
Precipitated calcium carbonate (PCC) can be used as the source of particulate calcium carbonate in the present invention, and can be produced by any of the known methods available in the art. TAPPI Monograph Series No. 30, "Paper Coating Pigments", pages 34-35 describes the three main commercial procedures for preparing precipitated calcium carbonate that is suitable for use in the preparation of products for use in the paper industry, but can also be used in the practice of the present invention. In all three procedures, a material fed with calcium carbonate, such as limestone, is first calcined to produce quicklime, and then the quicklime is turned off in water to give calcium hydroxide or lime milk. In the first procedure, the lime slurry is carbonated directly with gaseous carbon dioxide. This process has the advantage that no by-products are formed, and it is relatively easy to control the properties and purity of the calcium carbonate product. In the second procedure, the lime slurry is contacted with anhydrous sodium carbonate to produce, by double decomposition, a precipitate of calcium carbonate and a solution of sodium hydroxide. Sodium hydroxide can be substantially completely separated from calcium carbonate, if this procedure is used commercially. In the third main commercial procedure, the lime slurry is first contacted with ammonium chloride to give a solution of calcium chloride and gaseous ammonia. The calcium chloride solution is then contacted with anhydrous sodium carbonate to produce, by double decomposition, precipitated calcium carbonate and a sodium chloride solution. The crystals can be produced in a variety of different shapes and sizes, depending on the specific reaction procedure used. The three main forms of PCC crystals are aragonite, rhomboedrico and scalenoedric (eg, calcite), all of which are suitable for use in the present invention, including mixtures thereof.
Wet crushing of calcium carbonate involves the formation of an aqueous suspension of calcium carbonate which can then be crushed, optionally in the presence of a suitable dispersing agent. Reference may be made, for example, to document EP-A-614948 for more information regarding the wet milling of calcium carbonate.
In some circumstances, minor amounts of other minerals may be included, for example, one or more of caolm, calcined caolm, wollastonite, bauxite, talc or mica may also be present.
When the inorganic particulate material of the present invention is obtained from naturally occurring sources, some mineral impurities may contaminate the crushed material. For example, naturally occurring calcium carbonate may be present associated with other minerals. Therefore, in some embodiments, the inorganic particulate material includes a quantity of impurities. However, in general, the inorganic particulate material used in the invention will contain less than about 5% by weight, preferably less than about 1% by weight of other mineral impurities.
The inorganic particulate material used during the microfibrillation step of the method of the present invention will preferably have a particle size distribution in which at least 10% by weight of the particles have an e.s.d. (equivalent spherical diameter) less than 2 pm, for example, at least about 20% by weight, or at least about 30% by weight, or at least about 40% by weight, or at least about 50% by weight, or at less about 60% by weight, or at least about 70% by weight, or at least about 80% by weight, or at least about 90% by weight, or at least about 95% by weight, or about 100% of the particles It has an esd of less than 2 pm.
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Unless otherwise indicated, the properties of the particle size cited herein for inorganic particulate materials are measured in a known manner by sedimentation of the particulate material under conditions completely dispersed in an aqueous medium using a Sedigraph 5100 machine supplied by Micromeritics lnstruments Corporation, Norcross, Georgia, USA (phone: +1 770 662 3620; website: www.micromeritics.com), referred to herein as "Micromeritics Sedigraph 5100 unit". Said machine provides measurements and a graph of the percentage accumulated in weight of particles that have a size, referred to in the art as the "equivalent spherical diameter" (esd), smaller than given esd values. The average size of particles d50 is the value determined in this way of the esd of the particle in which there are 50% by weight of the particles having an equivalent spherical diameter smaller than that value of d50.
Alternatively, when indicated, the particle size properties cited herein for inorganic particulate materials are measured by the well-known conventional method used in the laser light scattering technique, using a Malvern Mastersizer machine supplied by Malvern Instruments Ltd (or by other methods that give essentially the same result). In the technique of laser light scattering, the size of powdered particles, suspensions and emulsions can be measured using the diffraction of a laser beam, based on an application of the Mie teona. Said machine provides measurements and a graph of the percentage in cumulative volume of particles that have a size, referred to in the art as the "equivalent spherical diameter" (e.s.d.), smaller than values of e.s.d. dices. The average size of d50 particles is the value determined in this way from the e.s.d. of the particle in which there is 50% by volume of the particles that have an equivalent spherical diameter smaller than that value of d50.
In another embodiment, the inorganic particulate material used during the microfibrillation step of the method of the present invention will preferably have a particle size distribution, measured using the Malvern Mastersizer machine, in which at least about 10% by volume of the particles have an esd less than 2 pm, for example, at least about 20% by volume, or at least about 30% by volume, or at least about 40% by volume, or at least about 50% by volume, or at least about 60% by volume volume, or at least about 70% by volume, or at least about 80% by volume, or at least about 90% by volume, or at least about 95% by volume, or about 100% by volume of the particles have an esd of less than 2 pm.
Unless otherwise indicated, the particle size properties of microfibrillated cellulose materials are as measured by the conventional well-known method used in the laser light scattering technique, using a Malvern Mastersizer machine supplied by Malvern lnstruments Ltd ( or by other methods that give essentially the same result).
Details of the procedure used to characterize particle size distributions of inorganic particulate mixtures and microfibrillated cellulose using a Malvern Mastersizer S. machine are provided below.
Another preferred inorganic particulate material for use in the method according to the first aspect of the present invention is caolm clay. Hereinafter, this section of the specification can be described in terms of the caolm, and in relation to aspects where the caolm is processed and / or treated. The invention should not be considered to be limited by such embodiments. Therefore, in some embodiments, caolm is used in an unprocessed form.
The caolm clay used in this invention can be a processed material derived from a natural source, in particular clay ore from raw natural caolm. Processed kaolm clay can typically contain at least about 50% by weight kaolinite. For example, commercially processed caolm clays mayone contain more than about 75% by weight of kaolinite and may contain more than about 90%, in some cases more than about 95% by weight of kaolinite.
The caolm clay used in the present invention can be prepared from the raw natural caolm clay ore by one or more other methods that are well known to the person skilled in the art, for example, by refining or enrichment steps.
For example, the clay ore can be bleached with a reducing bleaching agent, such as sodium hydrosulfite. If sodium hydrosulfite is used, the water can optionally be extracted from the bleached clay mineral, and optionally washed and optionally again extracted after the bleaching stage with sodium hydrosulfite.
The clay ore can be treated to remove impurities, e.g. eg, by flocculation, flotation or magnetic separation techniques, well known in the art. Alternatively, the clay mineral used in the first aspect of the invention may not be treated as a solid or as an aqueous suspension.
The process for preparing the caolm clay in particles used in the present invention may also include one or more fragmentation steps, e.g. eg crushing or grinding. Light fragmentation of a thick caolm is used to produce its proper delamination. Fragmentation can be carried out using pearls or granules of a plastic (eg, nylon), sand or auxiliary crushing or ceramic grinding. The thick caolm can be refined to
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separate impurities and improve physical properties using well known procedures. Caolm clay can be treated by a known particle size classification procedure, e.g. eg, screening and centrifugation (or both), to obtain particles having a desired value of d50 or particle size distribution.
The microfibrillation procedure
In accordance with the first aspect of the invention, there is provided a method of preparing a composition for use as a paper load or as a paper coating, comprising a microfibrillation step of a fibrous substrate comprising cellulose in the presence of a inorganic particulate material. According to particular embodiments of the present methods, the microfibrillation step is carried out in the presence of an inorganic particulate material that acts as a microfibrillation agent.
Microfibrillation means a procedure in which cellulose microfibrils are released or partially released as individual species or as smaller aggregates, compared to the pulp fibers before microfibrillation. Typical cellulose fibers (ie, pulp before microfibrillation) suitable for use in papermaking include aggregates larger than hundreds or thousands of individual cellulose microfibrils. Through cellulose microfibrillation, particular characteristics and properties are imparted, including but not limited to the characteristics and properties described herein, to microfibrillated cellulose and compositions that include microfibrillated cellulose.
The microfibrillation step can be carried out in any suitable apparatus, which includes, but is not limited to a refiner. In one embodiment, the microfibrillation step is carried out in a crushing vessel under wet crushing conditions. In another embodiment, the microfibrillation step is carried out in a homogenizer. Each of these embodiments is described in more detail below.
Wet crushing
Crushing is carried out properly in a conventional manner. The crushing can be a wear crushing process in the presence of a particulate grinding medium, or it can be an autogenous crushing process, that is, one in the absence of a crushing medium. By means of crushing, a means other than inorganic particulate material is understood to be co-crushed with the fibrous substrate comprising cellulose.
The particle crushing medium, when present, can be a natural or synthetic material. The grinding medium may comprise, for example, balls, beads or pellets of any mineral, ceramic or hard metal. Such materials may include, for example, alumina, zirconia, zirconium silicate, aluminum silicate or mullite-rich material that is produced by calcining the kaolimatic clay at a temperature in the range of about 1300 ° C to about 1800 ° C . For example, in some embodiments, a Carbolite® grinding medium is preferred. Alternatively, natural sand particles of a suitable particle size can be used.
In general, the type and size of the particles of the grinding medium that is selected for use in the invention may depend on properties such as, e.g. eg, the size of particles and the chemical composition, the feed suspension of the material to be crushed. Preferably, the particle grinding medium comprises particles having an average diameter in the range of about 0.1 mm to about 6.0 mm and more preferably in the range of about 0.2 mm to about 4.0 mm. The crushing medium (or means) may be present in an amount of up to about 70% by volume of the load. The grinding medium may be present in an amount of at least about 10% by volume of the cargo, for example, at least about 20% by volume of the cargo, or at least about 30% by volume of the cargo, or at less about 40% by volume of the cargo, or at least about 50% by volume of the cargo, or at least about 60% by volume of the cargo.
Crushing can be carried out in one or more stages. For example, a coarse inorganic particulate material can be crushed in the shredder vessel to a predetermined particle size distribution, after which the fibrous material comprising cellulose is added and the crushing is continued until the desired microfibrillation level is obtained. . The inorganic material in coarse particles used in accordance with the first aspect of this invention may initially have a particle size distribution in which less than about 20% by weight of the particles has an e.s.d. less than 2 pm, for example, less than about 15% by weight, or less than about 10% by weight of the particles has an e.s.d. less than 2 pm. In another embodiment the inorganic material in coarse particles used in accordance with the first aspect of this invention may initially have a particle size distribution, measured with a Malvern Mastersizer S machine, in which less than about 20% by weight of the particles has an esd less than 2 pm, for example, less than about 15% by volume, or less than about 10% by volume of the particles has an e.s.d. less than 2 pm.
The coarse particulate inorganic material can be crushed in wet or dry, in the absence or presence of a crushing medium. In the case of a wet crushing step, the coarse particulate inorganic material is preferably crushed in an aqueous suspension in the presence of a grinding medium. In said suspension,
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The inorganic bulk particulate material may preferably be present in an amount of about 5% to about 85% by weight of the suspension, more preferably in an amount of about 20% to about 80% by weight of the suspension. Most preferably, the coarse particulate inorganic material may be present in an amount of about 30% to about 75% by weight of the suspension. As described above, the coarse particulate inorganic material can be crushed to a particle size distribution such that at least about 10% by weight of the particles has an e.s.d. less than 2 pm, for example, at least about 20% by weight, or at least about 30% by weight, or at least about 40% by weight, or at least about 50% by weight, or at least about 60% by weight weight, or at least about 70% by weight, or at least about 80% by weight, or at least about 90% by weight, or at least about 95% by weight, or about 100% by weight of the particles have an esd less than 2 pm, after which the cellulose pulp is added and the two components are cotriturated to microfibrillate the cellulose pulp fibers. In another embodiment, the coarse inorganic particulate material is crushed to a particle size distribution, measured using the Malvern Mastersizer S machine, such that at least about 10% by volume of the particles have an esd of less than 2 pm, per example, at least about 20% by volume, or at least about 30% by volume, or at least about 40% by volume, or at least about 50% by volume, or at least about 60% by volume, or at least about 70% by volume, or at least about 80% by volume, or at least about 90% by volume, or at least about 95% by volume, or about 100% by volume of the particles have an esd of less than 2 pm, after which the cellulose pulp is added and the two components are cotriturated to microfibrillate the cellulose pulp fibers.
In one embodiment, the average particle size (d50) of the inorganic particulate material is reduced during the co-curing process. For example the d50 of the inorganic particulate material can be reduced by at least about 10% (measured by a Malvern Mastersizer S machine), for example, the d50 of the inorganic particulate material can be reduced by at least about 20%, or reduced by at least about 30%, or reduce by at least about 50%, or reduce by at least about 50%, or reduce by at least about 60%, or reduce by at least about 70%, or reduce by at least about 80 %, or reduce by at least approximately 90%. For example, an inorganic particulate material that has a d50 of 2.5 pm before co-curing and a d50 of 1.5 pm after co-curing, would have undergone a 40% reduction in particle size. In some embodiments, the average particle size of the inorganic particulate material is not significantly reduced during the co-curing process. By "not significantly reduced" it is understood that the d50 of the inorganic particulate material is reduced by less than
approximately 10%, for example, d50 of the inorganic particulate material is reduced by less than
approximately 5%
The fibrous substrate comprising cellulose can be microfibrillated in the presence of an inorganic material in
particles to obtain microfibrillated cellulose having a d50 in the range of about 5 pm at
approximately 500 pm, measured by laser light scattering. The fibrous substrate comprising cellulose can be microfibrillated in the presence of an inorganic particulate material to obtain microfibrillated cellulose having a d50 equal to or less than about 400 pm, for example, equal to or less than about 300 pm, or equal to or less than about 200 pm, or equal to or less than approximately 150 pm, or equal to or less than approximately 125 pm, or equal to or less than approximately 100 pm, or equal to or less than approximately 90 pm, or equal to or less than approximately 80 pm, or equal at or less than about 70 pm, or equal to or less than about 60 pm, or equal to or less than about 50 pm, or equal to or less than about 40 pm, or equal to or less than about 30 pm, or equal to or less than about 20 pm, or equal to or less than about 10 pm.
The fibrous substrate comprising cellulose can be microfibrillated in the presence of an inorganic particulate material to obtain microfibrillated cellulose having a size of modal fiber particles in the range of about 0.1-500 pm and a size of particles of the inorganic material in modal particles in the range of 0.25-20 pm. The fibrous substrate comprising cellulose can be microfibrillated in the presence of an inorganic particulate material to obtain microfibrillated cellulose having a size of modal fiber particles of at least about 0.5 pm, for example, at least about 10 pm, or at at least about 50 pm, or at least about 100 pm, or at least about 150 pm, or at least about 200 pm, or at least about 300 pm, or at least about 400 pm.
The fibrous substrate comprising cellulose can be microfibrillated in the presence of an inorganic particulate material to obtain microfibrillated cellulose having a fiber bias of 20 to 50, measured by Malvern. Fiber bias (that is, the bias of the fiber particle size distribution) is determined by the following formula:
Bias = 100 x (d30 / d70)
More particularly, microfibrillated cellulose can have a fiber bias of about 25 to about 40, or about 25 to about 35, or about 30 to
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approximately 40.
Crushing is suitably carried out in a crushing vessel such as a drum mill (e.g., bars, balls and autogenous), a stirred mill (e.g., SAM or IsaMill), a tower mill , a Stirred Media Detritor (SMD), or a shredding vessel comprising rotating parallel shredding plates between which the feed to be crushed is fed.
In one embodiment, the crushing vessel is a tower mill. The tower mill may comprise a static zone above one or more crushing zones. A static zone is a region located towards the top of the inside of the tower mill where there is minimal or no crushing and includes microfibrillated cellulose and particulate inorganic material. The static zone is a region where particles of the crushing medium settle in one or more crushing zones of the tower mill.
The tower mill may comprise a sorter above one or more crushing zones. In one embodiment, the classifier is mounted on the upper part adjacent to a static zone. The classifier can be a hydrocyclone.
The tower mill may comprise a sieve over one or more crushing zones. In one embodiment, the screen is located adjacent to a static zone and / or a classifier. The screen may be designed to separate the grinding media from the aqueous product suspension comprising microfibrillated cellulose and particulate inorganic material and to enhance sedimentation of the grinding media.
In one embodiment, the crushing is carried out under conditions of piston flow. Under conditions of piston flow, the flow through the tower is such that there is limited mixing of the crushing materials through the tower. This means that at different points along the length of the tower mill, the viscosity of the aqueous environment will vary as the fineness of microfibrillated cellulose increases. Therefore, in fact, the crushing region in the tower mill can be considered to comprise one or more crushing zones having a characteristic viscosity. One skilled in the art will understand that there are no marked boundaries between adjacent areas with respect to viscosity.
In one embodiment, water is added to the top of the mill near the static zone or the sorter or sieve above one or more crushing zones to reduce the viscosity of the aqueous suspension comprising microfibrillated cellulose and particulate inorganic material. By diluting the product of microfibrillated cellulose and inorganic particulate material at this point in the mill, it has been found that it improves the prevention of the hauling of the grinding medium to the static zone and / or the sorter and / or the sieve. In addition, limited mixing along the tower allows the processing of higher solids content below the tower and diluted at the top with limited return flow of dilution water back down the tower in one or more crushing zones Any suitable amount of water can be added that is effective to dilute the viscosity of the aqueous suspension of the product comprising microfibrillated cellulose and particulate inorganic material. Water can be added continuously during the crushing process, or at regular intervals or at irregular intervals.
In another embodiment, water can be added to one or more crushing zones by one or more water injection points located along the length of the tower mill, each water injection point is located in a position corresponding to one or more crushing zones. Advantageously, the ability to add water at different points along the tower allows greater adjustment of the crushing conditions in any or all positions along the mill.
The tower mill may comprise a drive shaft equipped with a series of drive rotor disks along its length. The action of the impeller rotor discs creates a series of discrete crushing zones along the mill.
In one embodiment, the crushing is carried out in a screening crusher, preferably a Stirred media detritor. The screening crusher may comprise one or more sieves having a nominal aperture size of at least about 250 pm, for example, the one or more sieves may have a nominal aperture size of at least about 300 pm, or at least about 350pm, or at least about 400 pm, or at least about 450 pm, or at least about 500 pm, or at least about
550 pm, or at least about 600 pm, or at least about 650 pm, or at least about
700 pm, or at least about 750 pm, or at least about 800 pm, or at least about
850 pm, or at least approximately 900 pm, or at least approximately 1000 pm.
The sizes of the sieves indicated immediately before can be applied to the embodiments of the tower mill described above.
As indicated above, the crushing can be carried out in the presence of a grinding medium. In one embodiment, the grinding medium is a coarse medium comprising particles having an average diameter in the range of about 1 mm to about 6 mm, for example about 2 mm, or about 3 mm, or about 4 mm, or about 5 mm
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In another embodiment, the grinding medium has a specific gravity of at least about 2.5, for example, at least about 3, or at least about 3.5, or at least about 4.0, or at least about 4, 5, or at least about 5.0, or at least about 5.5, or at least about 6.0.
In another embodiment, the grinding media comprises particles having an average diameter in the range of about 1 mm to about 6 mm and have a specific gravity of at least about 2.5.
In another embodiment, the grinding means comprises particles having an average diameter of approximately 3 mm and a specific gravity of approximately 2.7.
As described above, the grinding medium (or means) may be present in an amount of up to about 70% by volume of the charge. The grinding medium may be present in an amount of at least about 10% by volume of the cargo, for example, at least about 20% by volume of the cargo, or at least about 30% by volume of the cargo, or at less about 40% by volume of the cargo, or at least about 50% by volume of the cargo, or at least about 60% by volume of the cargo
In one embodiment, the grinding medium is present in an amount of approximately 50% by volume of the load.
By "load" is meant the composition that is the feed fed to the crushing vessel. The filler includes water, grinding media, fibrous substrate comprising cellulose and inorganic particulate material, and any other optional additives described herein. The use of a relatively thick and / or dense medium has the advantage of better sedimentation rates (that is, faster) and lower average dragged through the static and / or classifier and / or sieve (sieves).
An additional advantage of using relatively coarse crushing media is that the average particle size (d50) of the inorganic particulate material may not have been significantly reduced during the crushing process so that the energy imparted to the crushing medium is mainly spent on the microfibrillation of the fibrous substrate comprising cellulose.
An additional advantage of using relatively thick sieves is that a relatively coarse or dense crushing medium can be used in the microfibrillation step. In addition, the use of relatively thick sieves (i.e., having a nominal aperture of at least about 250 pm) allows a product with relatively high solids content to be processed and removed from the crusher, which allows a relatively high content feed of solids (comprising fibrous substrate comprising cellulose and inorganic particulate material) are processed in an economically viable process. As discussed above, it has been found that a feed having a high initial solid content is convenient in terms of energy sufficiency. In addition, it has also been found that the product produced (at a given energy) with lower solids content has a thicker particle size distribution.
As described in the "Background" section above, the present invention seeks to address the problem of preparing microfibrillated cellulose economically on an industrial scale.
Therefore, according to one embodiment, the fibrous substrate comprising cellulose and particulate inorganic material is present in the aqueous environment with an initial solid content of at least about 4% by weight, of which at least about 2% in Weight is fibrous substrate comprising cellulose. The initial solids content may be at least about 10% by weight, or at least about 20% by weight, or at least about 30% by weight, or at least about at least 40% by weight. At least about 5% by weight of the initial solids content may be fibrous substrate comprising cellulose, for example, at least about 10%, or at least about 15%, or at least about 20% by weight of the initial solids content may be a fibrous substrate comprising cellulose.
In another embodiment, the crushing is carried out in a cascade of crushing containers, one or more of which may comprise one or more crushing zones. For example, the fibrous substrate comprising cellulose and the inorganic particulate material can be crushed in a cascade of two or more crushing vessels, for example, a cascade of three or more crushing vessels, or a cascade of four or more containers crushing, or a cascade of five or more crushing vessels, or a cascade of six or more crushing vessels, or a cascade of seven or more crushing vessels, or a cascade of eight or more crushing vessels, or a cascade of nine or more crushing vessels, or a cascade comprising up to ten crushing vessels. The cascade of crushing vessels can be operatively connected in series or parallel or a combination of series and parallel. The exit of and / or the entrance to one or more of the crushing vessels in the cascade may be subject to one or more screening stages and / or one or more classification stages.
The total energy expended in a microfibrillation process can also be distributed throughout the cascade crushing vessels. Alternatively, the energy contribution may vary between some or all of the
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crushing vessels in the waterfall.
One skilled in the art will understand that the energy spent per container may vary between containers in the cascade depending on the amount of fibrous substrate that is microfibrillated in each container, and optionally the crushing speed in each container, the duration of crushing in each container. container, the type of crushing medium in each container and the type and amount of particulate inorganic material. The crushing conditions can be varied in each vessel in the cascade in order to control the distribution of the particle size of both microfibrillated cellulose and inorganic particulate material. For example, the size of the grinding media can be varied between successive containers in the cascade in order to reduce the crushing of the inorganic particulate material and direct the crushing of the fibrous substrate comprising cellulose.
In one embodiment, the crushing is carried out in a closed circuit. In another embodiment, the crushing is carried out in an open circuit. Crushing can be done in a batch mode. Crushing can be carried out in a discontinuous mode of recirculation.
As described above, the crushing circuit may include a pre-crushing stage in which the thick inorganic particles are crushed in a crushing container to a predetermined particle size distribution, after which the fibrous material comprising cellulose is Combine with the pre-crushed particulate inorganic material and continuous crushing in the same or different crushing vessel until the desired level of microfibrillation has been obtained.
Since the suspension of material to be crushed can be of a relatively high viscosity, a suitable dispersing agent can preferably be added to the suspension before crushing. The dispersing agent may be, for example, a water-soluble condensed phosphate, poly (silphic acid) or a salt thereof, or a polyelectrolyte, for example a water soluble salt of a poly (acrylic acid) or of a poly (methacrylic acid) that has an average molecular weight in number not exceeding 80,000. The amount of dispersing agent used in general is in the range of 0.1 to 2.0% by weight, based on the weight of the dry inorganic solid particulate material. The suspension can be properly crushed at a temperature in the range of 4 ° C to 100 ° C.
Other additives that may be included during the microfibrillation step include, carboxymethyl cellulose, amphoteric carboxymethyl cellulose, oxidizing agents, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), TEMPO derivatives and wood-degrading enzymes.
The pH of the suspension of material to be crushed may be about 7 or greater than about 7 (ie, basic), for example, the pH of the suspension may be about 8, or about 9, or about 10, or about 11. The pH of the suspension of the material to be crushed may be less than about 7 (ie, acid), for example, the pH of the suspension may be about 6, or about 5, or about 4, or approximately 3. The pH of the suspension of material to be crushed can be adjusted by adding a suitable amount of acid or base. Suitable bases include alkali metal hydroxides, such as, for example, NaOH. Other suitable bases are sodium carbonate and ammonia. Suitable acids include inorganic acids, such as chlortndric acid, sulfuric acid or organic acids. An illustrative acid is orthophosphoric acid.
The amount of the inorganic particulate material and the cellulose pulp in the mixture to be co-sourced may vary in a ratio of about 99.5: 0.5 to about 0.5: 99.5, based on the dry weight of the inorganic particulate material and the amount of dry fiber in the pulp, for example, a ratio of about 99.5: 0.5 to about 50:50 based on the dry weight of the inorganic particulate material and the amount of dry fiber in Pasta. For example, the ratio of the amount of inorganic particulate material and dry fiber can be from about 99.5: 0.5 to about 70:30. In one embodiment, the ratio of particulate inorganic material to dry fiber is approximately 80:20, or for example, approximately 85:15, or approximately 90:10, or approximately 91: 9, or approximately 92: 8, or approximately 93: 7, or about 94: 6, or about 95: 5, or about 96: 4, or about 97: 3, or about 98: 2, or about 99: 1. In a preferred embodiment, the weight ratio of the inorganic particulate material to the dry fiber is approximately 95: 5. In another preferred embodiment, the ratio of the inorganic particulate material to the dry fiber is approximately 90:10. In another preferred embodiment, the weight ratio of the inorganic particulate material to the dry fiber is approximately 85:15. In another preferred embodiment, the weight ratio of the inorganic particulate material to the dry fiber is approximately 80:20.
The total energy input in a typical crushing process to obtain the desired aqueous suspension composition can typically be between about 100 and 1500 kWht "1 based on the total dry weight of the inorganic particulate charge. The total energy input may be less than approximately 1000 kWht "1, for example, less than approximately 800 kWht" 1, less than approximately 600 kWht "1, less than approximately 500 kWht" 1, less than approximately 400 kWht "1, less than approximately 300 kWht, or less than approximately 200 kWht "1. Thus, the authors of the present invention have surprisingly found that a cellulose pulp can be microfibrillated with a relatively low energetic input when co-curing in the presence of particulate inorganic material. As will be evident, the energetic contribution Total per ton of dry fiber in the fibrous substrate comprising cellulose will be less than approximately 10,000
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kWht-1, for example, less than about 9000 kWht-1, or less than about 8000 kWht-1, or less than about 7000 kWht-1, or less than about 6000 kWht-1, or less than about 5000 kWht-1 , for example less than about 4000 kWht-1, less than about 3000 kWht-1, less than about 2000 kWht-1, less than about 1500 kWht-1, less than about 1200 kWht-1, less than about 1000 kWht-1 , or less than approximately 800 kWht-1. The total energy supply varies depending on the amount of dry fiber in the fibrous substrate that is microfibrillated, and optionally the crushing speed and the duration of crushing.
- Homogenization
The microfibrillation of the fibrous substrate comprising cellulose can be carried out in humid conditions in the presence of the inorganic particulate material by a method in which the mixture of cellulose pulp and inorganic particulate material is pressurized (for example, at a pressure of approximately 500 bar) and then it goes to an area of lower pressure. The speed at which the mixture is passed to the low pressure zone is high enough and the pressure of the low pressure zone is low enough to produce microfibrillation of the cellulose fibers. For example, the pressure drop can be done by forcing the mixture through an annular opening having a narrow inlet opening with a much larger outlet opening. The drastic decrease in pressure when the mixture is accelerated by a larger volume (that is, an area of lower pressure) induces cavitation which produces microfibrillation. In one embodiment, the microfibrillation of the fibrous substrate comprising cellulose can be performed in a homogenizer in wet conditions in the presence of particulate inorganic material. In the homogenizer, the mixture of cellulose pulp-inorganic particulate material is pressurized (for example, at a pressure of approximately 500 bar), and forced through a small nozzle or hole. The mixture can be pressurized at a pressure of about 100 to about 1000 bar, for example at a pressure equal to or greater than 300 bar, or equal to or greater than about 500, or equal to or greater than about 200 bar, or equal to or greater than Approximately 700 bar The homogenization subjects the fibers to high shear forces so that when the pressurized cellulose pulp leaves the nozzle or hole, the cavitation produces microfibrillation of the cellulose fibers in the pulp. Additional water can be added to improve the fluidity of the suspension through the homogenizer. The resulting aqueous suspension comprising microfibrillated cellulose and inorganic particulate material can be fed back to the inlet of the homogenizer for multiple passages through the homogenizer. In a preferred embodiment, the inorganic particulate material is a laminar structure mineral, such as caolm. Therefore, homogenization not only facilitates the microfibrillation of cellulose pulp, but also facilitates the delamination of the material into laminated structure particles.
A laminated particulate material, such as caolm, is understood to have a form factor of at least about 10, for example, at least about 15, or at least about 20, or at least about 30, or at least about 40 , or at least about 50, or at least
about 60, or at least about 70, or at least about 80, or at least
about 90, or at least about 100. The form factor, as used herein,
it is a measure of the ratio of the particle diameter to the thickness of the particle for a population of size and shape particles that measure, measured using methods, apparatus and equations of electrical conductivity, described in US Pat. No. 5,576,617.
A suspension of an inorganic laminated particulate material, such as caolm, can be treated in the homogenizer to a distribution of the predetermined particle size in the absence of the fibrous substrate comprising cellulose, after which the fibrous material comprising cellulose is added to the aqueous suspension of the particulate inorganic material and the combined suspension is processed in the homogenizer as described above. The homogenization procedure is continued, including one or more steps through the homogenizer, until the desired microfibrillation level has been obtained. Likewise, the rolled inorganic particulate material can be treated in a shredder until a distribution of the predetermined particle size and then combined with the fibrous material comprising cellulose followed by processing in the homogenizer.
An example homogenizer is a Keep Gaulin homogenizer (APV).
After the microfibrillation step is carried out, the aqueous suspension comprising microfibrillated cellulose and inorganic particulate material can be screened to separate the fiber over a certain size and to separate any crushing media. For example, the suspension can be screened using a sieve having a nominal aperture size selected in order to separate fibers that do not pass through the sieve. The nominal aperture size means the nominal central separation of opposite sides of a square opening or the nominal diameter of a round opening. The sieve can be a BSS sieve (according to BS 1796) having a nominal aperture size of 150 pm, for example, a nominal aperture size of 125 pm, or 106 pm, or 90 pm, or 74 pm, or 63 pm, or 53 pm, 45 pm, or 38 pm. In one embodiment, the aqueous suspension is screened using a sieve having a nominal opening of 125 pm. Then the water can optionally be removed from the aqueous suspension.
The aqueous suspension
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The aqueous suspensions of this invention produced in accordance with the methods described above are suitable for use in a method of making paper or coated paper.
Thus, the present invention is directed to an aqueous suspension comprising, consisting of, or consisting essentially of microfibrillated cellulose and an inorganic particulate material and other optional additives. The aqueous suspension is suitable for use in a method of making paper or coated paper. The other optional additives include dispersant, biocide, suspension auxiliaries, salt (s) and other additives, for example, starch or carboxymethyl cellulose or polymers, which can facilitate the interaction of mineral and fiber particles during or after crushing.
The inorganic particulate material may have a particle size distribution such that at least about 10% by weight, for example at least about 20% by weight, for example at least
about 30% by weight, for example at least about 40% by weight, for example at least
about 50% by weight, for example at least about 60% by weight, for example at least
about 70% by weight, for example at least about 80% by weight, for example at least
about 90% by weight, for example at least about 95% by weight, or for example about 100% of the particles have an e.s.d. less than 2 pm.
In another embodiment, the inorganic particulate material may have a particle size distribution, measured by a Malvern Mastersizer S machine, so that at least about 10% by volume, for example at least about 20% by volume, for example at at least about 30% by volume, for example at least about 40% by volume, for example at least about 50% by volume, for example at least about 60% by volume, for example at least about 70% by volume, for example at less about 80% by volume, for example at least about 90% by volume, for example at least about 95% by volume, or for example about 100% by volume of the particles have an esd less than 2 pm.
The amount of inorganic particulate material and cellulose pulp in the mixture to be co-sourced may vary in a ratio of about 99.5: 0.5 to about 0.5: 99.5, based on the dry weight of the material inorganic in particles and the amount of dry fiber in the paste, for example, a ratio of about 99.5: 0.5 to about 50:50 based on the dry weight of the inorganic material in particles and the amount of dry fiber in the paste pasta. For example, the ratio of the amount of inorganic material in particles and dry fiber can be from about 99.5: 0.5 to about 70:30. In one embodiment, the ratio of inorganic particulate material to dry fiber is approximately 80:20, or for example, approximately 85:15, or approximately 90:10, or approximately 91: 9, or approximately 92: 8, or approximately 93: 7, or about 94: 6, or about 95: 5, or about 96: 4, or about 97: 3, or about 98: 2, or about 99: 1. In a preferred embodiment, the weight ratio of the inorganic particulate material to the dry fiber is approximately 95: 5. In another preferred embodiment, the weight ratio of the inorganic particulate material to the dry fiber is approximately 90:10. In another preferred embodiment, the weight ratio of the inorganic particulate material to the dry fiber is approximately 85:15. In another preferred embodiment, the weight ratio of the inorganic particulate material to the dry fiber is approximately 80:20.
In one embodiment, the composition does not include fibers that are too large to pass through a BSS sieve (according to BS 1796) that has a nominal aperture size of 150 pm, for example, a nominal aperture size of 125 pm, 106 pm, or 90 pm, or 74 pm, or 63 pm, or 53 pm, 45 pm, or 38 pm. In one embodiment, the aqueous suspension is screened using a BBS sieve having a nominal aperture of 125 pm.
Therefore, it will be understood that the amount (i.e.,% by weight) of microfibrillated cellulose in the aqueous suspension after crushing or homogenization may be less than the amount of dry fiber in the pulp if the crushed or homogenized suspension is treated to separate the fibers above a selected size. Therefore, the relative amounts of paste and inorganic material in particles fed to the grinder or homogenizer can be adjusted depending on the amount of microfibrillated cellulose that is required in the aqueous suspension after separating the fibers over a selected size.
In one embodiment, the inorganic particulate material is an alkaline earth metal carbonate, for example, calcium carbonate. The inorganic particulate material may be crushed calcium carbonate (GCC) or precipitated calcium carbonate (PCC), or a mixture of GCC and PC. In another embodiment, the inorganic particulate material is a naturally rolled mineral, for example, caolm. The inorganic particulate material may be a mixture of caolm and calcium carbonate, for example, a mixture of caolm and GCC, or a mixture of caolm and PCC, or a mixture of caolm, GCC and PCC.
In another embodiment, the aqueous suspension is treated to separate at least part or substantially all of the water to form a partially dry or essentially completely dry product. For example, at least about 10% by volume of water can be separated in the aqueous suspension from the aqueous suspension, for example, at least about 20% by volume, or at least about 30% by volume, or at least about 40% by volume, or at least about 50% by volume, or at least about 60% by volume, or at least about 70% by volume or at least about
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80% by volume or at least about 90% by volume, or at least about 100% by volume of water in the aqueous suspension. Any suitable technique can be used to separate water from the aqueous suspension, including, for example, by gravity, ford-assisted drainage, with or without pressure or evaporation, or by filtration, or by a combination of these techniques. The partially dried or essentially completely dried product will comprise microfibrillated cellulose and particulate inorganic material and any other optional additives that can be added to the aqueous suspension before drying. The partially dry or essentially completely dry product can be stored or packaged for sale. The partially dry or essentially completely dry product may optionally be rehydrated and incorporated into compositions for the manufacture of paper and other paper products, as described herein.
Paper products and procedures for preparing them
The aqueous suspension comprising microfibrillated cellulose and inorganic particulate material can be incorporated into papermaking compositions. The term "paper product", used in connection with the present invention, should be understood to mean all forms of paper, including cardboard, such as, for example, white coated cardboard, coating cardboard, cardboard, coated cardboard, and the like. There are numerous types of paper, coated or uncoated, which can be made in accordance with the present invention, which include paper suitable for books, magazines, newspapers, and the like, and office papers. The paper can be calendered or superheated as appropriate; for example, supercalendered magazine paper for rotogravure and offset printing can be made in accordance with the present methods. Paper suitable for light weight coating (LWC), medium weight coating (MWC) or finishing pigmentation machine (MFP) can also be made in accordance with the present methods. Coated paper and cardboard having barrier properties suitable for food packaging and the like, can also be made in accordance with the present methods.
In a typical papermaking process, a pulp containing cellulose is prepared by any suitable chemical or mechanical treatment, or combinations thereof, which are all well known in the art. The paste can come from any suitable source such as wood, herbs (e.g., sugar cane, bamboo) or rags (e.g., textile waste, cotton, hemp or linen). The paste can be bleached according to procedures that are well known to those skilled in the art and the procedures suitable for use in the present invention will be readily apparent. The bleached cellulose pulp can be beaten, refined or both, to a refining of the predetermined pulp (described in the art as the Canadian degree of refining (CSF) in cm3). Then a suitable paper pulp is prepared from the whipped and bleached pulp.
The papermaking composition of the present invention typically comprises, in addition to the aqueous suspension of microfibrillated cellulose and inorganic particulate material, paper pulp and other conventional additives known in the art. The papermaking composition of the present invention may comprise up to about 50% by weight of inorganic particulate material from the aqueous suspension comprising microfibrillated cellulose and inorganic particulate material based on the total dry content of the composition for manufacturing. of paper. For example, the papermaking composition may comprise at least about 2% by weight, or at least about 5% by weight, or at least about 10% by weight, or at least about 15% by weight, or at least about 20% by weight, or at least about 25% by weight, or at least about 30% by weight, or at least about 35% by weight, or at least about 40% by weight, or at least about 45% by weight , or at least about 50% by weight, or at least about 60% by weight, or at least about 70% by weight, or at least about 80% by weight of particulate inorganic material from the aqueous suspension comprising microfibrillated cellulose and inorganic particulate material based on the total dry content of the papermaking composition. The microfibrillated cellulose material is characterized by a fiber bias of 20 to 50, or about 25 to about 40, or about 25 to 35, or about 30 to about 40. The papermaking composition can also Containing a non-ionic, cationic or anionic retention aid or microparticle retention system in an amount in the range of about 0.1 to 2% by weight, based on the dry weight of the aqueous suspension comprising microfibrillated cellulose and inorganic material in particles. It may also contain a sizing agent that can be, for example, a long chain alkyl kethene dimer, a wax emulsion or a succinic acid derivative. The composition may also contain dye and / or an optical gloss agent. The composition may also comprise dry and wet strength auxiliaries, such as, for example, starch or copolymers of epichlorohydrin.
In accordance with the eighth aspect described above, the present invention is directed to a process for making a paper product comprising: (i) obtaining or preparing a fibrous substrate comprising cellulose in the form of a paste suitable for making a paper product ; (ii) preparing a papermaking composition from the pulp of step (i), the aqueous suspension of this invention comprising microfibrillated cellulose and particulate inorganic material, and other optional additives (such as, for example, a retention aid and other additives such as those described above); and (iii) forming a paper product from said composition for the manufacture of paper. As indicated above, the step of forming a pulp can take place in the crushing container or homogenizer by adding the fibrous substrate comprising cellulose in a dry state, for example, in the form of a waste or waste of dry paper. directly in the shredder bowl.
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The aqueous environment in the shredder bowl will then facilitate the formation of a paste.
In one embodiment, an additional filler component (i.e., a filler component other than inorganic particulate material that is co-ground with the fibrous substrate comprising cellulose) can be added to the papermaking composition in step (ii ). The example loading components are PCC, GCC, caolm or mixtures thereof. An example of PCC is PCC scalenoedrico. In one embodiment, the weight ratio of the inorganic particulate material to the additional filler component in the papermaking composition is from about 1: 1 to about 1:30, for example, from about 1: 1 to about 1:20 , for example, from about 1: 1 to about 1:15, for example from about 1: 1 to about 1:10, for example from about 1: 1 to about 1: 7, for example, from about 1: 3 to about 1: 6, or about 1: 1, or about 1: 2, or about 1: 3, or about 1: 4, or about 1: 5. Paper products made from said papermaking compositions may have greater strength compared to paper products comprising only inorganic particulate material, such as, for example, PCC, as filler. Paper products made from such papermaking compositions may have greater strength compared to a paper product in which the inorganic particulate material and a fibrous substrate comprising cellulose are prepared (e.g., crushed ) separately and mixed to form a papermaking composition. Likewise, paper products prepared from a papermaking composition according to the present invention may have a resistance that is comparable to paper products that comprise less inorganic particulate material. In other words, paper products can be prepared from a papermaking composition according to the present with larger amounts of load without loss of resistance.
The stages in the formation of a final paper product from a papermaking composition are conventional and well known in the art, and generally comprise the formation of paper sheets having an objective basis weight, depending on the type of paper being made.
Additional economic benefits can be achieved by the methods of the present invention, in that the cellulose substrate for making the aqueous suspension can be obtained from the same cellulose pulp formed to make the papermaking composition and paper product final. Thus, and in accordance with the ninth aspect described above, the present invention is directed to an integrated process for making a paper product comprising: (i) obtaining or preparing a fibrous substrate comprising cellulose in the form of a paste suitable for make a paper product; (ii) microfibrillating a part of said fibrous substrate comprising cellulose according to the first aspect of the invention to prepare an aqueous suspension comprising microfibrillated cellulose and particulate inorganic material; (iii) preparing a composition for the manufacture of paper from the pulp in step (i), the aqueous suspension prepared in step (ii), and other optional additives; and (iv) forming a paper product from said composition for the manufacture of paper.
Therefore, since the cellulose substrate for preparing the aqueous suspension has already been prepared for the purpose of making the papermaking compositions, the step of forming the aqueous suspension does not necessarily require a separate stage of preparing the fibrous substrate. which comprises cellulose.
It has surprisingly been found that paper products prepared using the aqueous suspension of the present invention have improved physical and mechanical properties while at the same time allowing the incorporation of particulate inorganic material at relatively high loading levels. Therefore, improved paper can be prepared with relatively lower cost. For example, it has been surprisingly found that paper products prepared from papermaking compositions comprising the aqueous suspension of the present invention have a better retention of the inorganic particulate load compared to paper products that They do not contain any microfibrillated cellulose. It has also been surprisingly found that paper products prepared from papermaking compositions comprising the aqueous suspension of the present invention have better burst resistance and tensile strength. In addition, the incorporation of microfibrillated cellulose has been found to reduce porosity compared to paper comprising the same amount of filler but not microfibrillated cellulose. This is advantageous since high load levels in general are associated with relatively high porosity values and are detrimental to printability.
Paper coating composition and coating procedure
The aqueous suspension of the present invention can be used as a coating composition without the addition of additional additives. However, optionally, a small amount of thickener such as carboxymethyl cellulose or acrylic thickeners that swell in water or associated thickeners can be added.
The coating composition according to the present invention may contain one or more additional optional components, if desired. Such additional components, when present, are suitably selected from known additives for paper coating compositions. Some of these optional additives may provide more than one function in the coating composition. Examples of known classes of optional additives are as follows:
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(a) one or more additional pigments: the compositions described herein may be used as pigments alone in paper coating compositions, or they may be used in conjunction with each other or with other known pigments, such as, for example, calcium sulfate, white saten and the so-called "plastic pigment". When a mixture of pigments is used, the total content of pigment solids is preferably present in the composition in an amount of at least about 75% by weight of the total weight of the dry components of the coating composition;
(b) one or more binding or coagglutinating agents: for example, latex, which may optionally be carboxylated, which includes: a styrene-butadiene rubber latex; a latex of acrylic polymer; a polyvinyl acetate latex; or a latex of styrene-acrylic copolymer, starch derivatives, sodium carboxymethyl cellulose, polyvinyl alcohol and proteins;
(c) one or more crosslinking agents; for example, at levels up to about 5% by weight; p. eg glyoxal, melamine-formaldehyde resins; ammonium and zirconium carbonates; one or more dry or wet repellent enhancement additives: p. e.g., at levels up to about 2% by weight, e.g. eg, melamine resin, emulsions of polyethylene, urea-formaldehyde, melamine-formaldehyde, polyamide, calcium stearate, styrene-maleic antidrido and others; one or more abrasion resistance additives and improvement by dry or wet friction: p. e.g., at levels up to about 2% by weight, e.g. eg, glyoxal-based resins, oxidized polyethylenes, melamine resins, urea-formaldehyde, melamine-formaldehyde, polyethylene wax, calcium stearate and others; one or more water resistance additives; p. e.g., at levels up to about 2% by weight, e.g. eg, oxidized polyethylenes, ketone resin, anionic latex, polyurethane, SMA, glyoxal, melamine resin, urea-formaldehyde, melamine-formaldehyde, polyamide, glyoxal, stearates and other commercially available materials for this function ;
(d) one or more water retention aids: for example, at levels up to about 2% by weight, e.g. eg, sodium carboxymethyl cellulose, hydroxyethyl cellulose, PVOH (polyvinyl alcohol), starches, proteins, polyacrylates, gums, alginates, polyacrylamide-bentonite, and other commercially available products sold for such applications;
(e) one or more viscosity modifiers and / or thickeners: for example, at levels up to about 2% by weight, e.g. eg, associative acrylic thickeners, polyacrylates, copolymers in emulsion, dicianamides, triols, polyoxyethylene ether, urea, sulfated castor oil, polyvinyl pyrrolidone, CMC (carboxymethyl celluloses, for example, sodium carboxymethyl cellulose), sodium alginate, copical sodium, silica gum, sodium gum, silica gum of acrylic acid, HMC (hydroxymethyl celluloses), HEC (hydroxyethyl celluloses) and others;
(f) one or more lubricity / calendering aides: for example, at levels up to about 2% by weight, e.g. eg, calcium stearate, ammonium stearate, zinc stearate, wax emulsions, waxes, alkyl ketene dimers, glycols; one or more maintenance additives for bright inks; p. e.g., at levels up to about 2% by weight, e.g. eg, oxidized polyethylenes, polyethylene emulsions, waxes, casema, guar gum, CMC, HMC, calcium stearate, ammonium stearate, sodium alginate and others;
(g) one or more dispersants: the dispersant is a chemical additive capable, when present in sufficient quantity, of acting on the particles of inorganic particulate material to prevent or effectively limit the flocculation or agglomeration of the particles to a desired extent, in accordance with normal processing requirements. The dispersant can be present at levels of up to about 1% by weight, and includes, for example, polyelectrolytes, such as polyacrylates and copolymers containing polyacrylate species, especially polyacrylate salts (e.g., sodium and aluminum optionally with a sodium phosphate condensed with group II), non-ionic surfactants, alkanolamine and other reagents commonly used for this function. The dispersant can be selected, for example, from conventional dispersant materials commonly used in the processing and grinding of inorganic particulate materials. Such dispersants will be recognized by those skilled in the art. In general they are water soluble salts capable of supplying anionic species that in their effective amounts can be adsorbed on the surface of the inorganic particles and thus inhibit the aggregation of the particles. Unsolvated salts suitably include alkali metal cations such as sodium. Solvation can be helped in some cases by making the aqueous suspension slightly alkaline. Examples of suitable dispersants include: water soluble condensed phosphates, e.g. eg, polymetaphosphate salts [general form of sodium salts (NaPO3) x] such as tetrasodium metaphosphate or the so-called "sodium hexametaphosphate" (Graham salt); water-soluble poly (silphic acid) salts; polyelectrolytes; salts of homopolymers or copolymers of acrylic acid or methacrylic acid, or salts of polymers of other derivatives of acrylic acid, which suitably have a weighted average molecular weight of less than about 20,000. Especially preferred are sodium hexametaphosphate and poly (sodium acrylate), the latter having a weight average molecular weight in the range of about 1,500 to about 10,000;
(h) one or more defoamers: for example, at levels up to about 1% by weight, e.g. eg, mixtures of surfactants, tributyl phosphate, polyoxyethylene fatty esters plus fatty alcohols, fatty acid soaps, silicone emulsions and other compositions containing silicone, wax and inorganic particulate materials in mineral oil, mixtures of emulsified hydrocarbons and other compounds sold in the market to carry out this function;
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(i) one or more optical brightening agents (OBA) and fluorescent whitening agents (FWA): for example, at levels up to about 1% by weight, e.g. eg, stilbene derivatives;
(j) one or more dyes: for example, at levels up to about 0.5% by weight;
(k) one or more biocidal / decomposition control agents: for example, at levels up to about 1% by weight, e.g. eg, oxidizing biocides such as gaseous chlorine, gaseous chlorine dioxide, sodium hypochlorite, sodium hypobromite, hydrogen, peroxide, peracetic oxide, ammonium bromide / sodium hypochlorite, or non-oxidizing biocides such as GLUT (Glutaraldehyde, CAS No. 90045-36 -6), ISO (CIT / MIT) (Isothiazolinone, CAS No. 55956-849 and 96118-96-6), ISO (BIT / MIT) (Isothiazolinone), ISO (BIT) (Isothiazolinone, CAS No. 2634-33 -5), DBNPA, BNPD (Bronopol), NaOPP, carbamate, thione (Dazomet), EDdM - dimetanol (O-formial), HT - Triazine (N-formial), THPS - tetrakis (O-formial), TMAD - diurea (N-formial), metaborate, sodium dodecylbenzenesulfonate, thiocyanate, organosulfide, sodium benzoate and other compounds sold in the market for this function, p. eg, the variety of biocidal polymers sold by Nalco;
(l) one or more leveling and leveling aids: for example, at levels up to about 2% by weight, e.g. eg, non-ionic polyol, polyethylene emulsions, fatty acid, esters and alcohols derivatives, alcohol / ethylene oxide, calcium stearate and other compounds sold in the market for this function;
(m) one or more grease and oil resistance additives: for example, at levels up to about 2% by weight, e.g. eg, oxidized polyethylenes, latex, SMA (styrene-maleic anhydride), polyamide, waxes, alginate, protema, CMC, and HMC.
Any of the above additives and types of additives may be used alone or mixed with each other and with other additives, if desired.
For all the above additives, the indicated weight percentages are based on the dry weight of the particulate inorganic material (100%) present in the composition. When the additive is present in a minimum amount, the minimum amount may be approximately 0.01% by weight, based on the dry weight of pigment
The coating process is carried out using conventional techniques that are well known to the person skilled in the art. The coating process may also involve calendering or supercalandering of the coated product.
The methods of coating paper and other sheet materials, and the apparatus for carrying out the methods, are widely published and well known. Such known methods and apparatus can be conveniently used to prepare coated paper. For example, there is a review of these methods published in Pulp and Paper International, May 1994, page 18 and following. The sheets can be coated in the sheet forming machine, that is, "in the machine" or "out of the machine" in a coating machine or coating machine. The use of compositions with high solids content in the coating method is desirable because it allows less water to evaporate later. However, as is well known in the art, the level of solids should not be so high that problems of high viscosity and leveling are introduced. Coating methods can be performed using an apparatus comprising (i) an application to apply the coating composition to the material to be coated, and (ii) a dosing device to ensure that a correct level of coating composition is applied , the dosing device is downstream of it. Alternatively, the correct amount of the coating composition can be applied to the applicator by means of the dosing device, e.g. eg, as a movie press. At the points of application and dosage of the coating, the continuous paper support has a support roller, p. eg, by one or two applicators, to nothing (that is, only tension). The time that the coating is in contact with the paper before the excess is finally removed is the stop time, and this can be short, long or variable.
The coating is usually added by a coating head in a coating station. According to the desired quality, paper grades are uncoated, single coated, double coated and even triple coated. When more than one coating is provided, the initial coating (precoating) may have a cheaper and optionally thicker pigment formulation in the coating composition. A coating device that applies the coating on each side of the paper will have two or four coating heads, depending on the number of coating layers applied on each side. The majority of the coating heads apply coating only on one side at a time, but some roller liners (eg, film presses, gate rollers, and glue presses) cover both sides in one pass.
Examples of known coaters that can be used include, without limitation, pneumatic blade coaters, pallet coaters, roller bar coats, bar coats, multi head coats, roller coater, roller coater or pallets, high coater gloss, laboratory coatings, etch coatings, coating coatings, liquid application systems, reverse roller coatings, curtain coatings, spray coatings and extrusion coatings.
Water can be added to solids comprising the coating composition to give a concentration of
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solids which is preferably such that, when the composition is applied on a sheet with a desired target coating weight, the composition has a rheology that is suitable to allow the composition to be applied with a pressure (i.e., a trowel pressure) between 1 and 1.5 bar.
Calendering is a well known procedure in which the smoothness and gloss of the paper is improved and the bulge is reduced by passing a sheet of coated paper between rollers or laminators one or more times. Normally, elastomer-coated laminators are used to give pressure to high solids compositions. An elevated temperature can be applied. One or more steps (e.g., up to about 12, or sometimes higher) can be applied through the rollers.
Coated paper products prepared in accordance with the present invention and containing optical brightening agent in the coating may have a medium gloss according to ISO 11475 which is at least 2 units larger, for example at least 3 units major, compared to a coated paper product that does not comprise microfibrillated cellulose, which has been prepared in accordance with the present invention. Coated paper products according to the present invention may have a Parker Print Surf smoothness measured in accordance with ISO 8971-4 (1992) which is at least 0.5 pm smoother, for example at least about 0.6 pm smoother, or at least about 0.7 pm smoother, compared to a coated paper product that does not comprise microfibrillated cellulose that has been prepared in accordance with the present invention.
For the avoidance of doubt, this application addresses the subject matter described in the following numbered paragraphs:
1. A paper product comprising a paper coating composition that includes a coprocessed microfibrillated cellulose composition and inorganic particulate material, wherein the paper product has:
i) a first tensile strength greater than a second tensile strength of the paper product comprising the paper coating composition devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material;
ii) a first tear strength greater than a second tear resistance of the paper product comprising the paper coating composition devoid of the co-processed microfibrillated cellulose composition and particulate inorganic material; I
iii) a first gloss greater than a second gloss of the paper product comprising the paper coating composition devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material, and / or
iv) a first burst resistance greater than a second burst resistance of the paper product comprising the paper coating composition devoid of the co-processed microfibrillated cellulose composition and particulate inorganic material; I
v) a first sheet light scattering coefficient greater than a second sheet light scattering coefficient of the paper product comprising the paper coating composition devoid of the co-processed microfibrillated cellulose composition and inorganic material in particles; I
vi) a first porosity less than a second porosity of the paper product comprising the paper coating composition devoid of the composition of coprocessed microfibrillated cellulose and particulate inorganic material.
2. The paper product of paragraph 1, wherein the paper coating composition comprises a functional coating for the packaging of liquids, barrier coatings or printed electronic applications.
3. The paper product of paragraph 1 or 2, which further comprises a second coating comprising a polymer, a metal, an aqueous composition, or a combination thereof.
4. The paper product of paragraphs 1, 2 or 3, which also has a first wet vapor transmission rate (MVTR) greater than a second MVTR of the paper product comprising the paper coating composition devoid of a composition of coprocessed microfibrillated cellulose and inorganic particulate material.
5. The paper product of any of paragraphs 1-4, wherein the paper comprises from about 25% by weight to about 35% by weight of the composition of coprocessed microfibrillated cellulose and particulate inorganic material.
Microfibrillation in the absence of the crushable particulate inorganic material
In another aspect, the present invention is directed to a method for preparing an aqueous suspension comprising microfibrillated cellulose, the method comprising a microfibrillation step of a fibrous substrate that
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it comprises cellulose in an aqueous environment, by crushing in the presence of a crushing medium that is to be separated after the crushing is completed, where the crushing is carried out in a tower mill or a screening crusher, and where the Crushing is carried out in the absence of the crushable particulate inorganic material.
A crushable particulate inorganic material is a material that is crushed in the presence of the crushing medium.
The particle crushing medium may be of a natural or synthetic material. The grinding medium may comprise, for example, balls, beads or pellets of any mineral, ceramic or hard metal. Such materials may include, for example, alumina, zirconia, zirconium silicate, aluminum silicate or mullite-rich material that is produced by calcining the kaolimatic clay at a temperature in the range of about 1300 ° C to about 1800 ° C . For example, in some embodiments, a Carbolite® grinding medium is preferred. Alternatively, natural sand particles of a suitable particle size can be used.
In general, the type of and the size of the particles of the grinding medium that is selected for use in the invention may depend on properties such as, e.g. eg, the size of particles and the chemical composition, the feed suspension of the material to be crushed. Preferably, the particle grinding medium comprises particles having an average diameter in the range of about 0.5 mm to about 6 mm. In one embodiment, the particles have an average diameter of at least about 3 mm.
The grinding medium may comprise particles having a specific gravity of at least about 2.5. The grinding medium may comprise particles having a specific gravity of at least about 3, or at least about 4 or at least about 5, or at least about 6.
The crushing medium (or means) may be present in an amount of up to about 70% by volume of the load. The grinding medium may be present in an amount of at least about 10% by volume of the cargo, for example, at least about 20% by volume of the cargo, or at least about 30% by volume of the cargo, or at less about 40% by volume of the cargo, or at least about 50% by volume of the cargo, or at least about 60% by volume of the cargo.
The fibrous substrate comprising cellulose can be microfibrillated to obtain microfibrillated cellulose having a d50 in the range of about 5 pm to about 500 pm, measured by laser light scattering. The fibrous substrate comprising cellulose can be microfibrillated to obtain microfibrillated cellulose having a d50 equal to or less than about 400 pm, for example, for example equal to or less than about 300 pm, or equal to or less than about 200 pm, or equal to or less than approximately 150 pm, or equal to or less than approximately 125 pm, or equal to or less than approximately 100 pm, or equal to or less than approximately 90 pm, or equal to or less than approximately 80 pm, or equal to or less than approximately 70 pm , or equal to or less than approximately 60 pm, or equal to or less than approximately 50 pm, or equal to or less than approximately 40 pm, or equal to or less than approximately 30 pm, or equal to or less than approximately 20 pm, or equal to or less from about 10 pm.
The fibrous substrate comprising cellulose can be microfibrillated to obtain microfibrillated cellulose having a size of modal fiber particles in the range of about 0.1-500 pm, measured by laser light scattering. The fibrous substrate comprising cellulose can be microfibrillated in the presence to obtain microfibrillated cellulose having a size of modal fiber particles of at least about 0.5 pm, for example, at least about 10 pm, or at least about 50 pm, or at least about 100 pm, or at least about 150 pm, or at least about 200 pm, or at least about 300 pm, or at least about 400 pm.
The fibrous substrate comprising cellulose can be microfibrillated to obtain microfibrillated cellulose having a fiber bias of 10 to 50, measured by Malvern (laser light scattering.). Fiber bias (that is, the bias of the fiber particle size distribution) is determined by the following formula:
Bias = 100 x (d30 / d70)
More particularly, microfibrillated cellulose can have a fiber bias of about 25 to about 40, or about 25 to about 35, or about 30 to about 40.
In one embodiment, the crushing vessel is a tower mill. The tower mill may comprise a static zone above one or more crushing zones. A static zone is a region located towards the top of the inside of the tower mill where there is minimal or no crushing and includes microfibrillated cellulose and particulate inorganic material. The static zone is a region where particles of the crushing medium settle in one or more crushing zones of the tower mill.
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The tower mill may comprise a sorter above one or more crushing zones. In one embodiment, the classifier is mounted at the top and located adjacent to a static zone. The classifier can be a hydrocyclone.
The tower mill may comprise a sieve over one or more crushing zones. In one embodiment, the screen is located adjacent to a static zone and / or a classifier. The sieve may be designed to separate the grinding media from the aqueous suspension of the product comprising microfibrillated cellulose and to enhance the sedimentation of the grinding media.
In one embodiment, the crushing is carried out under conditions of piston flow. Under conditions of piston flow, the flow through the tower is such that there is limited mixing of the crushing materials through the tower. This means that at different points along the length of the tower mill, the viscosity of the aqueous environment will vary as the fineness of microfibrillated cellulose increases. Therefore, in fact, the crushing region in the tower mill can be considered to comprise one or more crushing zones having a characteristic viscosity. One skilled in the art will understand that there are no marked boundaries between adjacent areas with respect to viscosity.
In one embodiment, water is added to the top of the mill next to the static zone or the sorter or sieve above one or more crushing zones to reduce the viscosity of the aqueous suspension comprising microfibrillated cellulose in these areas in the mill . By diluting the microfibrillated cellulose product at this point in the mill, it has been found that it improves the prevention of shredding of the crushing medium into the static zone and / or the sorter and / or sieve. In addition, limited mixing along the tower allows the processing of higher solids content below the tower and diluted at the top with limited return flow of dilution water back down the tower in one or more crushing zones Any suitable amount of water can be added that is effective to dilute the viscosity of the aqueous suspension of the product comprising microfibrillated cellulose and particulate inorganic material. Water can be added continuously during the crushing process, or at regular intervals or at irregular intervals.
In another embodiment, water can be added to one or more crushing zones by one or more water injection points located along the length of the tower mill, the point or each water injection point being located in a position. which corresponds to one or more crushing zones. Advantageously, the ability to add water at different points along the tower allows greater adjustment of the crushing conditions in any or all positions along the mill.
The tower mill may comprise a vertical drive shaft equipped with a series of drive rotor disks along its length. The action of the impeller rotor discs creates a series of discrete crushing zones along the mill.
In another embodiment, the crushing is carried out in a screening crusher, preferably a Stirred media detritor. The screening crusher may comprise one or more sieves having a nominal aperture size of at least about 250 pm, for example, the one or more sieves may have a nominal aperture size of at least about 300 pm, or at least about 350pm, or at least about 400 pm, or at least about 450 pm, or at least about 500 pm, or at least about
550 pm, or at least about 600 pm, or at least about 650 pm, or at least about
700 pm, or at least about 750 pm, or at least about 800 pm, or at least about
850 pm, or at least approximately 900 pm, or at least approximately 1000 pm.
The sizes of the sieves indicated immediately before can be applied to the embodiments of the tower mill described above.
As indicated above, the crushing can be carried out in the presence of a grinding medium. In one embodiment, the grinding medium is a coarse medium comprising particles having an average diameter in the range of about 1 mm to about 6 mm, for example about 2 mm, or about 3 mm, or about 4 mm, or about 5 mm
In another embodiment, the grinding medium has a specific gravity of at least about 2.5, for example, at least about 3, or at least about 3.5, or at least about 4.0, or at least about 4, 5, or at least about 5.0, or at least about 5.5, or at least about 6.0.
As described above, the grinding medium (or means) may be present in an amount of up to about 70% by volume of the charge. The grinding medium may be present in an amount of at least about 10% by volume of the cargo, for example, at least about 20% by volume of the cargo, or at least about 30% by volume of the cargo, or at less about 40% by volume of the cargo, or at least about 50% by volume of the cargo, or at least about 60% by volume of the cargo
In one embodiment, the grinding medium is present in an amount of approximately 50% by volume of the load.
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By "load" is meant the composition that is the feed fed to the crushing vessel. The filler includes water, grinding media, fibrous substrate comprising cellulose, and any other optional additives (other than those described herein).
The use of a relatively thick and / or dense medium has the advantage of better sedimentation rates (that is, faster) and less average dragged along the static and / or classifier and / or sieve (sieves).
An additional advantage of using relatively thick sieves is that a relatively coarse or dense crushing medium can be used in the microfibrillation step. In addition, the use of relatively thick sieves (i.e., having a nominal aperture of at least about 250 pm) allows a product with relatively high solids content to be processed and removed from the disposer, which allows a feed with relatively high solids content (which comprises fibrous substrate comprising cellulose and inorganic particulate material) is processed in an economically viable process. As discussed above, it has been found that a feed having a high initial solid content is convenient in terms of energy sufficiency. In addition, it has also been found that the product produced (at a given energy) with lower solids content has a thicker particle size distribution.
As described in the "Background" section above, the present invention seeks to address the problem of preparing microfibrillated cellulose economically on an industrial scale.
Therefore, according to one embodiment, the fibrous substrate comprising cellulose is present in the aqueous environment with an initial solid content of at least about 1% by weight. The fibrous substrate comprising cellulose may be present in the aqueous environment with an initial solid content of at least about 2% by weight, for example, at least about 3% by weight, or at least about 4% by weight. Typically, the initial solids content will be at most about 10% by weight.
In another embodiment, the crushing is carried out in a crushing vessel cascade, one or more of which may comprise one or more crushing zones. For example, the fibrous substrate comprising cellulose can be crushed in a cascade of two or more crushing vessels, for example, a cascade of three or more crushing vessels, or a cascade of four or more crushing vessels, or a cascade of five or more crushing vessels, or a cascade of six or more crushing vessels, or a cascade of seven or more crushing vessels, or a cascade of eight or more crushing vessels, or a cascade of nine or more recipients of crushing, or a cascade comprising up to ten crushing vessels. The cascade of crushing vessels can be operatively connected in series or parallel or a combination of series and parallel. The exit of and / or the entrance to one or more of the crushing vessels in the cascade may be subject to one or more screening stages and / or one or more classification stages.
The total energy expended in a microfibrillation process can also be distributed throughout the cascade crushing vessels. Alternatively, the energy input may vary between some or all of the crushing vessels in the waterfall.
One skilled in the art will understand that the energy spent per container may vary between containers in the cascade depending on the amount of fibrous substrate that is microfibrillated in each container, and optionally the crushing speed in each container, the duration of crushing in each container. container, the type of crushing medium in each container. The crushing conditions can be varied in each vessel in the cascade in order to control the distribution of the particle size of the microfibrillated cellulose.
In one embodiment, the crushing is carried out in a closed circuit. In another embodiment, the crushing is carried out in an open circuit.
Since the suspension of material to be crushed can be of a relatively high viscosity, a suitable dispersing agent can preferably be added to the suspension before crushing. The dispersing agent may be, for example, a water-soluble condensed phosphate, poly (silphic acid) or a salt thereof, or a polyelectrolyte, for example a water soluble salt of a poly (acrylic acid) or of a poly (methacrylic acid) that has an average molecular weight in number not exceeding 80,000. The amount of dispersing agent used in general is in the range of 0.1 to 2.0% by weight, based on the weight of the dry inorganic solid particulate material. The suspension can be properly crushed at a temperature in the range of 4 ° C to 100 ° C.
Other additives that may be included during the microfibrillation stage include: carboxymethyl cellulose, amphoteric carboxymethyl cellulose, oxidizing agents, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), TEMPO derivatives and wood-degrading enzymes.
The pH of the suspension of material to be crushed may be about 7 or greater than about 7 (ie, basic), for example, the pH of the suspension may be about 8, or about 9, or about 10, or about 11. The pH of the suspension of the material to be crushed may be less than about 7 (ie, acid), for example, the pH of the suspension may be about 6, or about 5, or about 4, or approximately 3. The pH of the suspension of material to be crushed can be adjusted by adding a suitable amount of acid or base. The bases
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Suitable include alkali metal hydroxides, such as, for example, NaOH. Other suitable bases are sodium carbonate and ammonia. Suitable acids include inorganic acids, such as hydrochloric acid, sulfuric acid or organic acids. An illustrative acid is orthophosphoric acid.
The total energy input in a typical crushing process to obtain the desired aqueous suspension composition may typically be between about 100 and 1500 kWht "1 based on the total dry weight of the inorganic charge in particles. The total energy input may be less than approximately 1000 kWht "1, for example, less than approximately 800 kWht" 1, less than approximately 600 kWht "1, less than approximately 500 kWht" 1, less than approximately 400 kWht "1, less than approximately 300 kWht, or less than approximately 200 kWht "1. Thus, the authors of the present invention have surprisingly found that a cellulose pulp can be microfibrillated with a relatively low energy input when it is cotriturated in the presence of particulate inorganic material. As will be evident, the energy input total per ton of dry fiber in the fibrous substrate comprising cellulose will be less than approximately 10,000 kWht "1, for example, men or that approximately 9000 kWht "1, or less than approximately 8000 kWht" 1, or less than approximately 7000 kWht "1, or less than approximately 6000 kWht" 1, or less than
approximately 5000 kWht "1, for example, less than approximately 4000 kWht" 1, less than
approximately 3000 kWht "1, less than approximately 2000 kWht" 1, less than approximately 1500 kWht "1, less than approximately 1200 kWht" 1, less than approximately 1000 kWht "1 or less than
approximately 800 kWht "1. The total energy supply varies depending on the amount of dry fiber in the
fibrous substrate that is microfibrillated, and optionally the crushing speed and the crushing duration.
The following procedure can be used to characterize the size distributions of mineral mixture particles (GCC or caolm) and microfibrillated cellulose pulp fibers.
"Calcium carbonate
A sample of co-suspended suspension is weighed enough to give 3 g of dry material in a beaker, diluted to 60 g with deionized water, and mixed with 5 cm3 of a 1.5% poly (sodium acrylate) solution in p / v active. More deionized water is added with stirring to a final suspension weight of 80 g.
"Caolm
A sample of co-suspended suspension is weighed enough to give 5 g of dry material in a beaker, diluted to 60 g with deionized water, and mixed with 5 cm3 of a 1.0% by weight sodium carbonate solution and 0.5% by weight sodium hexametaphosphate. More deionized water is added with stirring to a final suspension weight of 80 g.
Then the suspension is added in 1 cm3 almuot parts to water in the sample preparation unit attached to the Mastersizer S until it has the optimum level of darkening (usually 10 "15%). Then the analysis procedure is carried out by light scattering The range of the instrument was 300RF: 0.05 "900, and the beam length was adjusted to 2.4 mm.
For the coturated samples containing calcium carbonate and fiber, the refractive index is used for
calcium carbonate (1,596). For the cotolurated samples of caolm and fiber the caolm IR (1,5295) is used.
The distribution of the size of particles is calculated from the teona of Mie and gives the result as a
distribution based on differential volume. The presence of two different peaks is interpreted as coming from the
mineral (finest peak) and fiber (thickest peak).
The finest mineral peak conforms to the measured data points and is mathematically subtracted from the distribution to give the fiber peak, which becomes an accumulated distribution. Similarly, the fiber peak is mathematically subtracted from the original distribution to leave the mineral peak, which also becomes an accumulated distribution. Then, both cumulative curves can be used to calculate the average particle size (d50) and distribution bias (d30 / d70 x 100). The differential curve can be used to find the modal particle size for both the mineral and fiber fraction.
Examples
Unless otherwise specified, paper properties were measured according to the following methods:
"Burst resistance: Messemer Buchnel burst meter in accordance with SCAN P24.
"Tensile strength: Testometrics traction meter according to SCAN P16.
"Bendtsen Porosity: Measured using a Bendtsen Model 5 porosity meter according to SCAN P21, SCAN P60, BS 4420 and Tappi UM535.
"Mass density: This is the redproco of the bulk density measured in accordance with SCAN P7.
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- ISO Brightness: The ISO brightness of handmade paper sheets was measured by means of an Elrepho Datacolour 3300 brightness meter equipped with a No. 8 filter (457 nm wavelength), in accordance with ISO 2470: 1999E.
- Opacity: The opacity of a paper sample is measured by an Elrepho Datacolor 3300 spectrophotometer
using a suitable wavelength to measure opacity. The standard test method is ISO 2471.
First, a measurement of the percentage of incident light reflected with a stack of at least ten sheets of
paper in front of a black cavity (Rinfinito). Then, the stack of sheets is replaced by a single sheet of paper, and
makes a second measurement of the percentage of reflectance of the individual sheet on the black cover (R). Then, the opacity percentage is calculated from the formula: Opacity percentage = 100 x R / Rinfinito.
- Tear resistance: TAPPI T 414 om-04 method (internal tear resistance of the paper (Elmendorf type method)).
- Internal resistance (z address) using a Scott junction meter in accordance with TAPPI T569.
- Brightness: The TAPPI T 480 om-05 method (specular gloss of paper and cardboard at 75 degrees) can be used.
- Rigidity: The method of measurement of stiffness described in J.C. Husband, L.F. Gate, N. Norouzi, and D. Blair, "The Influence of Kaolin Shape Factor on the Stiffness of Coated Papers," TAPPI Journal, June 2009, p. 12-17 (see in particular the section entitled 'Experimental Methods'); and J.C. Husband, J.S. Preston, L.F. Gate, A. Storer, and P. Creaton, "The Influence of Pigment Particle Shape on the ln-Plane tensile Strength Properties of Kaolin-based Coating Layers", TAPPI Journal, December 2006, p. 3-8 (see in particular the section entitled 'Experimental Methods').
- Folding resistance L&W (force needed to bend a sheet by a given angle in mN): measured according to ScAn-P29: 84.
- Cationic demand (or anionic charge): measured in Mutek PCD 03; the samples were titrated with Polydadmac (average molecular weight of approximately 60000) with conc. 1 mEq / l (acquired in PTE AB / Selcuk D0len). The paste mixture was filtered before determination but not white water samples. Before testing the sample, a calibration test is carried out to check the approximate consumption of polyelectrolyte. In the sample test, the polyelectrolytes are dosed in batches (approximately 10 times) with intervals of 30 s.
- The light absorption and scattering coefficients of the sheet are measured using reflectance data from the Elrepho instrument: Rinf = reflectance of a 10-sheet stack. Ro = reflectance of 1 leaf in front of a black cup. These values and the substance (gm-2) of the sheet are introduced into the Kubelka-Munk equations described in "Paper Optics" by Nils Pauler, (published by Lorentzen and Wettre, ISBN 91-971-765-6-7) , P. 29-36.
- The retention to the first step is determined based on the measurement of solids in the input box (HD) and the white water tray (WW) and is calculated according to the following formula: Retention = [(HBsolids- WWsolids ) / HBs6lids] x 100
- The retention of ashes is determined following the same principles as in the retention to the first step, but based on the weight of the ash component in the input box (HB) and in the white water tray (WW), and it is calculated according to the following formula: Ashes retention = [(HBcenizas-WWcenizas) / HBcenizas] x 100
- The training index (PTS) is determined using the DOMAS software developed by PTS in accordance with the measurement method described in section 10-1 of its manual, “DOMAS 2.4 User Guide”
Example 1
Prepared coprocessed load
- Composition 1
The starting materials for the crushing work consisted of a pulp suspension (of bleached Northern kraft pine) and a crushed calcium carbonate (GGC) charge, Intracarb 60 ™, which comprises approximately 60% by volume of particles smaller than 2 p.m. The paste was mixed in a Cellier mixer with the GCC to give a nominal addition of 6% by weight of the paste. This suspension, which feeds 26.5% of solids, is then fed to a mill of agitated medium at 180 kW that contains ceramic crushing medium (King, 3 mm) with a concentration of medium in volume of 50%. The mixture was crushed until an energy contribution of between 2000 and 3000 kWht-1 (expressed in paste alone) was spent and then the paste / mineral mixture was separated from the medium using a 1 mm sieve. The product has a fiber content (by ashes) of 6.5% by weight, and an average fiber size (D50) of 129 pm measured using a Malvern Mastersizer S ™ device. The psd bias of the fiber (D30 / D70 x 100) was 31.7.
- Composition 2
The preparation of this load according to the procedure indicated in composition 1. The paste was mixed in a
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Cellier mixer with Incarb 60 to give a 20% paste addition. This suspension, which fears 10-11% of solids, is then fed to a mill of agitated medium at 180 kW that contains ceramic crushing medium (King, 3 mm) with a concentration of medium in volume of 50%. The mixture was crushed until a contribution of Jan enea of between 2500 and 4000 kWht "1 (expressed in paste alone) was spent and then the paste / mineral mixture was separated from the medium using a 1 mm sieve. The product had a content fiber (by ashes) of 19.7% by weight, and an average fiber size (D50) of 79.7 pm measured using a Malvern Mastersizer S ™ device. The psd bias of the fiber (D30 / D70 x 100) it was 29.3 Before the addition to the paper machine the fiber content was reduced to 11.4% by weight, mixing in a ratio of approximately 50/50 with the gGc (Intracarb 60 ™).
Example 2
Preparation of base paper
A mixture of 80% by weight of eucalyptus paste (Sodra Tofte) refined at 27 ° SR with 4.5% solids and 20% by weight of soft wood kraft paste (Sodra Monsteras) refined at 26 ° SR was prepared with 3.5% solids, in a pilot scale team. This paste mix was used to make a paper reel using a continuous pilot scale paper machine that operated at 800 m.min "1. The pulp was fed to the double wire laminator through a 13 mm slit of a box UMV10 input The target paper weight was 75 gm-2 and the loads and load level are shown in table 1.
Table 1. Properties of uncoated base paper before calendering
 Load
 IC60 control Comp. 1 Comp. 2
 Load,% by weight  19.9 27.8 27.9 28.5
 Weight, g.m-2  74.5 74.1 77.8 71.9
 Tensile strength N.m.g'1  34.0 26.5 26.9 29.4
 Porosity Bendtsen, cm3.min ''  735 749 367 296
A 2 component auxiliary retention system was used consisting of a cationic polyacrylamide, Percal 47NS ™, (BASF) with a dose of 300 - 380 gt "1 and a microparticle bentonite, Hydrocol SH ™ with 2 kg.t-1 The press section consists of a double roller press lined with felt, operating with a linear load of 10 kN.m-1, followed by two Metso SymBelt presses with a shoe length of 250 mm running at 600 and 800 kN. m-1, respectively The rollers in the two shoe presses are inverted with respect to each other.
The paper was dried using heated cylinders.
Application of a barrier coating
A coating was applied to each of the base papers. The formulation consisted of 100 parts of a high form factor caolm (Barrisurf HX ™) and 100 parts of a styrene-butadiene copolymer latex (DL930 ™, Styron). The solids content was 50.1% by weight and the Brookfield viscosity at 100 rpm was 80 mPa.s. The coatings were applied manually using a wound wire rod to give a coating weight of 13-14 g.m-2. Drying was carried out using a hot air dryer.
Example 3
Then the wet steam transmission rate (MVTR) over 2 days was tested on the coated papers of Example 2. The method was based on TAPPI T448 but used silica gel as a desiccant and a relative humidity of 50%. The amount of moisture transferred through the paper was measured over the first and second days and then averaged. The results are summarized in table 2.
The oil resistance was also tested on the papers using a solution based on Sudan IV red oil in dibutyl phthalate using an IGT printing unit. A controlled volume of the fluid (5.8 pI) was applied to the paper using a syringe and passed through the printing roller at a pressure of 5 kgf and a speed of 0.5 m.s-1. The area covered by the fluid dye was measured using image analysis and was used as an indication of the ability of the coating to resist penetration of oil-based fluids. The results are summarized in table 2.
Table 2. Properties of coated base paper
 Load
 IC60 control Comp. 1 Comp. 2
 Load,% by weight  19.9 27.8 27.9 28.5
 MVTR, g.m'2 / day  44.1 40.4 40.4 36.3
 Area taken, pixels  62592 70855 73749 75672
These results show that the paper it contains is the highest fiber level (composition 2), which has a slower transmission rate than the control. Papers coated with both composition 1 and 2 have larger staining zones indicating better fluid resistance.
5 Example 4
Prepared coprocessed load
- Composition 3
The starting materials for the crushing work consisted of a pulp suspension (of Botnia pine) and a load of crushed calcium carbonate, Intracarb 60 ™. The paste was mixed in a Cellier mixer with the Intracarb 10 to give a nominal addition of 20% by weight of the paste. This suspension, which feeds 10-11% of solids later, is fed to a mill of agitated medium at 180 kW that contains ceramic crushing medium (King, 3 mm) with a concentration of medium in volume of 50%. The mixture was crushed until an energy contribution of between 2500 and 4000 kWht-1 was consumed and then the paste / mineral mixture was separated from the medium using a 1 mm sieve. The product has a fiber content (by ashes) of 19.7% by weight, and an average fiber size (D50) of 79.7 pm 15 measured using a Malvern Mastersizer S ™ device. The psd bias of the fiber (D30 / D70 x 100) was 29.3. Before adding to the paper machine (see example 5 below) the fiber content was reduced by mixing 9 parts by weight of the composition containing 19.7% by weight of fiber with 23 parts of Intracarb 60 of new contribution to give a fiber content, measured by ashes, of 5.8% by weight.
- Composition 4
20 A second loading composition was prepared by mixing 50 parts by weight of composition 3, which contains 19.7% by weight of fiber, with 50 parts of Intracarb 60 of new contribution to give a fiber content, measured by ashes, 11.4% by weight.
Example 5
Paper preparation
25 A mixture of 80% by weight of eucalyptus paste (Sodra Tofte) refined at 27 ° SR with 4.5% solids and 20% by weight of soft wood kraft paste (Sodra Monsteras) refined at 26 ° SR was prepared with 3.5% solids, in a pilot scale team. This paste mix was used to make a continuous paper roll using a pilot scale paper machine that operated at 800 m.min-1. The pulp was fed to the double wire laminator through a 13 mm slit of a UMV10 input box. The target paper weight was 75 gm-2 and 30 loads and load level are shown in Table 1. A 2 component auxiliary retention system was used consisting of a cationic polyacrylamide, Percal 47NS ™, (BASF) with a dose of 300-380 gt-1 and a bentonite in microparticles, Hydrocol SH ™ with 2 kg.t-1. The pressing section consists of a double roller press lined with felt, operating with a linear load of 10 kN.m-1, followed by two Metso SymBelt presses with the shoe length of 250 mm running at 600 and 800 kN.m -1, respectively. The rollers in the two shoe presses 35 are inverted with respect to each other.
The paper was dried using heated cylinders.
Table 3 below indicates the final wet measurements made during the papermaking stage. The paper properties are summarized in table 4.
These data show that co-charged charges do not contribute significantly to anionic debris in the recirculation of white water, and does not have a detrimental effect on total retention, while improving the retention of ashes. Finally, paper formation is improved by the addition of co-charged cargo.
Table 3. Parameters of the paper machine
 IC60 control Comp. 3 Comp. 4
 Load,% by weight  19.9 27.8 27.4 28.5
 Retention assistant dose, g.t-1  300 380 380 380
 Whitewater cationic demand, small q-1  0.0225 0.0195 0.0195 0.0210
 Retention at 1st total step,% by weight  72.4 73.9 74.1 70.8
 Ashes retention,% by weight  43.7 35.1 51.1 44.7
 training index, PTS  842 800 636 668
Table 4. Paper properties
 IC60 control Comp. 3 Comp. 4
 Load,% by weight  19.9 27.8 27.4 28.5
 Weight, g.m-2  74.5 74.1 77.3 71.9
 burst resistance index, N.m.g-1  19.3 15.5 18.1 19.8
 tensile strength index, N.m.g-1  34.0 26.5 27.4 29.4
 tear strength index, N.m.g-1  4.12 3.41 3.83 4.12
 Union Resistance Scott, J.m-2  136.6 122.2 134.2 131.8
 Leaf light scattering coefficient, m2kg-1, filters 8 and 10  61.5 (F8) 68.0 (F8) 69.9 (F8) 71.3 (F8)
 58.0 (F10)  63.8 (F10) 65.4 (F10) 66.2 (F10)
 Leaf light absorption coefficient, 0 1 J m2kg, filters 8 and 10  0.381 (F8) 0.385 (F8) 0.407 (F8) 0.419 (F8)
 0.136 (F10)  0.143 (F10) 0.160 (F10) 0.175 (F10)
The results show that papers containing coturated fillers (compositions 3 and 4) have an unusual combination of resistance properties. Normally in the refining of the paste, if the tensile strength increases, the tear decreases. In these examples, both tensile and tear resistance increase at the same time. It also improves Scott's internal bond strength.
Normally, if the tensile strength increases, the light scattering of the sheet decreases. In this case both increase.
10 Example 6
Preparation of co-charged cargo
The starting materials for the crushing work consisted of a pulp suspension (of Botnia pine) and a load of crushed calcium carbonate, Intracarb 60 ™. The paste was mixed in a Cellier mixer with the GCC to give an addition of 20% by weight of the paste. This suspension, which fears 8.8% of solids, is then fed to a 15 mill of agitated medium at 180 kW that contains ceramic crushing medium (King, 3 mm) with a 50% medium volume concentration. The mixture was triturated until an energy contribution of between 2500 kWht-1 was consumed and then the paste / mineral mixture was separated from the medium using a 1 mm sieve. The product has a fiber content (by ashes) of 19.0% by weight, and an average fiber size (d50) of 79 pm measured using a Malvern Mastersizer S ™ device. The psd bias of the fiber (d30 / d70 x 100) was 30.7.
20 Example 7
Preparation of base paper
A mixture of 56% by weight of Fibria eucalyptus pulp refined at 33 SR (100 kWh / t), 14% of soft wood kraft pulp Botnia RMA 90 beaten at 31 SR, and 30% by weight of waste without pulp was prepared coated mechanics containing 50% by weight of GCC (Royal Web Silk), with 3% solids in water using a hydrodisintegrator of
pilot scale wood pulp
The pulp mix was used to make a continuous paper roll using a pilot scale Fourdrinier machine running at 12 m.min-1. The target paper weight was 73-82 gm-2 and the loads and load levels are shown in Table 1. A cationic polymeric retention aid (Percal E622, BASF) was added with a dose of 5 200 gt-1 (10% load) or 300 gt-1 (15-20% load). The paper was dried using heated cylinders
The base paper was calendered by 1 roller in the machine using a steel roller calender at 20 kN pressure. The properties of the paper after calendering are summarized in Table 5.
These results show that the paper containing the billed load has greater resistance to bursting and traction than the control. The resistance to folding also increases. However, porosity is greatly reduced. 10 The sheets that contain the greatest amount of co-charged cargo have better surface smoothness than those containing control plaster.
Table 5. Properties of base paper without uncoated mechanical pulp after calendering
 Control Base 1 Base 2 Base 3
 5% waste load 5% waste load 5% waste load 5% waste load
 10% of IC60 * 10% of ex. 6 15% of ex. 6 20% of ex. 6
 Load,% by weight  15.1 15.8 19.7 23.4
 Weight, g.m-2  72.8 74.4 77.6 82.2
 Tensile strength, geometric mean, N.m.g-1  33.3 35.0 31.4 33.8
 Burst Resistance, N.m.g-1  19.9 22.2 21.2 21.4
 Folding force, geometric mean, L&W, mN  3.22 3.41 4.15 4.2
 Bendtsen porosity, cm3.min-1  1202 842 592 577
 Lisura Bendtsen, lower face, cm3.min-1  350 340 342 286
 ISO brightness  76.7 76.6 77.5 78.0
 Opacity,%  80.6 80.6 84.4 85.9
* Intracarb 60 "VI
Example 8
15 A coating mixture was prepared according to the following formulation:
- 85 parts of ultrafine crushed calcium carbonate (Carbital 95TM) comprising approximately 95% by volume of particles smaller than 2 pm
-15 parts high-gloss caolm (Hydragloss 90 ™ KaMin)
-11 parts percent styrene-butadiene-acrylonitrile latex (DL920 ™, Styron)
20 - 0.3 parts per cent of CMC (Finnfix, CP Kelco)
-1 part per cent of calcium stearate (Nopcote C104).
The pH was adjusted to 8.0 with NaOH and the solids content to 65.5% by weight. The viscosity measured using a Brookfield viscometer at 100 rpm was 270 mPa.s. This was applied to samples of the base paper in Table 5 using a laboratory coater (Heli-Coater ™) at a speed of 600 m.min-1. Coating weights of 25 between 7.0 and 12.0 g.m-2 were applied and adjusted by blade displacement control.
After conditioning at 23 ° C and 50% RH, all coated paper samples produced afterwards were superheated for 10 rollers using a Perkins laboratory calender. The pressure was 50 bar at a roller temperature of 65 ° C and a speed of 40 m.min-1.
The smoothness (Parker Print Surf, ISO 8971-4), brightness at 75 ° TAPPI (T480), and covering using a burn procedure followed by analysis of the gray level image was tested on the coated and calendered strips. The procedure involves treating the paper with an alcoholic solution of ammonium chloride, followed by heating at 200 ° C for 10 minutes to carbonize the base paper fibers. The gray level of the paper is a measure of the ability of the coating layer to cover the blackened fibers. Gray level values close to 0 indicate little coverage (black) while higher values indicate more whiteness and therefore better coverage.
The results for a coating weight of 12 g.m-2 are summarized in table 6.
Printing properties were also tested on coated paper samples. Papers 10 were printed using an IGT printing unit at a speed of 0.5 m.s'1 and a pressure of 500 N. A magenta offset ink with sheet feed was used, applying a volume of 0.1 cm3. The gloss of the printed ink layer was measured using a Hunterlab 75 ° gloss meter according to TAPPI reference T480. The density of the ink was measured using a Gretag Spectroeye ™ densitometer. The coating repellency rate was measured with the IGT Printing Unit in acceleration mode using a low viscosity reference oil. The printing speed 15 accelerated from 0-6 m.s "1 and the distance on the coated strip was measured when the first damage occurred and was expressed as a printing speed. Higher values means that the coating is stronger.
Table 6. Properties of coated paper
 Base  Load,% by weight Brightness at 75 ° TAPPI Smoothness PPS pm, 1000 Pa Burned, medium gray level Print brightness, 75 ° Density of print Dry repel speed -1 cm.s
 Control  15.1 64 1.29 111.6 70 1.50 183
 Base 1  15.8 63 1.21 114.6 70 1.51 194
 Base 2  19.7 71 1.17 140.9 77 1.53 191
 Base 3  23.4 68 1.30 129.9 75 1.46 198
The results show that replacing a standard GCC load with a co-charged load containing microfibrillated cellulose produces improvements in the quality of the coated sheet when the paper is subsequently coated. The surface of the coated paper has higher gloss, better smoothness and the coating layer has better coverage according to the burn test (higher gray level values). The printing properties also improve with the ink layer that has the highest brightness. It was also found that the resistance to dry repelling increased when the load containing microfibrillated cellulose was used in the base.
25 Example 9
Preparation of the co-charged cargo
The starting materials for the crushing work consisted of a pulp suspension (from Botnia pine) and a crushed calcium carbonate filler, Polcarb 60 ™, which comprised approximately 60% by volume of particles smaller than 2 pm. The paste was mixed in a Cellier mixer with the Polcarb to give an addition of 30-20% by weight of the paste. This suspension, which fears 8.7% of solids after being fed to a mill of medium
stirred at 180 kW containing ceramic crushing medium (King, 3 mm) with a 50% medium volume concentration. The mixture was triturated until an energy contribution of between 2500 kWht-1 was consumed and then the paste / mineral mixture was separated from the medium using a 1 mm sieve. The product has a fiber content (by calcination) of 20.7% by weight, and an average fiber size (d50) of 79 pm measured using a Malvern 35 Mastersizer S ™ device. The psd bias of the fiber (d30 / d70x 100) was 29.5.
Example 10
Preparation of base paper
A mixture of 40% by weight of pressurized crushed wood pulp, 40% of soft wood kraft pulp Botnia RMA 90 beaten at 31 SR, and 20% by weight of coated LWC wastes was prepared, the manufacture containing 40 GCC / caolm 50/50, with 3% solids in water using a pilot scale wood pulp hydrodisintegrator
The pulp mix was used to make a continuous paper roll using a pilot scale Fourdrinier machine running at 16 m.min-1. The target paper weight was 38-43 gm-2 and the loads and load levels are shown in Table 7. A cationic polymeric retention aid (Percol 230L, BASF) was added with a dose of 200 gt-1 ( 10% load) or 300 gt-1 (15-20% load). The paper was dried using heated cylinders
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The base paper was calendered by 1 roller in the machine using a steel roller calender at 20 kN pressure. The properties of the paper after calendering are summarized in Table 7.
These results show that the paper containing the billed load has greater resistance to bursting and traction than the control. The resistance to folding also increases. However, porosity is greatly reduced. The sheets that contain the highest amount of coturfaced filler have better surface smoothness compared to those containing control plaster.
Table 7. Properties of uncoated base paper after calendering
 Control Base 1 Base 2 Base 3
 5% waste load 5% waste load 5% waste load 5% waste load
 6% Polcarb 60 5% ex. 9 10% of ex. 9 14% of ex. 9
 Load,% by weight  11.2 10.1 15.4 18.8
 Weight, g.m-2  38.2 38.2 42.0 43.0
 Tensile strength, geometric mean, N.m.g-1  26.8 32.4 30.4 28.4
 Burst Resistance, N.m.g'1  14.8 17.4 16.0 15.4
 Folding force, geometric mean, L&W, mN  3.22 3.41 4.15 4.2
 Porosity Bendtsen, cm3.min ''  1202 842 592 577
 Lisura Bendtsen, lower face, cm ^ min'1  350 340 342 286
 ISO brightness  76.7 76.6 77.5 78.0
 Opacity,%  80.6 80.6 84.4 85.9
Example 11
A coating mixture was prepared according to the following formulation:
- 60 parts of fine crushed calcium carbonate (Carbital 90TM) comprising approximately 90% by volume of particles smaller than 2 pm
- 40 parts of fine Brazilian caolm (Capim DG ™)
- 8 parts per cent of styrene-butadiene-acrylonitrile latex (DL920 ™, Styron)
- 4 parts per cent of starch (Cargill C * film)
-1 part per cent of calcium stearate (Nopcote C104).
The pH was adjusted to 8.0 with NaOH and the solids content to 67.5% by weight. The viscosity measured using a Brookfield viscometer at 100 rpm was 270 mPa.s. This was applied to samples of the base paper in Table 7 using a laboratory liner (Heli-Coater ™) at a speed of 600 m.min'1. Coating weights between 7.0 and 12.0 g.m-2 were applied and adjusted by blade displacement control.
After conditioning at 23 ° C and 50% RH, all coated paper samples produced in Examples 3 and 4 were then superheated for 10 rollers using a Perkins laboratory calender. The pressure was 50 bar at a roller temperature of 65 ° C and a speed of 40 m.min'1.
The smoothness (Parker Print Surf, ISO 8971-4), brightness at 75 ° TAPPI (T480), and coating according to example 8 above were tested on the coated and calendered strips.
Print properties were also tested on coated paper samples according to example 8 above.
The interpolated results at a coating weight of 10 g.m-2 are summarized in Table 8.
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Table 8. Properties of coated paper
 Base  Load,% by weight Brightness at 75 ° TAPPI Lisura PPS pm, 1000 Pa Burned, medium gray level Print brightness, 75 °
 Control  11.2 48 1.36 142.3 62
 Base 1  10.1 50 1.35 135.9 62
 Base 2  15.4 54 1.17 161.0 66
 Base 3  18.8 52 1.20 148.5 65
The results show that replacing a standard plaster load with a co-charged load containing microfibrillated cellulose produces improvements in the quality of the coated sheet when the paper is subsequently coated. The surface of the coated paper has higher gloss, better smoothness and the coating layer has better coverage according to the burn test (higher gray level values). The printing properties also improve with the ink layer that has the highest brightness.
Example 11
400 g of unrefined bleached soft wood kraft pulp (Botnia RM90 pine) were immersed in 20 liters of water for 6 hours, then crushed in a mechanical mixer. The pulp thus obtained was then poured into a Valley laboratory blender and refined under load for 28 min to obtain a sample of 525 cm3 beaten refined pulp of Canadian refining grade (CSF).
The water was then removed from the paste using a consistency meter (Testing Machines lnc.) To obtain a block of wet paste with 23.0-24.0% by weight solids. This was later used in co-experiments as detailed below:
143 g of a 60HS ™ Carbital suspension (77.7% by weight of solids; approximately 60% by volume of particles smaller than 2 pm) were weighed in a crushing vessel. Then 51.0 g of wet paste were added and mixed with the carbonate. Then 1485 g of 3 mm King crushing medium were added followed by 423 g of water to give a 50% medium volume concentration. The mixture is crushed together at 1000 rpm until an energy contribution of 5,000-12,500 kWh / ton (expressed in fiber) is consumed. The product was separated from the medium using a 600 pm BSS sieve. The solids content of the resulting suspension was between 22.0-25.0% by weight and a Brookfield viscosity (100 rpm) of 1400-2930 mPa.s. The fiber content of the product was analyzed by calcination at 450 ° C and the size of the mineral and paste fractions were measured using a Malvern Mastersizer.
Additional samples based on the same GCC and pulp were prepared using similar conditions but with higher pulp addition levels. The properties of the samples are indicated in table 9.
Table 9. MFC-GCC suspension co-financing conditions and properties
 Sample  % by weight MFC in the ore Energfa kWh / t MFC MFC D50, pm, (Malvern)% by weight of solids Brookfield viscosity, 100 rpm, mPa.s
 one  11.1 7500 41.6 22.0 2930
 2  10.9 10,000 16.5 23.9 1685
 3  10.9 12,500 12.5 25.0 1405
 4  17.2 5,000 43 14.9 1815
 5  15.7 10,000 16.4 17.4 1030
 6  15.3 12,500 12.3 18.4 960
 7  24.1 12,500 11.7 13.5 1055
Example 12
131 g of a Barrisurf HX ™ suspension (53.0% by weight solids; form factor = 100) were weighed in a crushing vessel. Then 33.0 g of 22.5% wet paste by weight solids were added and mixed with the caolm. Then 1485 g of 3 mm King crushing medium were added followed by 429 g of water to give a 50% medium volume concentration. The mixture is triturated together at 1000 rpm until an energy contribution between 5,000 and 12,500 kWh / ton (expressed in fiber) is consumed. The products were separated from the medium using a 600 pm BSS sieve. The solids content of the resulting suspensions was between 13.5 -15.9% by weight and Brookfield viscosity values (100 rpm) of 1940 and 2600 mPa.s. The fiber content of the product was analyzed by calcination at 450 ° C and the size of the mineral and paste fractions were measured using a Malvern Mastersizer.
10 Additional samples based on the same caolm and paste were prepared using similar conditions but with higher levels of paste addition. The properties of the samples are indicated in table 10.
Table 10. Conditions and properties of MFC-caolm co-suspensions
 Sample  % by weight MFC in the ore Energfa kWh / t MFC MFC D50, pm, (Malvern)% by weight of solids Brookfield viscosity, 100 rpm, mPa.s
 8  12.6 5000 52.2 13.5 2632
 9  13.0 7500 34.3 14.3 2184
 10  12.5 10,000 23 14.6 1940
 eleven  13.4 12,500 18.2 15.9 2280
 12  18.6 5000 42.5 14.1 4190
 13  16.6 7500 24.8 16.2 4190
 14  15.9 10,000 17 16.0 3156
 fifteen  16.4 12,500 13.6 16.1 2332
 16  22.5 5000 41.9 14.3 6020
 17  21.2 7500 28.2 14.4 5220
 18  21.4 10,000 16.5 14.8 3740
 19  20.0 12,500 11.9 18.1 4550
 twenty  27.7 7500 31.4 13.6 4750
 twenty-one  28.4 10,000 21.4 15.6 5050
 22  32.3 12,500 13.6 17.4 6490
Example 13
15 Portions of the above suspensions were applied onto a poly (ethylene terephthalate) film (Terinex Ltd.) using a 150 pm thick film wound wire rod (Sheen lnstruments Ud, Kingston, United Kingdom). The coatings were dried by application of a hot air gun. The dried coatings were removed from the PET film and cut into 4 mm wide weight bar shapes using a cuter designed for rubber testing. The tensile properties of the coatings were measured using a tensile tester (Testometric 350., Rochdale, United Kingdom). The procedure is described in the article by J.C. Husband, J.S. Preston, L.F. Gate, A. Storer and P. Creaton, "The Influence of Pigment Particle Shape on the In-Plane tensile Strength Properties of Kaolin-based Coating Layers": TAPPI Journal, September 2006, p. 3-8 (see in particular the section entitled "Experimental Methods"). The tensile strength of the coated films was calculated from the breaking load and the elastic modulus from the initial slope of the tension curve versus elongation. The procedure is described in the article by J.C. Husband, L.F. Gate, N. Norouzi, and D. Blair, "The Influence of Kaolin Shape Factor on the Stiffness of Coated Papers": TAPPI Journal, June 2009, page 12-17 (see in particular the section entitled "Experimental Methods") .
The results of the mechanical properties are summarized in tables 11 and 12.
Table 11. Mechanical properties of MFC - CCG coatings
 Sample  % by weight MFC in the mineral Energfa kWh / t MFC Tensile strength, MPa Elastic module, GPa
 one  11.1 7500 0.78 0.44
 2  10.9 10,000 0.90 0.68
 3  10.9 12,500 0.74 0.65
 4  17.2 5,000 0.68 0.35
 5  15.7 10,000 1.33 0.75
 6  15.3 12,500 1.36 0.83
 7  24.1 12,500
These results show that a combination of MFC and caolm with a high dimension ratio can produce resistance and elastic modulus values. The elastic module translates directly into rigidity of the improved coated paper 5, for example.
Table 12. Coated MFC-Barrisurf HX coating conditions and properties
 Sample  % by weight MFC in the mineral Energfa kWh / t MFC Tensile strength, MPa Elastic module, GPa
 8  12.6 5000 1.93 1.29
 9  13.0 7500 2.96 1.68
 10  12.5 10,000 2.55 1.66
 eleven  13.4 12,500 2.41 1.69
 12  18.6 5000 2.25 1.45
 13  16.6 7500 3.27 2.14
 14  15.9 10,000 4.31 2.64
 fifteen  16.4 12,500 2.98 2.16
 16  22.5 5000 2.91 2.11
 17  21.2 7500 5.71 2.94
 18  21.4 10,000 5.95 2.91
 19  20.0 12,500 3.26 2.53
 twenty  27.7 7500 6.62 2.86
 twenty-one  28.4 10,000 5.53 2.54
 22  32.3 12,500 5.33 2.67

权利要求:
Claims (15)
[1]
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Four. Five
1. An article comprising:
i) a paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material; Y
ii) one or more functional coatings on the paper product; wherein microfibrillated cellulose has a fiber bias of 20 to 50.
[2]
2. The article of claim 1, wherein the functional coating is a polymer, a metal, an aqueous composition or a combination thereof.
[3]
3. The article of claim 1 or claim 2, wherein the functional coating is an aqueous composition comprising a laminated or hyperlaminated caolm.
[4]
4. The article of any one of the preceding claims, comprising a packaging material.
[5]
5. The article of any one of the preceding claims, wherein the functional coating is a liquid barrier layer, for example, a water based liquid barrier layer.
[6]
6. The article of any one of claims 1-4, wherein the functional coating is a printed electronic layer.
[7]
7. The article of any one of the preceding claims, wherein the paper product comprises from about 0.5% by weight to about 50% by weight of the composition of coprocessed microfibrillated cellulose and inorganic particulate material, for example, of approximately 25% by weight to approximately 35% by weight of the composition of coprocessed microfibrillated cellulose and inorganic particulate material.
[8]
8. A paper product comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, wherein the paper product has:
i) a first tensile strength greater than a second tensile strength of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; I
ii) a first tear strength greater than a second tear resistance of the paper product devoid of the composition of coprocessed microfibrillated cellulose and particulate inorganic material; I
iii) a first burst resistance greater than a second burst resistance of the paper product devoid of the composition of coprocessed microfibrillated cellulose and particulate inorganic material; I
iv) a first coefficient of scattering of the sheet light greater than a second scattering coefficient of the sheet light of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; I
v) a first porosity less than a second porosity of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; I
vi) a first resistance in the z direction (internal bond) than a second resistance in the z direction (internal link) of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; I
vii) a first training index smaller than a second training product index paper devoid of the composition of co-processed microfibrillated cellulose and inorganic particulate material; Y
wherein the paper product further comprises a paper coating composition comprising a functional coating for liquid packaging, barrier coatings, printed electronic applications, or a coating composition comprising a composition of coprocessed microfibrillated cellulose and inorganic material in particles, optionally where microfibrillated cellulose has a fiber bias of 20 to 50.
[9]
9. The paper product of claim 8, which further comprises a second coating comprising a polymer, a metal, an aqueous composition or a combination thereof, which also optionally has a first wet vapor transmission rate (MVTR) less than a second MVTR of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material.
[10]
10. The paper product of any of claims 8-9, wherein the paper comprises from about 0.5% by weight to about 50% by weight of the microfibrillated cellulose composition
39
5
10
fifteen
twenty
25
30
35
40
Four. Five
coprocessed and inorganic particulate material, for example, from about 25% by weight to about 35% by weight of the composition of coprocessed microfibrillated cellulose and inorganic particulate material.
[11]
11. A paper product according to claim 8, which has a first gloss greater than a second gloss of the paper product devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material.
[12]
12. A coated paper product, wherein the coating comprises a composition of coprocessed microfibrillated cellulose and inorganic particulate material, and wherein the coated paper product has:
i. a first gloss greater than a second gloss of the coated paper product comprising a coating composition devoid of the co-processed microfibrillated cellulose composition and inorganic particulate material; I
ii. a first stiffness greater than a second stiffness of the coated paper product comprising a coating composition devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; I
iii. a first barrier property that is better compared to a second barrier property of the coated paper product comprising a coating composition devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material;
where microfibrillated cellulose has a fiber bias of 20 to 50,
optionally where the inorganic part is caolm, for example, hyperlaminated caolm.
[13]
13. A polymeric composition comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, wherein microfibrillated cellulose has a fiber bias of 20 to 50, optionally where the composition of coprocessed microfibrillated cellulose and inorganic particulate material is substantially homogeneously dispersed in the polymer composition.
[14]
14. A papermaking composition comprising a composition of coprocessed microfibrillated cellulose and inorganic particulate material, where (A) the papermaking composition has:
(i) a first cationic demand smaller than a second cationic demand of the composition for the manufacture of paper devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; I
(ii) a first retention at the first step greater than a second retention at the first step of the composition for the manufacture of paper devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; I
(iii) a first retention of ashes greater than a second retention of ashes of the composition for the manufacture of paper devoid of the composition of coprocessed microfibrillated cellulose and inorganic particulate material; Y
where microfibrillated cellulose has a fiber bias of 20 to 50,
or where (B) the papermaking composition is substantially devoid of retention aids and where microfibrillated cellulose has a fiber bias of 20 to 50.
[15]
15. The article, paper product, polymeric composition or papermaking composition of any one of the preceding claims, wherein:
(i) the particulate inorganic material comprises an alkaline earth metal carbonate or sulfate, such as calcium carbonate, magnesium carbonate, dolomite, gypsum, a hydrated Kandite clay such as kaolm, haloisite or ball clay, an anhydrous Kandite clay ( calcined) such as metacaolm or fully calcined caolm, talc, mica, huntite, hydromagnesite, crushed glass, perlite or diatomaceous earth, or combinations thereof; I
(ii) microfibrillated cellulose has a d50 in the range of about 25 pm to about 250 pm, more preferably from about 30 pm to about 150 pm, even more preferably from about 50 pm to about 140 pm, still more preferably about 70 pm to about 130 pm, and most preferably from about 50 pm to about 120 pm; I
(iii) microfibrillated cellulose has a distribution of the monomodal particle size or a distribution of the multimodal particle size.

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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GB201019288|2010-11-15|

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GBGB1019288.8A|GB201019288D0|2010-11-15|2010-11-15|Compositions|

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GB201113559|2011-08-05|

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GBGB1113559.7A|GB201113559D0|2010-11-15|2011-08-05|Compositions|

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PCT/GB2011/052181|WO2012066308A2|2010-11-15|2011-11-09|Compositions|

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