process for preparing self-binding pigment particles, self-binding pigment particle suspension, use

专利摘要:
PROCESS FOR PREPARING SELF-BINDING PIGMENT PARTICLES, SELF-BINDING PIGMENT PARTICLE SUSPENSION, USE OF A SELF-BINDING PIGMENT PARTICLE SUSPENSION, AND, PAPER PRODUCT. The present invention relates to a process for preparing self-binding pigment particles from an aqueous suspension of calcium carbonate-containing material, wherein an anionic binder and at least one cationic polymer are mixed with the suspension.
公开号:BR112014027630B1
申请号:R112014027630-7
申请日:2013-05-02
公开日:2021-07-06
发明作者:Patrick A. C. Gane；Joachim Schoelkopf；Daniel Gantenbein
申请人:Omya International Ag；
IPC主号:

专利说明:

[0001] The invention relates to a process for preparing self-binding pepper particles, a self-binding pigment particle suspension as well as a paper product comprising the self-binding pigment particles and the use of the self-binding pigment particle suspension .
[0002] Mineral materials and binders are among the main constituents used in the manufacture of numerous products such as paints, paper and plastic materials. In this way, mineral materials contribute to the mechanical and optical properties, while the binder, generally based on latex and in the form of aqueous suspensions or dispersions, provides the necessary adhesion and cohesion for the respective constituents of the final product to be produced.
[0003] In order to avoid the logistical difficulties of handling mineral materials and binders separately, and also to avoid unwanted physical and chemical interactions developed in comparable mixtures of mineral materials and binders, self-binding pepper particles have been developed and are known by the industry. In this regard, self-bonding pepper particles having both mineral material and binder properties can be directly implemented in a variety of applications. This unique product called the self-bonding pepper particles refers to distinct, solid particles formed of mineral and binder material that are intimately bonded together. The internal cohesive forces are such as to provide the self-bonding pepper particles with excellent mechanical stability.
[0004] Self-binding pepper particles can be produced from mineral materials containing calcium carbonate, for example, from natural mineral pepper materials that are usually prepared by a process that implements at least one step of grinding the materials minerals in the presence of a binder. Milling refers to an operation that leads to a reduction in particle size, that is, the mineral materials in the self-bonding pepper particles have a smaller diameter than the starting mineral material used to produce them. Such self-binding pepper particles are described in several of the documents, including WO 2006/008657, WO 2006/128814, and WO 2008/139292.
[0005] For completeness, the Applicant would like to mention the following applications on its behalf, which also refer to the processes for preparing the self-bonding pepper particles: Unpublished European Patent Applications with deposit numbers 11 160 900.4 , 11 160 926.9, 11 179 604.1, and 11 179 572.0.
[0006] Processes for preparing self-binding pepper particles known in the art are often limited to preparing or comminuting suspensions having a low solids content. However, the preparation of suspensions with low solids content has the disadvantage that the mill product obtained has to be concentrated before being sent to other facilities for further processing. During the time- and energy-consuming concentration step, very often an unwanted loss of non-polymeric binder is observed, and, in addition, unwanted agglomerates are formed. Furthermore, prior art processes often lead to a suspension having a high total organic content of the aqueous phase of the milled suspension. In addition, the addition of dispersant, however, INTER ALIA affects the adsorption of the binder to the particles during comminution.
[0007] Self-binding pepper particles containing binders that are based on polymers that are derived from natural or renewable resources are a particular point of interest for environmental reasons. However, such self-binding pepper particles are often formed from negatively charged modified polysaccharides, which can be unfavorable for some application fields. For example, due to their negative surface charge such pepper particles are difficult to retain during papermaking processes. This leads to a high consumption of the self-bonding pepper particles and aids in additional retention during paper production to achieve the desired filler load on the paper.
[0008] Another problem, which very often significantly impacts the mechanical and optical properties of papers and paper coatings made from such self-binding pepper particles, is encountered with respect to the bond between the fibers and such self-binding pepper particles. The self-binding pepper particle suspension often detracts from the mechanical and optical properties of the corresponding end products. One reason for this may be the shape of the self-binding pepper particles, which would prevent the interaction between the self-binding pepper particles and the paper fibers. Thus, to produce paper articles with well-matched mechanical and optical properties, the limits of interaction between the self-binding pepper particles and the fibers in the paper have to be optimised.
[0009] Furthermore, high filler levels in paper are desirable as these would provide the possibility to reduce the amount of wood fibers in the paper. Also, papers with a high filler content will dry faster, and as a result, the paper machine can run faster. Consequently, the addition of high filler levels can reduce paper production costs and can save natural resources. However, such high filler levels often reduce the area of contact between the remaining fibers. As a result, retaining high amounts of filler with a suboptimal shape produces a weaker sheet that can break more easily on paper machines, glue presses, coaters, winders, printing presses, printing machines, or copying machines.
[00010] US 5,611,890 relates to a strong, soft filled tissue paper comprising a non-cellulosic particulate filler, wherein said filler comprises from 5 to 50% by weight of said tissue paper. WO 03/087472 discloses a filler treatment which comprises preparing swollen starch latex compositions, and adding said compositions to a filler suspension. The use of these treated fillers during papermaking improves filler retention and produces filled papers, where the addition of filler has only a minimal negative effect on strength properties. A papermaking filler material that has been surface treated with a cationic polymer is described in CA 2,037,525. The article “Improvement of paper properties using starch-modified precipitated calcium carbonate filler” by Zhao ET AL., TAPPI Journal 2005, vol. 4(2), is concentrated with commercial precipitated calcium carbonate fillers that have been modified with raw corn and potato starches. These modified fillers have been used in the manufacture of paper fillers to improve strength in papers with high filler content.
[00011] In view of the foregoing, the improvement of the production process of the self-bonding pigment particle remains of interest to the skilled technician. It would be especially desirable to provide a process for making the self-bonding pigment particles, in which the mineral pigment particles do not have to be co-milled with the binder as milling is a very expensive and time-consuming step. In addition, the particle structure of mineral pigment particles may change during milling and therefore the characteristics of mineral pigment particles may be different after milling. Additionally, it would also be desirable to provide a process for manufacturing the self-bonding pigment particles, which could be applied to mineral pigment suspensions having a high solids content, thus avoiding an energy and time consuming concentration step and, for example, the formation of significant amounts of unwanted agglomerates. In addition, it would be desirable to provide self-binding pigment particles that improve the bond between fibers in papers and paper coatings and self-binding pigment particles, and thus allow the production of paper articles with well-matched mechanical and optical properties. In particular, it is desirable to provide a process for making the self-bonding pigment particles, which allows the provision of a filler material that shows good retention in papermaking processes, and avoids the use of large amounts of retention aids.
[00012] According to one aspect of the present invention, the foregoing and other objectives are solved by means of a process for preparing the self-binding pigment particles in which the process comprises the following steps: a) providing an aqueous suspension comprising at least minus one calcium carbonate-containing material, b) providing at least one acid or acid salt, wherein the acid anion or acid salt is capable of forming water-insoluble calcium salts, c) providing an anionic polymeric binder, wherein said binder comprises at least one modified polysaccharide, d) providing at least one cationic polymer, e) mixing the aqueous suspension of step a) with the at least one acid or acid salt of step b), and f) mixing the suspension of step e), the anionic polymeric binder of step c) and the at least one cationic polymer of step d).
[00013] According to another aspect, the present invention relates to a suspension of self-binding pigment particle which is obtainable by the process according to the present invention.
[00014] Another aspect of the present invention relates to the use of the inventive self-binding pigment particle suspension in paper, plastics, paint, coatings, concrete and/or agricultural applications.
[00015] In yet another aspect the present invention relates to a paper product comprising self-binding pigment particles, wherein the particles are at least partially coated with a water-insoluble calcium salt formed from an acid or acid salt, an anionic binder comprising at least one modified polysaccharide, and at least one cationic polymer.
[00016] Advantageous embodiments of the inventive method are defined below.
[00017] According to an embodiment in step f) of the inventive process, the suspension obtained by step e) is, in a first step, mixed with the anionic polymeric binder of step c), and then, in a second step , is mixed with the at least one cationic polymer from step d). According to another embodiment in step f) of the inventive process, the suspension obtained from step e) is mixed with the anionic polymeric binder from step c) and the at least one cationic polymer from step d) in one step. According to yet another embodiment in step f) of the inventive process, the suspension obtained by step e) is, in a first step, mixed with the at least one cationic polymer from step d), and then, in a second step, is mixed with the anionic polymeric binder of step c).
[00018] According to an embodiment the suspension obtained by step e) is concentrated before step f). The concentration of the step can be carried out by using thermal and/or mechanical methods well known to the skilled person.
[00019] According to an embodiment the at least one calcium carbonate-containing material is selected from calcium carbonate, calcium carbonate-containing minerals, mixed calcium carbonate-based fillers, or mixtures thereof, preferably the calcium carbonate-containing material is calcium carbonate, more preferably precipitated calcium carbonate (PCC) and most preferably it is scalenohedral PCC (S-PCC), rhombohedral PCC (R-PCC), prismatic PCC (P-PCC) , cubic PCC (C-PCC), or a mixture thereof. According to another embodiment the at least one calcium carbonate-containing material of step a) is provided in particulate form having a d50 value of the weighted average particle diameter 0.1 to 100 µm, preferably 0.2 to 50 µm, more preferably from 0.5 to 25 µm, and most preferably from 1.0 to 10 µm. According to yet another embodiment the at least one calcium carbonate-containing material of step a) is provided in the form of particles having a specific surface area of from 0.1 to 200 m 2 /g, preferably from 0.5 to 100 m2/g, more preferably from 1.0 to 50 m2/g, and more preferably from 2.0 to 10 m2/g.
[00020] According to an embodiment the aqueous suspension of step a) has a solid content from 1 to 99% by weight, preferably from 15 to 70% by weight, more preferably from 10 to 50% by weight, and more preferably from 12 to 40% by weight, based on the total weight of the suspension. According to another embodiment, the suspension from step a) further comprises minerals such as talc, kaolin, TiO2, bentonite and their mixtures.
[00021] According to an embodiment the at least one acid or acid salt of step b) are added in an amount of from 0.001 to 40% by weight, preferably from 0.005 to 20% by weight, more preferably from 0. 01 to 10% by weight, and more preferably from 0.05 to 5% by weight, based on the total weight of the dry calcium carbonate containing material. According to another embodiment the at least one acid or acid salt of step b) are selected from the group comprising citric acid, oxalic acid, phosphoric acid, sulfuric acid, arsenic acid and iodic acid or salts thereof, and their mixtures.
[00022] According to an embodiment the suspension obtained by step e) has a solid content of 2 to 99% by weight, preferably from 10 to 60% by weight, more preferably from 15 to 45% by weight, and more preferably from 20 to 30% by weight, based on the total weight of the suspension.
[00023] According to an embodiment the at least one modified polysaccharide is a carboxymethyl derivative and/or a carboxymethyl hydroxypropyl derivative and/or a carboxymethyl hydroxyethyl derivative of a polysaccharide, preferably a carboxymethylcellulose, an anionic guar , an anionic starch, or xanthan gum. According to another embodiment the at least one modified polysaccharide has a degree of substitution of the hydroxyl groups in the range from 0.4 to 2.0, preferably from 0.5 to 1.8, more preferably from 0.6 to 1.6, and more preferably from 0.7 to 1.5. According to yet another embodiment the intrinsic viscosity of the at least one modified polysaccharide is in the range from 5 to 500 ml/g, preferably from 10 to 450 ml/g, more preferably from 50 to 350 ml/g, and more preferably from 100 to 200 ml/g.
[00024] According to an embodiment the binder of step c) is in the form of an aqueous solution or dry material, preferably in the form of a solution having a binder concentration of 1 to 70% by weight, preferably 2 to 55% by weight, more preferably 5 to 50% by weight, and more preferably 30 to 50% by weight, based on the total weight of the solution. According to another embodiment the binder of step c) is added in an amount of from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, and more preferably from 0.05 to 5% by weight, based on the total weight of the dry calcium carbonate containing material.
[00025] According to an embodiment the at least one cationic polymer of step d) is selected from the group comprising polyethyleneimines, polyacrylamides, cationic epichlorohydrin resins, cationic starch, cationic guar, and mixtures thereof. According to yet another embodiment the at least one cationic polymer of step d) is in the form of a solution or dry material, preferably in the form of a solution having a concentration of 0.5 to 70% by weight, preferably of 1 to 25% by weight, more preferably from 1.5 to 20% by weight, and more preferably from 2 to 10% by weight, based on the total weight of the solution. According to yet another embodiment the at least one cationic polymer of step d) is added in an amount of from 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, and more preferably from 0.05 to 5% by weight, based on the total weight of the dry calcium carbonate containing material.
[00026] According to one embodiment the self-binding pigment particle suspension is used in the final wet process of a paper machine, in cigarette paper, cardboard, and/or coating applications, or as a support for printing by rotogravure and/or offset and/or inkjet and/or continuous inkjet printing and/or flexography and/or electrophotography and/or decorative surfaces. According to another embodiment the self-binding pigment particle suspension is used to reduce the exposure to sunlight and UV of the plant leaves.
[00027] According to an embodiment the inventive paper product has a higher tensile index compared to a paper product, in which the inventive self-binding pigment particles are replaced by the same amount of material particles containing carbonate calcium, preferably the tensile index is at least 5% higher, more preferably at least 7% higher, and more preferably at least 10% higher compared to the tensile index of a paper product, wherein the Inventive self-binding pigments are replaced by the same amount of material particles that contain calcium carbonate.
[00028] It should be understood that for the purpose of the present invention, the following terms have the following meanings:
[00029] A "suspension" or "slurry" in the meaning of the present invention comprises insoluble solids and water, and optionally other additives, and usually contains large amounts of solids and thus is more viscous and may be of higher density than that the liquid form that is formed.
[00030] A "calcium carbonate-containing material" in the meaning of the present invention may be a mineral material or a synthetic material having a calcium carbonate content of at least 50% by weight, preferably 75% by weight, plus preferably 90% by weight, and more preferably 95% by weight, based on the total weight of the calcium carbonate containing material. The term "calcium carbonate-containing dry material" is understood to refer to particles of calcium carbonate-containing material having a total surface moisture content of less than 0.5% by weight, preferably less than 0. 2% by weight and more preferably less than 0.1% by weight, based on the total weight of the particles.
[00031] The "ground calcium carbonate" (GCC) in the meaning of the present invention is a calcium carbonate obtained from natural surfaces, such as limestone, marble, calcite or chalk, processed through such wet and/or dry treatment. such as grinding, sieving and/or fractionating, for example by a cyclone or classifier.
[00032] The "precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthesized material, generally obtained by the precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous or by the precipitation of a calcium and a carbonate source in water. Additionally, precipitated calcium carbonate can also be the product of introducing calcium and carbonate salts, calcium chloride and sodium carbonate, for example, into an aqueous environment.
[00033] An "acid" in the meaning of the present invention is defined as a Br0nsted-Lowry acid, that is to say, it is a supplier of H3O+ ion. An “acid anion” is defined as a deprotonated form of an H3O+ ion supplier, ie it is a conjugate base of an acid. An “acid salt” is defined as an H3O+ ion supplier that is at least partially neutralized by a non-hydrogen cation. A “salt” is defined as an electrically neutral ionic compound formed from non-hydrogenated anions and cations. A "salt" can comprise the anhydrous form as well as forms comprising crystalline water (hydrate).
[00034] For the purpose of the present application, “water-insoluble materials are defined as materials that require more than 100 ml of water per gram of material to dissolve the material at 20°C as defined by the European Pharmacopoeia. Preferably the materials are dissolved in a pH form of 7.5 to 14.
[00035] An "anionic polymeric binder" in the meaning of the present invention is defined as a polymer that is capable of binding to the surface of the calcium carbonate-containing material and to itself and/or to certain other materials on drying. Bonding includes ionic interactions and/or hydrogen-hydrogen bridge bonds between groups on the surface of particles of calcium carbonate-containing material and the functional groups of the polymer. Furthermore, the terms "anionic polymer" or "anionic polymeric binder" in the meaning of the present invention refer to a polymer having a net negative charge. Said compound is typically modified with anionic groups. The term “anionic” does not exclude the presence of cationic groups as long as the sum of the individual charges is negative.
[00036] The term "cationic polymer" in the meaning of the present invention refers to a polymer having a net positive charge. Said compound is typically modified with cationic groups. The term “cationic” does not exclude the presence of anionic groups as long as the sum of the individual charges is positive.
[00037] The "particle size" of the calcium carbonate-containing material in the meaning of the present invention is defined by its particle size distribution. The DX value represents the relative diameter at which X% by weight of the particles have diameters less than DX. This means that the D20 value is the particle size at which 20% by weight of all particles are smaller, and the D75 value is the particle size at which 75% by weight of all the particles are smaller. The D50 value is thus the weighted average particle size, i.e. 50% by weight of all grains are larger or smaller than this particle size. For the purpose of the present invention particle size is specified as D50 weighted average particle size unless otherwise indicated. To determine the D50 weighted average particle size value for particles having a d50 value of 0.2 and 5 µm, a Sedigraph 5120 device from the company Micromeritics, USA, can be used.
[00038] A "specific BET surface area" (SSA) in the meaning of the present invention is defined as the surface area of the mineral pigment divided by the mass of the mineral pigment. As used herein, the specific surface area is measured by nitrogen adsorption using the BET isotherm (ISO 9277:2010) and is specified in m2/g.
[00039] For the purposes of the present invention, the term "viscosity" with reference to coating formulations, refers to Brookfield viscosity. Brookfield viscosity can be measured by a Brookfield viscometer at 23°C at 100 rpm and is specified in mPa^s.
[00040] The term "intrinsic viscosity" as used in the context of the present invention is a measure of the ability of a polymer in the solution to enhance the viscosity of the solution and is specified in ml/g.
[00041] The term "degree of substitution" as used in the context of the present invention is specified with respect to the total amount of substituted or modified groups per unit of unmodified monomer of the original polysaccharide.
[00042] The "modified polysaccharides" in the meaning of the present invention are polysaccharides, in which at least a part of the hydroxyl groups is carboxylated. Additionally, modified polysaccharides may contain other modifications such as aldehyde groups.
[00043] Where the term “comprising” is used in the present description and claims, it does not exclude other elements. For the purpose of the present invention, the term "consisting of" is considered to be a preferred embodiment of the term "comprising of". If thereafter a group is defined to comprise at least a certain number of embodiments, this is also to be understood as disclosing a group, which preferably consists only of these embodiments.
[00044] Where an indefinite or definite article is used when referring to a singular name, for example "a", "an" or "the", this includes a plural of this name unless something else is specifically stated.
[00045] Terms such as "obtainable" or "definable" and "obtained" or "defined" are used interchangeably. This, for example, means that, unless the context is clearly otherwise stated, the term "obtained" is not intended to indicate that, for example, an embodiment must be obtained, for example, by the sequence of steps following the term "obtained" although such a limited understanding is always encompassed by the terms "obtained" or "defined" as a preferred embodiment.
[00046] The inventive process for preparing the self-bonding pigment particles provides several advantages. Firstly, the inventive process provides a good adsorption of the binder by the particle surface and thus no further step of comminuting the calcium carbonate-containing material together with the binder has to be carried out. Second, the self-bonding pigment particles obtained by the inventive process show improved bonding to fibers in paper product processes, and therefore the filler loaded into the paper can be increased while maintaining the mechanical strength properties of the paper. Additionally, the formation of unwanted aggregates is reduced by the application of the inventive process since a subsequent concentration step can be avoided due to processing a high solids content slurry as shown above.
[00047] In the following the details and preferred embodiments of the inventive process will be presented in more detail. It should be understood that these technical details and embodiments also apply to the inventive self-binding pigment particle suspensions and their uses. Step a)
[00048] In step a) of the process according to the present invention an aqueous suspension comprising at least one calcium carbonate-containing material is provided. According to an embodiment of the present invention, the aqueous suspension is obtained by mixing the particles of calcium carbonate-containing material with water.
[00049] The calcium carbonate containing material can be selected from calcium carbonate, calcium carbonate containing minerals, mixed carbonate based filler, or mixtures thereof.
[00050] According to an embodiment of the present invention, the calcium carbonate-containing material is a calcium carbonate. Calcium carbonate can be selected from ground calcium carbonate and/or precipitated calcium carbonate.
[00051] Ground (or natural) calcium carbonate (GCC) is understood to be a naturally occurring form of calcium carbonate, extracted from sedimentary rocks such as limestone or chalk, or from metamorphic marble rocks. Calcium carbonate is known to exist as three types of crystalline polymorphs: calcite, aragonite and vaterite. Calcite, the most common crystalline polyform, is considered to be the most stable crystalline form of calcium carbonate. The least common is aragonite, which has an orthorhombic crystal structure in the form of a separate or grouped needle. Vaterite is the rarest calcium carbonate polymorph and is generally unstable. Ground calcium carbonate is almost exclusively of the calcitic, ie trigonal-rhombohedral, polymorph and represents the most stable of the calcium carbonate polymorphs. The term "source" of calcium carbonate in the sense of the present application refers to the naturally occurring mineral material from which calcium carbonate is obtained. The calcium carbonate source may further comprise naturally occurring components such as magnesium carbonate, aluminum silicate etc.
[00052] According to an embodiment of the present invention the GCC is obtained by dry milling. According to another embodiment of the present invention the GCC is obtained by wet milling and subsequent drying.
[00053] In general, the milling step can be performed with any conventional milling device, for example, under conditions such that the refinement predominantly results from impacts with a secondary body, that is, in one or more of: a mill. ball, a rod mill, a vibrating mill, a roller crusher, a centrifugal impact mill, a vertical pearl mill, a friction mill, a pin mill, a hammer mill, a pulverizer, a shredder, a deagglomerator, a knife cutter, or other such equipment known to the qualified technician. In the case of mineral powder containing calcium carbonate comprises a wet ground material which contains mineral calcium carbonate, the grinding step can be carried out under conditions such that autogenous grinding takes place and/or by grinding with a horizontal ball, and/or other such processes known to the skilled technician. The wet processed ground material which contains mineral calcium carbonate thus obtained can be washed and dehydrated by known processes, for example by flocculation, filtration or forced evaporation before drying. The subsequent drying step can be carried out in a single step such as spray drying, or in at least two steps. It is also common for such mineral material to undergo a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities.
[00054] According to an embodiment of the present invention the source of ground calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone, or mixtures thereof. Preferably, the ground calcium carbonate source is selected from marble.
[00055] According to an embodiment, the suspension of process step a) comprises a ground calcium carbonate. According to another embodiment of the present invention, the suspension from process step a) comprises a mixture of two or more ground calcium carbonate selected from sources other than ground calcium carbonate. For example, the suspension of at least one ground calcium carbonate can comprise a GCC selected from dolomite and a GCC selected from marble.
[00056] According to an embodiment of the present invention, the suspension of process step a) consists of at least one ground calcium carbonate. The suspension from process step a) can consist of one ground calcium carbonate, or it can consist of two or more ground calcium carbonates selected from different sources of ground calcium carbonate.
[00057] The "precipitated calcium carbonate" (PCC) in the meaning of the present invention is a synthesized material, generally obtained by precipitation following the reaction of carbon dioxide and lime in an aqueous environment or by precipitation from an ion source calcium and carbonate in water or by precipitating calcium and carbonate ions, for example from CaCl2 and Na2CO3, from solution. Precipitated calcium carbonate exists in three primary crystal forms: calcite, aragonite, and vaterite, and three are very different polymorphs (crystalline habits) for each of these crystal forms. Calcite has a triangular structure with typical crystalline habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, pinachoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC). Aragonite is an orthorhombic structure with crystal habits typical of hexagonal prismatic twin crystals, as well as a diverse assortment of fine elongated prismatic crystals, curved blade, steep pyramidal, chisel-shaped, branched tree, and coral or earthworm-shaped.
[00058] According to a preferred embodiment of the present invention, the calcium carbonate-containing material is precipitated calcium carbonate (PCC).
[00059] Precipitated calcium carbonate may have other advantages compared to ground calcium carbonate. For example, unlike ground calcium carbonate, which is extracted from large natural ore deposits, PCC particles are prepared synthetically and therefore the size and particle size distribution can be adjusted during preparation. Furthermore, depending on the reaction conditions the shape and crystallinity of the PCC particles can be adjusted. Additionally, PCC mineral pigment particles are not contaminated with impurities and therefore can show a better gloss compared to GCC.
[00060] Another advantage of PCC is the fact that PCC particles typically have many tips on their outer surface, and thus are relatively rough. It is believed that these particle ends can intertwine with the paper fibers, resulting in improved bonding between the particles and the fibers. Therefore, the use of PCC as filler in paper application can control the paper structure more optimally, and thus, can improve the mechanical properties of the paper.
[00061] According to an embodiment, the suspension of process step a) comprises a precipitated calcium carbonate. According to a preferred embodiment of the present invention, the precipitated calcium carbonate comprises scalenohedral precipitated calcium carbonate (S-PCC).
[00062] According to another embodiment of the present invention, the suspension of process step a) comprises a mixture of two or more precipitated calcium carbonates selected from sources other than the precipitated calcium carbonate. For example, the suspension of at least one precipitated calcium carbonate may comprise a PCC selected from S-PCC and a PCC selected from R-PCC.
[00063] According to another preferred embodiment of the present invention, the suspension of process step a) consists of at least one precipitated calcium carbonate. The suspension from step a) can consist of one type of PCC, or it can consist of a mixture of two or more types of PCC.
[00064] According to an embodiment of the present invention, the calcium-carbonate-containing minerals comprise dolomite.
[00065] According to one embodiment, mixed carbonate-based fillers are selected from calcium associated with magnesium and analogues or derivatives, various materials such as clay or talc or analogues or derivatives, and mixtures of these fillers such as, for example, mixtures of talc-calcium carbonate or calcium carbonate-kaolin, or mixtures of natural calcium carbonate with aluminum hydroxide, mica or with synthetic or natural fibers or mineral costructures such as talc-calcium carbonate costructures or talc-titanium dioxide or calcium carbonate-titanium dioxide.
[00066] According to another embodiment of the present invention the aqueous suspension comprising the at least one calcium carbonate-containing material comprises another mineral such as talc, kaolin, TiO2, bentonite, or mixtures thereof.
[00067] According to a preferred embodiment of the present invention, the at least one calcium carbonate-containing material is provided in particulate form having a weighted average particle diameter d50 of 0.1 to 100 µm, preferably 0 .2 to 50 µm, more preferably 0.5 to 25 µm, and most preferably 1.0 to 10 µm.
[00068] According to a preferred embodiment of the present invention, the at least one calcium carbonate-containing material is provided in particulate form having a specific surface area from 0.1 to 200 m2/g, preferably from 0 from 0.5 to 100 m2/g, more preferably from 1.0 to 50 m2/g, and most preferably from 2.0 to 10 m2/g, measured using nitrogen and the BET method in accordance with ISO 9277:2010.
[00069] The at least one calcium carbonate-containing material is suspended in water, and thus forms an aqueous suspension or slurry of calcium carbonate-containing material. According to an embodiment of the present invention, the aqueous suspension provided in process step a) has a solid content from 1 to 99% by weight, preferably from 15 to 70% by weight, more preferably from 10 to 50% by weight, and more preferably from 12 to 40% by weight, based on the total weight of the suspension. The suspension from process step a) can be supplied undispersed or dispersed, i.e. the suspension includes a dispersant. According to a preferred embodiment, the suspension from step a) is non-dispersed, i.e. it does not contain a dispersant. Step b)
[00070] In step b) of the process according to the present invention at least one acid or acid salt are provided, wherein the acid anion or acid salt are capable of forming water-insoluble calcium salts.
[00071] According to an embodiment of the present invention, the at least one acid or acid salt is selected from the group consisting of strong acids having a pKa value of less than or equal to 0 to 25°C, and medium-strong acids having a pKa value of between 0 and 8, inclusive, and weak acids having a pKa value of between 8 and 20, inclusive, at 25°C.
[00072] According to an embodiment of the present invention, the at least one acid is selected from the group comprising citric acid, oxalic acid, phosphoric acid, sulfuric acid, arsenic acid, and iodic acid.
[00073] According to an embodiment of the present invention, the at least one acid is an organic acid selected from the group comprising citric acid and oxalic acid. According to another embodiment of the inventive process, the at least one acid is an inorganic acid selected from the group comprising phosphoric acid, sulfuric acid, arsenic acid and iodic acid.
[00074] According to yet another preferred embodiment of the present invention, the at least one acid is a non-polymeric acid having a molecular weight of less than 1000 g/mol, preferably less than 750 g/mol , and more preferably less than 500 g/mol.
[00075] According to another embodiment of the present invention, the at least one acid is liquid at 25°C and 1 bar. According to another embodiment of the present invention the at least one acid is solid at 25°C and 1 bar.
[00076] According to an embodiment of the present invention, the at least one acid is dissolved in water. According to an embodiment of the present invention the solution of the at least one acid is a low concentration solution having a concentration of less than 0.1 M. According to another embodiment of the present invention, the solution of the at least one acid is a highly concentrated solution having a concentration of more than 0.1M. According to a preferred embodiment of the present invention the solution of the at least one acid has a concentration of about 0.1M.
[00077] An "acid salt" in the meaning of the present invention is defined as an H3O+ ion supplier that is at least partially neutralized by a non-hydrogen cation, and therefore the "acid salt" comprises at least one " acid anion” and at least one cation other than hydrogen.
[00078] According to an embodiment the non-hydrogen cation can have a positive charge, two positive charges or three positive charges. Cations that have a positive charge are selected from the group comprising Na+, K+ and NH4+, cations that have two positive charges are selected from the group comprising Mg2+ and Sr2+, and cations that have three positive charges are selected from the group comprising Al3+ and Fe2+. Preferably the cation is a sodium cation.
[00079] According to an embodiment of the inventive process, said at least one acid salt is selected from the group comprising sodium citrate dihydrogen, potassium citrate dihydrogen, disodium hydrogen citrate, dipotassium hydrogen citrate, citrate of trisodium, tripotassium citrate, disodium oxalate, dipotassium oxalate, magnesium oxalate, sodium hydrogen sulfate, sodium and potassium sulfate, disodium sulfate, dipotassium sulfate, magnesium sulfate, sodium dihydrogen phosphate, sodium dihydrogen phosphate potassium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate and tripotassium phosphate.
[00080] According to a preferred embodiment, the at least one acid salt is trisodium citrate.
[00081] According to an embodiment of the present invention the at least one acid salt is provided in the form of a solution. According to an embodiment of the present invention, the at least one acid salt is dissolved in water. According to another embodiment of the present invention the at least one acid salt is dissolved in an organic solvent, preferably selected from the group comprising, methanol, ethanol, acetone, and mixtures thereof. If the acid salt is provided in the form of a solution, the solution is preferably prepared in which the acid salt is added to a solvent, preferably water, having a temperature of at least 1°C, preferably from 20°C to 100°C, more preferably from 25°C to 80°C and more preferably from 30°C to 60°C.
[00082] In a preferred embodiment, the acid salt is added to water at about room temperature, that is, at a temperature of 20°C ± 2°C.
[00083] According to an embodiment of the present invention the solution of the at least one acid salt is a low concentration solution having a concentration of less than 0.1 M, preferably less than 0.05 M, and more preferably less than 0.025M. According to another embodiment of the present invention the solution of the at least one acid salt is a highly concentrated solution having a concentration of more than 0.1M, preferably more than 0.2M and more preferably more than 0.5M. According to a preferred embodiment of the present invention the solution of the at least one acid salt has a concentration of about 0.1M.
[00084] According to an alternative embodiment, the acid salt is provided in dry form, for example in the form of a dry powder.
[00085] According to an embodiment of the inventive process, the at least one acid or acid salt are added in an amount of from 0.001 to 40% by weight, preferably from 0.005 to 20% by weight, more preferably from 0. 01 to 10% by weight and more preferably from 0.05 to 5% by weight, based on the total amount of dry calcium carbonate containing material. Step c)
[00086] In step c) of the process according to the present invention an anionic polymeric binder is provided, wherein said binder comprises at least one modified polysaccharide.
[00087] The "modified polysaccharides" in the meaning of the present invention are polysaccharides, in which at least a part of the hydroxyl groups is carboxylated. Additionally, modified polysaccharides may contain other modifications such as aldehyde groups.
[00088] The modified polysaccharides according to the present invention may comprise the following structure:
where a part of the hydroxyl groups is carboxylated and "n" is indirectly represented by the intrinsic viscosity.
[00089] Polysaccharides are polymeric carbohydrate structures, formed of repeating units (at least 10) joined together by glycosidic bonds. Depending on the spatial arrangement of the glycosidic bonds, one can distinguish between α- and β-glycosidic bonds. These structures can be linear, but they can also contain varying degrees of branching. Polysaccharides can also contain minor repeat unit modifications. Exemplary polysaccharides are starch, cellulose, or glycogen, but also structural polysaccharides such as cellulose and chitin.
[00090] According to an embodiment of the present invention, the at least one modified polysaccharide has a degree of substitution of the hydroxyl groups in the range from 0.4 to 2.0, preferably from 0.5 to 1.8, more preferably from 0.6 to 1.6, and more preferably from 0.7 to 1.5.
[00091] According to an embodiment of the present invention, the modified polysaccharide is a carboxymethyl derivative and/or a carboxymethyl hydroxypropyl derivative and/or a carboxymethyl hydroxyethyl derivative of a polysaccharide. For example, the modified polysaccharide can be a carboxymethyl cellulose (CMC), an anionic starch, an anionic guar, xanthan gum, or mixtures thereof.
[00092] According to a preferred embodiment of the present invention, the at least one modified polysaccharide is carboxymethyl cellulose (CMC).
[00093] Carboxymethyl cellulose (CMC) can be prepared from cellulose by reaction with monochloroacetic acid in the presence of caustic soda to form the sodium salt of carboxymethyl cellulose. Each repeating unit of D-glucose contains three hydroxyl groups capable of etherification, to give a maximum charge density of the three carboxyl groups per monomer unit (ie, a degree of substitution of three).
[00094] The molecular weight and intrinsic viscosity of binder materials based on carboxymethylcellulose can be adjusted by any method that is known to the person skilled in the art, for example, by the addition of peroxides. Reference is made to DE 1 543 116 A1 which describes a method for preparing low viscosity, water-soluble CMC by oxidative degradation with H2O2 and to DE 44 11 681 A1 which describes the dependence of polysaccharide ether degradation on the amount of agent of oxidation, temperature and duration of treatment.
[00095] According to a preferred embodiment of the present invention, carboxymethylcellulose has an intrinsic viscosity in the range from 5 to 500 ml/g, preferably from 10 to 450 ml/g, more preferably from 50 to 350 ml/g and more preferably from 100 to 200 ml/g.
[00096] According to another preferred embodiment of the present invention, the at least one modified polysaccharide is an anionic starch.
[00097] Anionic starch is preferably chemically modified with anionic groups selected from the group comprising carboxyl groups, carboxymethyl groups, carboxymethyl hydroxy-propyl groups, carboxymethyl hydroxyethyl groups, phosphate groups, sulfonate groups and mixtures thereof. The anionic starch can be chosen from chemically modified starches that originate from starches selected from the group comprising wheat starch, corn starch, rice starch, potato starch, tapioca starch, arrowroot starch, sorghum starch and the mixtures thereof. Anionic starch can also be obtained from genetically modified sources which comprise starches enriched with amylopectin. In a preferred embodiment, the anionic starch is selected from those enriched in amylopectin, that is to say chemically modified starch is preferably selected from the group consisting of rice starch, potato starch, and mixtures thereof. Methods for preparing such anionic starches are known to the skilled person. The molecular weight of anionic starch can range from 1,000 to 1,000,000 g/mol and is generally about 220,000 g/mol. The molecular weight of anionic starch can be adjusted by treatment with hydrogen peroxide (H2O2).
[00098] According to another preferred embodiment of the present invention, the at least one modified polysaccharide is an anionic guar.
[00099] Guar comprises a natural heteropolysaccharide (guar gum) which consists of galactose units and mannose units usually in the ratio of 1:2 and is the endosperm component of guar seeds. In general, guar comprises a linear chain of 1,4-linked β-D-manopyranosyl units with 1,6-linked α-D-galactopyranosyl units. Guar seeds containing about 14 to 17% by weight husks, 35 to 42% by weight endosperm and 43 to 47% by weight embryo, are usually dry milled and sieved to separate the endosperm which is commercial industrial guar. A guar derivative can be obtained, for example, by modifying the heteropolysaccharide through the use of enzymes, acids, medium oxidation, temperature, radiation etc. Methods for preparing such guar derivatives are known to the skilled person. For example, a modification can be achieved by using a commercially available α-D-galactosidase enzyme that is useful for removing α-D-galactopyranosyl units. By controlling the length of time guar gum is exposed to the α-D-galactosidase enzyme, the degree to which α-D-galactopyranosyl units are removed from the linear chain of mannose units can be controlled. Additionally or alternatively, a modification of guar can be obtained by etherification of guar with propylene oxide or ethylene oxide resulting in a hydroxypropyl guar or hydroxyethyl guar.
[000100] According to an embodiment of the present invention, the anionic guar is a carboxymethyl guar (CMG) and/or a carboxymethyl hydroxypropyl guar (CMHPG) and/or a carboxymethyl hydroxyethyl guar (CMHEG). For example, carboxymethyl guar is obtained by reacting Um guar with monochloroacetic acid in the presence of caustic soda.
[000101] According to an embodiment of the present invention, the anionic polymeric binder of process step c) comprises a modified polysaccharide. According to another embodiment of the present invention, the anionic binder of process step c) comprises two or more modified polysaccharides. According to a preferred embodiment of the present invention, the anionic polymeric binder of process step c) consists of at least one modified polysaccharide. The anionic polymeric binder of process step c) may consist of one type of modified polysaccharide, or it may consist of a mixture of two or more types of modified polysaccharide.
[000102] According to an embodiment of the present invention, the anionic polymeric binder used in the process according to the present invention has a pH from 4.5 to 12, preferably from 7 to 11, and more preferably from 8.0 to 10.5.
[000103] The anionic polymeric binder can be supplied as a solution or dry material. According to a preferred embodiment, the anionic polymeric binder is in the form of an aqueous solution.
[000104] According to a preferred embodiment of the present invention, the anionic polymeric binder is in the form of an aqueous solution having a binder concentration of 1 to 70% by weight, preferably 2 to 55% by weight, more preferably from 5 to 50% by weight, and more preferably from 30 to 50% by weight, based on the total weight of the solution.
[000105] The modified polysaccharide solution can be concentrated, for example, by ultrafiltration or thermal or drying. The dried modified polysaccharide is preferably produced by thermal drying, more preferably spray drying and has a solids content of more than 90, preferably 95 to 99.9% by weight, based on the total weight of the modified polysaccharide.
[000106] According to an embodiment of the present invention the binder of step c) is added in an amount of 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, and more preferably from 0.05 to 5% by weight, based on the total weight of the dry calcium carbonate containing material.
[000107] According to a preferred embodiment of the present invention, the anionic binder of step c) is at least one carboxymethylcellulose added in an amount of 0.05 to 5% by weight, preferably 0.1 to 2.5 % by weight, based on the total weight of dry calcium carbonate-containing material. Step d)
[000108] In step d) of the process according to the present invention at least one cationic polymer is provided.
[000109] The inventors of the present application surprisingly found that the addition of at least one cationic polymer can lead to better retention of the self-bonding pigment particles during papermaking processes. Without being bound by any theory, it is believed that the anionic polymeric binder anionic charge is at least partially neutralized by the cationic polymer.
[000110] The inventors have also found that the addition of at least one cationic polymer can reduce the amount of free polymer in the obtained high-binding pigment particle suspension. Without being bound by any theory, it is believed that the cationic polymer can improve the adhesion or adsorption of the anionic binder and/or the at least one cationic polymer on the ground calcium carbonate particles. This finding was very surprising since it is known that dispersion of ground calcium carbonate with cationic starch can result in the suspension of the pigment particle containing high amounts of free polymer.
[000111] Furthermore, the inventors surprisingly found that self-bonding properties of the pigment particles are also improved. As a result, paper products comprising the inventive self-binding particles as filler material exhibit improved strength, and also allow the production of papers with high content of material filler. A further advantage is the physical and optical properties of paper comprising the inventive self-binding pigment particles as filler material to any substantial degree.
[000112] According to an embodiment of the present invention, the at least one cationic polymer is selected from polyamines, polyethyleneimines, polyacrylamides, cationic epichlorohydrin resins, polydiallyldimethylammonium chloride, cationic starch, cationic guar, or mixtures thereof.
[000113] According to an embodiment of the present invention, the at least one cationic polymer is a polyamine, preferably a polyethyleneimine (PEI) being selected from the group comprising branched polyethyleneimines, linear polyethyleneimines and mixtures of the foregoing. Preferably, the ratio of primary, secondary and tertiary amine functions in the inventive branched polyethyleneimines is in the range of 1:0, 86:0, 42 to 1:1, 20:0.76, before a possible modification of the branched polyethyleneimines.
[000114] According to a preferred embodiment of the present invention, the at least one polyethyleneimine is selected from the group of modified and unmodified polyethyleneimines. Examples for branched polyethyleneimines are homopolymers of ethyleneimine (aziridine) or their higher homologues and also graft polymers of polyamidoamines or polyvinylamines with ethyleneimine or their higher homologues. Polyethyleneimines can be cross-linked or uncross-linked, quaternized and/or modified by reaction with alkylene oxides, dialkyl or alkylene carbonates or C1-C8 carboxylic acids. Polyethyleneimines can be modified by reaction with alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate or propylene carbonate , or C1-C8 carboxylic acids. Modified PTIs can include alkoxylated polyethyleneimines such as propoxylated polyethyleneimines (PPEIs) and ethoxylated polyethyleneimines (EPEIs). Other preferred modified polyethyleneimines can be obtained by reacting the unmodified PTIs with one or more C1-C28 fatty acids, preferably with one or more C6-C18 fatty acids and especially preferred with C10-C14 fatty acids, e.g. Of coconut.
[000115] Polyethyleneimine can have a weighted average molecular weight Mw in the range of 1000 g/mol and 1 000 000 g/mol. In another preferred embodiment of the present invention the polyethyleneimine is selected from the group of linear polyethyleneimines having a weight average molecular weight Mw of from 100 to 700 g/mol, and preferably from 146 to 232 g/mol, and preferably is selected from triethylenetetramine , pentaethyleneexamine and tetraethylenepentamine. According to another preferred embodiment the polyethyleneimine is selected from the group of branched polyethyleneimines having a weight average molecular weight Mw of from 500 to 8000 g/mol and preferably from 800 to 1200 g/mol.
[000116] According to an embodiment of the present invention, the at least one cationic polymer is a cationic starch.
[000117] Cationic starch is preferably chemically modified with cationic groups selected from the group comprising amino groups, ammonium groups, ammonium groups, sulphonium groups, phosphonium groups, and mixtures thereof. Cationic starch can be chosen from chemically modified starches that originate from virtually any of the natural surfaces provide starch in reasonable amounts. For example, the cationic starch can be chosen from chemically modified starches that originate from starches selected from the group comprising wheat starch, corn starch, rice starch, potato starch, tapioca starch, arrowroot starch, sorghum and mixtures thereof. In a preferred embodiment, the cationic starch is selected from those enriched in amylopectin, that is to say chemically modified starch is preferably selected from the group consisting of rice starch, potato starch, and mixtures thereof. Cationic starch can also be obtained from genetically modified sources which comprise starches enriched with amylopectin. Methods for preparing such cationic starches are known to the skilled person. The molecular weight of cationic starch can range from 1,000 to 1,000,000 g/mol and is generally about 220,000 g/mol. The molecular weight of cationic starch can be adjusted by treatment with hydrogen peroxide (H2O2).
[000118] According to another embodiment of the present invention, the at least one cationic polymer is A cationic guar.
[000119] Guar comprises a natural heteropolysaccharide (guar gum) which consists of galactose units and mannose units usually in the ratio of 1:2 and is the endosperm component of guar seeds. In general, guar comprises a linear chain of 1,4-linked β-D-manopyranosyl units with 1,6-linked α-D-galactopyranosyl units. Guar seeds containing about 14 to 17% by weight husks, 35 to 42% by weight endosperm and 43 to 47% by weight embryo, are usually ground to dry and sieved to separate the endosperm which is commercial industrial guar . A guar derivative can be obtained, for example, by modifying the heteropolysaccharide through the use of enzymes, acids, medium oxidation, temperature, radiation etc. The methods for preparing such guar derivatives are known to the skilled person. For example, a modification can be achieved by using a commercially available α-D-galactosidase enzyme that is useful for removing α-D-galactopyranosyl units. By controlling the length of time guar gum is exposed to the α-D-galactosidase enzyme, the degree to which α-D-galactopyranosyl units are removed from the linear chain of mannose units can be controlled. A cationic guar can be obtained by reacting guar with derivatives of quaternary ammonium salts.
[000120] According to yet another embodiment of the present invention, the at least one cationic polymer is polydiallyldimethylammonium chloride (polyDADMAC).
[000121] PolyDADMAC (polydiallyldimethylammonium chloride) is a linear homopolymer of diallyldimethylammonium chloride (DADMAC) having the following structure:

[000122] The linear homopolymer formed from a monomer that has a quaternary ammonium and two unsaturated -CH=CH2 functionalities is polymerized by free radical polymerization of DADMAC. In the structure of polyDADMAC the quaternary ammonium groups are on the rings that are included in the backbone of the polymer chain. This composition means that polyDADMAC macromolecules tend to be very hard, having a longer persistence duration than, for example, polyamines. For this reason, polyDADMAC is expected to have a more extended conformation in the solution. The polyDADMAC may have a weight average molecular weight Mw in the range of 10,000 to 1,000,000 g/mol and preferably in the range of 100,000 to 500,000 g/mol.
[000123] Furthermore the examples of cationic polymer that are suitable for the process of the present invention are polyacrylamides, or cationic epichlorohydrin resins.
[000124] According to an exemplary embodiment, polyacrylamides include monomers of dialkyl-aminoethyl (meth)acrylates, dialkylaminoethyl(meth)acrylamides, dialkylaminomethyl(meth)-acrylamides, and dialkylamino-1,3-propyl(meth) acrylamides, preferably copolymerized with non-ionic monomers, preferably arylamide.
[000125] According to another embodiment, cationic epichlorohydrin resins are copolymers comprising as monomer one or more dicarboxylic acids and one or more monomers from the group of diamines, triamines, dialkanolamines or trialkanolamines and epichlorohydrin.
[000126] Preferably saturated or unsaturated, branched or unbranched C2-C10 dicarboxylic acids, preferably C3-C9 dicarboxylic acids, C4-C8 dicarboxylic acids, C5C7 dicarboxylic acids, in particular adipic acid are used as the dicarboxylic acid monomers. Especially suitable as the second monomer of the binder polymer are substituted and unsubstituted linear and branched diamines and triamines, in particular N-(2-aminoethyl)-1,2-ethanediamine. Preferably used dialkanolamines and trialkanolamines include, for example, diethanolamine, N-alkyl dialkanolamines such as N-methyl and N-ethyldiethanolamine and triethanolamine. For monitoring and controlling molecular weight and/or chain length, one or more monovalent amines such as monoalkanolamines can be used during polycondensation. Monoethanol is preferably used. The resulting intermediate product is further reacted with epichlorohydrin.
[000127] According to a preferred embodiment of the present invention, the cationic epichlorohydrin resin is a copolymer of adipic acid with N-(2-aminoethyl)-1,2-ethanediamine and epichlorohydrin.
[000128] According to an embodiment of the present invention, the at least one cationic polymer is a mixture of two or more of the aforementioned polymers. According to another embodiment of the present invention, the at least one cationic polymer consists of one of the aforementioned polymers.
[000129] According to a preferred embodiment, the at least one cationic polymer is polyDADMAC. According to another preferred embodiment, the at least one cationic polymer is a cationic starch.
[000130] The at least one cationic polymer can be provided in an aqueous form, for example, in the form of a water-based solution, or in the form of an organic solution, for example, in an organic solvent selected from the group comprising methanol, ethanol, acetone, and mixtures thereof. However, the at least one cationic polymer can also be provided in the form of an emulsion or a dispersion in water and/or organic solvents, or in the form of a mixture of a solution and/or an emulsion and/or a dispersion in water and /or organic solvents.
[000131] If the at least one cationic polymer is provided in the form of a solution, the solution is preferably prepared in which the at least one cationic polymer is added to a solvent, preferably water, having a temperature of at least 50°C preferably from 50°C to 100°C, more preferably from 60°C to 98°C and more preferably from 70°C to 96°C. For example, the solution is prepared in which the at least one cationic polymer is added to water having a temperature of 80°C to 96°C, such as 90°C to 96°C. Alternatively, the solution is prepared in which the at least one cationic polymer is added to a solvent, preferably water, having a temperature of below 50°C, preferably from 5°C to 50°C, more preferably from 10°C to 40°C and more preferably from 15°C to 30°C.
[000132] In a preferred embodiment, the solution of the cationic polymer is prepared in which the at least one cationic polymer is added to the water around room temperature, that is, at 20°C ± 2°C.
[000133] According to an alternative embodiment, the at least one cationic polymer is provided in dry form, for example in the form of a dry powder.
[000134] In case the at least one cationic polymer is provided in the form of a dispersion, the particle size of the cationic polymer may have a D50 value from 10 to 500 nm, preferably from 20 to 100 nm, and more preferably from 25 to 80 nm.
[000135] The cationic polymer of step d) can be provided in the form of a solution or dry material, preferably in the form of a solution having a concentration of 0.5 to 70% by weight, preferably from 1 to 25% by weight, more preferably from 1.5 to 20% by weight, and more preferably from 2 to 10% by weight, based on the total weight of the solution.
[000136] According to an embodiment of the present invention, the cationic polymer is added in an amount such that the charge density of the obtained self-binding pigment particles is lower compared to the self-binding pigment particles not containing cationic polymer. For example, the cationic polymer can be added in an amount such that the charge density of the obtained self-bonding pigment particle is between -100 and -5 µEq/g, preferably between -80 and -10 µEq/g, and more preferably between -70 and -15 µEq/g.
[000137] According to an embodiment of the present invention, the cationic polymer of step d) is added in an amount of 0.001 to 20% by weight, preferably from 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, and more preferably from 0.05 to 5% by weight or from 0.5 to 1.5% by weight, based on the total weight of the dry calcium carbonate containing material.
[000138] According to a preferred embodiment of the present invention, the at least one cationic polymer of step d) is polyDADMAC, preferably added in an amount from 0.05 to 5% by weight, more preferably from 0.5 to 1.5 % by weight, based on the total weight of the dry calcium carbonate-containing material from step a).
[000139] According to another preferred embodiment of the present invention, the at least one cationic polymer of step d) is cationic starch, preferably added in an amount of 0.05 to 5% by weight, more preferably of 0. 5 to 1.5% by weight, based on the total weight of the dry calcium carbonate-containing material from step a).
[000140] According to a preferred embodiment of the present invention, the anionic binder of step c) is at least one carboxymethylcellulose, and the at least one cationic polymer of step d) is a cationic starch, in which the binder is added in an amount of from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight and more preferably from 0.1 to 2.5 % by weight, based on the total weight of the dry calcium carbonate containing material.
[000141] According to an exemplary embodiment, the anionic binder of step c) is a carboxymethylcellulose, and the at least one cationic polymer of step d) is a cationic starch, in which the binder is added in an amount of about of 0.5% by weight, and the cationic polymer is added in an amount of about 2.0% by weight, based on the total weight of the dry calcium carbonate containing material.
[000142] According to another exemplary embodiment, the calcium carbonate-containing material is calcium carbonate, preferably precipitated calcium carbonate, the anionic binder of step c) is a carboxymethylcellulose, and the at least one polymer The cationic from step d) is a cationic starch, wherein the binder is added in an amount of about 0.5% by weight, and the cationic polymer is added in an amount of about 2.0% by weight, based in the total weight of the dry calcium carbonate-containing material.
[000143] According to yet another exemplary embodiment, the material containing calcium carbonate is calcium carbonate, preferably precipitated calcium carbonate, the at least one acid or acid salt of step b) are citrate trisodium, the anionic binder of step c) is a carboxymethylcellulose, and the at least one cationic polymer of step d) is a cationic starch, wherein the acid or acid salt is added in an amount of about 0.09% in weight, the binder is added in an amount of about 0.5% by weight, and the cationic polymer is added in an amount of about 2.0% by weight, based on the total weight of the calcium carbonate-containing material dry. Step e)
[000144] In step e) of the process according to the present invention, the aqueous suspension of step a) is mixed with the at least one acid or acid salt of step b).
[000145] The inventors of the present invention surprisingly found that the addition of an acid or acid salt to the aqueous suspension of step a) can improve the properties of the self-binding particles. For example the use of at least one acid or acid salt can lead to self-bonding pigment particles with improved properties. For example, such self-bonding pigment particles show improved binding to paper fibers when used as a filler. Without being bound by any theory it is believed that the improved binding to fibers is based on the limits of interaction between calcium carbonate containing pigment particles and the fibers.
[000146] The addition of an acid or acid salt to the aqueous suspension of step a) modifies the surface of particles of calcium carbonate-containing material, and may be especially advantageous for precipitated calcium carbonate particles. PCC particles have many points on their outer surface and thus are relatively rough. It is believed that these tips can intertwine with the paper fibers during papermaking processes, resulting in improved bonding between the particles and the fibers. However, precipitated calcium carbonate particles can release Ca2 ions from the core of the inner particle over time, and therefore lowered limits of interaction between pigment particles and fibers can be the result.
[000147] Surprisingly, the inventors have found that one way to overcome this problem is to treat the aqueous suspension of calcium carbonate containing material with acids or acid salts. Without being bound by any theory, it is believed that during the treatment of precipitated calcium carbonate particles with acid or acid salt, water insoluble calcium salts are formed, which can inhibit the release of Ca2+ ions from the calcium carbonate particles hasty. As a result, the bond between the precipitated calcium carbonate pigment particles and the paper fibers can be improved as the tips of the precipitated calcium carbonate pigment particles are no longer "degraded" or "dissolved" by the release of calcium. This can allow INTER ALIA to increase the filler loading on the paper while maintaining the strength properties of the paper.
[000148] According to an embodiment of the inventive process, the at least one acid or acid salt is added to the aqueous suspension of step a). According to another embodiment of the inventive process, the aqueous suspension from step a) is added to at least one acid or acid salt.
[000149] According to an embodiment of the inventive process, the at least one acid or acid salt are added in the form of a suspension or solution to the aqueous suspension of step a). According to another embodiment of the inventive process, the at least one acid or acid salt is added in the form of a solid to the aqueous suspension of step a). For example, the acid or acid salt can be added in the form of a powder or granule.
[000150] According to an embodiment of the inventive process the at least one acid or acid salt and the aqueous suspension of step a) are mixed under shear. According to another embodiment of the inventive process, shear is stirred after mixing the acid or acid salt and the aqueous suspension of step a). Shear is introduced, for example, by agitation.
[000151] Mixing can be carried out under mixing and/or homogenizing conditions. The skilled person will adapt these mixing and/or homogenizing conditions such as mixing speed and temperature according to their process equipment. For example, mixing and homogenization can take place by means of a coulter mixer. The coulter mixers function by the principle of a mechanically produced fluidized bed. The coulter blades rotate close to the inner wall of a horizontal cylindrical drum and transport the mix components from the product bed and into the open mix space. The mechanically produced fluidized bed guarantees intense mixing of uniform large batches in a very short time. Cutters and/or dispersers are used to disperse lumps in a dry operation. Equipment that can be used in the inventive process is available, for example, from Gebrüder Lodige Maschinenbau GmbH, Germany or from Silverson (U.S.A.). Furthermore, a tubular mixing apparatus, for example, from Ystral GmbH, Ballrechten-Dottingen, Germany can be used. Another type of equipment that can be used in the inventive process is a MEGATRON® Inline Homogenizer from Kinematika AG, Switzerland.
[000152] According to an embodiment of the present invention, the process step e) is carried out using a fluidized bed mixer or coulter mixer.
[000153] Process step e) can be carried out at room temperature, ie at 20°C ± 2°C, or at other temperatures. According to one embodiment the process step e) is carried out at a temperature from 5 to 140°C, preferably from 10 to 110°C, and more preferably from 20 to 105°C. Heat can be introduced by internal shear or by an external source or a combination of these.
[000154] According to an exemplary embodiment of the invention, the suspension from step a) and/or the at least one acid or acid salt from step b) are preheated before these components are mixed in the process step and ).
[000155] According to an embodiment of the present invention, the process step e) is carried out for at least 1 s, preferably for at least 1 min, for example, for at least 15 min, 30 min, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, or 10 hours.
[000156] According to an embodiment of the inventive process the suspension obtained in step e) is used without any further treatment in step f). According to another embodiment of the inventive process, the suspension obtained in step e) is concentrated above before step f).
[000157] The solid contents of the suspension can be adjusted by methods known to the qualified person. To adjust the solid content of the suspension obtained in step e), the suspension can be partially or completely dehydrated by a filtration, centrifugation or thermal separation process. For example, the suspension can be partially or fully dehydrated by a filtration process such as nanofiltration or a thermal separation process such as an evaporation process. Alternatively, water can be added to the suspension (for example resulting from filtration) until the desired solid content is obtained. Additionally or alternatively, a self-binding pigment particle suspension having an appropriate lower content of solid particles may be added to the particulate material of the mixed suspension until the desired solid content is obtained.
[000158] According to an embodiment of the inventive process the suspension obtained by step e) has a solid content of 2 to 99% by weight, preferably from 10 to 60% by weight, more preferably from 15 to 45% by weight weight, and more preferably from 20 to 30% by weight, based on the total weight of the suspension. Step f)
[000159] In step f) of the process according to the present invention the aqueous suspension obtained by step e) is mixed with the anionic polymeric binder of step c) and the at least one cationic polymer of step d).
[000160] According to another embodiment of the inventive process the suspension obtained in step e) is above concentrated before step f). Overconcentration can be accomplished by using thermal and/or mechanical methods well known to the skilled person.
[000161] According to an embodiment of the inventive process, the suspension obtained by step e) is, in a first step, mixed with the anionic polymeric binder of step c), and then, in a second step, it is mixed with the at least one cationic polymer from step d).
[000162] According to an embodiment of the inventive process, the suspension obtained by step e) is, in a first step, mixed with the at least one cationic polymer from step d), and then, in a second step, it is mixed with the anionic polymeric binder of step c).
[000163] According to another embodiment of the inventive process the suspension obtained by step e) is mixed with the anionic polymeric binder from step c) and the at least one cationic polymer from step d) in one step.
[000164] According to an exemplary embodiment of the present invention, in a first step, the suspension obtained by step e) is mixed with the anionic polymeric binder of step c), wherein said binder is provided in the form of a solution, and then, in a second step, the at least one cationic polymer from step d) is added to the suspension in the form of a dry powder.
[000165] According to another exemplary embodiment of the present invention, in a first step, the at least one cationic polymer from step d) is mixed with the anionic polymeric binder from step c) to form a pre-mixed mixture, in that the cationic polymer and the binder are supplied in the form of a solution, and then, in a second step, the premixed solution is mixed with the suspension obtained by step e).
[000166] According to another exemplary embodiment of the present invention, in a first step, the suspension obtained by step e) is mixed with the anionic polymeric binder of step c), and then, in a second step, the suspension The mixture is added to at least one cationic polymer from step d), wherein the cationic polymer is in the form of a solution. The cationic polymer solution may also contain pulp fibers to be used in the papermaking process. According to an embodiment of the present invention, the self-binding pigment particles are produced IN SITU during a paper-making process, in which, in a first step, the suspension obtained by step e) is mixed with the anionic polymeric binder of step c), and then, in a second step, the mixed suspension is added to the cationic polymer of step d), wherein the at least one cationic polymer is in the form of a suspension containing pulp fibers.
[000167] The mixing of step f) can be carried out under mixing and/or homogenizing conditions. The skilled person will adapt these mixing and/or homogenizing conditions such as mixing speed and temperature according to their process equipment. For example, mixing and homogenization can take place by means of a coulter mixer. The coulter mixers function by the principle of a mechanically produced fluidized bed. The coulter blades rotate close to the inner wall of a horizontal cylindrical drum and transport the mix components from the product bed and into the open mix space. The mechanically produced fluidized bed guarantees intense mixing of uniform large batches in a very short time. Cutters and/or dispersers are used to disperse lumps in a dry operation. Equipment that can be used in the inventive process is available, for example, from Gebrüder Lodige Maschinenbau GmbH, Germany or from Silverson (U.S.A.). Furthermore, a tubular mixing apparatus, for example, from Ystral GmbH, Ballrechten-Dottingen, Germany can be used. Another type of equipment that can be used in the inventive process is a MEGATRON® Inline homogenizer from Kinematika AG, Switzerland.
[000168] According to an embodiment of the present invention, the process step f) is carried out using a fluidized bed mixer or coulter mixer.
[000169] The process step f) can be carried out at room temperature, that is, at 20°C ± 2°C, or at other temperatures. According to one embodiment the process step f) is carried out at a temperature from 5 to 140°C, preferably from 10 to 110°C, and more preferably from 20 to 105°C. Heat can be introduced by internal shear or by an external source or a combination of these.
[000170] According to an exemplary embodiment of the invention, the suspension obtained by step e) and/or the anionic polymeric binder of step c) and/or the at least one cationic polymer of step d) are mixed in the step of process f) and thereafter are heated to a temperature of 50 to 120°C, or 60 to 110°C, or preferably 70 to 105°C for about 30 minutes, or preferably for about 60 minutes.
[000171] According to an embodiment of the present invention, the process step f) is carried out for at least 1 s, preferably for at least 1 min, for example, for at least 15 min, 30 min, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, or 10 hours.
[000172] To ensure a better dispersion, a dispersant can also be added to any of the components used in the inventive process, for example, in the form of an aqueous solution and/or a powder of a dispersant. A suitable dispersant is preferably selected from the group comprising homopolymers or copolymers of polycarboxylic acid salts based on, for example, carboxylic acid, metacarboxylic acid, maleic acid, fumaric acid or itaconic acid and acrylamide or mixtures thereof. Carboxylic acid homopolymers or copolymers are especially preferred. The weight average molecular weight Mw of such products is preferably in the range of 2000 to 15000 g/mol, with a weight average molecular weight Mw of 3000 to 7000 g/mol or 3500 to 6000 g/mol being especially preferred. According to an exemplary embodiment, the dispersant is sodium polyacrylate having a weight average molecular weight Mw of from 2000 to 15000 g/mol, preferably from 3000 to 7000 g/mol, and more preferably from 3500 to 6,000 g/mol.
[000173] According to a preferred embodiment, no dispersant is added in process step f).
[000174] The mixing step can be carried out at a high solids content, that is, at a solids content of 50 to 80% by weight, based on the total weight of the suspension. However, the mixing step can be carried out at a solids content of more than 80% by weight, based on the total weight of the suspension, for example using a coulter mixer.
[000175] The solids contents of the suspension can be adjusted by the methods known to the qualified person. To adjust the solid content of an aqueous suspension, the suspension can be partially or fully dehydrated by a filtration, centrifugation or thermal separation process. For example, the suspension can be partially or fully dehydrated by a filtration process such as nanofiltration or a thermal separation process such as an evaporation process. Alternatively, water can be added to solid material (for example resulting from filtration) until the desired solid content is obtained. Additionally or alternatively, a self-binding pigment particle suspension or other pigment particle suspension having an appropriate lower content of solid particles may be added to the particulate material of the mixed suspension until the desired solid content is obtained. The further added self-binding pigment particle suspension or other pigment particle suspensions can be dispersed or non-dispersed.
[000176] According to an embodiment of the present invention, the solid content of the mixed suspension of step f) is adjusted so that it is from 10 to 80% by weight, more preferably from 20 to 70% by weight , more preferably from 40 to 65% by weight, based on the total weight of the suspension.
[000177] According to a preferred embodiment of the present invention, the solid content of the mixed suspension of step f) is adjusted to a high solid content so that it is 50 to 80% by weight, more preferably from 60 to 79% by weight, more preferably from 65 to 78% by weight, based on the total weight of the suspension. Other optional process steps
[000178] According to an optional embodiment of the present invention, the process further comprises a step of concentrating the suspension of the self-binding pigment particles obtained by the process of the present invention.
[000179] The solid content of the obtained self-binding pigment particle suspension can be adjusted by the concentration methods known to the skilled person. The suspension concentration of the corresponding pigment material can be obtained by means of a thermal process, for example in an evaporator, or by means of a mechanical process, for example in a filter press such as nanofiltration, and/or centrifuge.
[000180] The solid content of the self-binding pigment particle suspension obtained by the process of the present invention can be concentrated so that it is from 10 to 80% by weight, more preferably from 20 to 70% by weight, most preferably from 40 to 60% by weight, based on the total weight of the suspension. According to a preferred embodiment, the solid content of the obtained self-binding pigment particle suspension is concentrated to medium solid content so that it is from 50 to 60% by weight. Alternatively, the solid content of the obtained self-binding pigment particle suspension can be concentrated to a high solid content so that it is from 50 to 80% by weight, more preferably from 60 to 79% by weight, most preferably from 65 to 78% by weight, based on the total weight of the suspension.
[000181] According to an optional embodiment of the present invention, the step of concentrating the self-binding particle suspension obtained by the process of the present invention is carried out such that a dry product is obtained. The term "dry product" is understood to refer to pigment particles having a total surface moisture content of less than 0.5% by weight, preferably less than 0.2% by weight and more preferably less than 0.1% by weight, based on the total weight of the pigment particles.
[000182] If the inventive process further comprises the optional step of concentrating the obtained self-binding pigment particle suspension obtained such that a dry product or a suspension having a solid content of at least 65% by weight, more preferably at least 80 % by weight and more preferably at least 90% by weight, based on the total weight of the self-binding pigment particle suspension, is obtained, the dry product or suspension may be rediluted. If the dry product or the suspension is rediluted, the solid content in the obtained suspension is adjusted such that it is at least 1% by weight, preferably from 1% by weight to 80% by weight, more preferably from 5% by weight to 60% by weight, even more preferably from 10% by weight to 50% by weight, and more preferably from 15% by weight to 45% by weight, based on the total weight of the self-binding pigment particle suspension.
[000183] In a preferred embodiment of the present invention, the process of the present invention can lead directly to the suspension of self-binding pigment particles with high solids, that is, to a suspension having a solid content of 50 to 80% by weight , based on the total weight of the self-binding pigment particle suspension, which means that an additional concentration step is not implemented in the process of the present invention. The self-bonding pigment particle suspension
[000184] According to another aspect, the present invention provides a suspension of self-binding pigment particle which is obtainable by the process according to the present invention.
[000185] The inventive self-bonding pigment particles may have a specific surface area from 0.1 to 200 m2/g, preferably from 1 to 25 m2/g, more preferably from 2 to 15 m2/g, and most preferably from 3 at 12 m2/g, measured using nitrogen and the BET method in accordance with ISO 9277:2010.
[000186] According to another aspect of the present invention, the suspension of self-binding pigment particle obtainable by the inventive process is used in paper, plastics, paint, coatings, concrete and/or agricultural applications. For example, the inventive particle suspension can be used as a filler material in these applications.
[000187] According to an exemplary embodiment of the present invention, the self-cleaning particle suspension obtainable by the inventive process is used in paper, for example, in the final wet process of a paper machine, preferably in cigarette paper, cardboard and /or coating applications, or preferably as support for rotogravure and/or offset printing and/or inkjet and/or continuous inkjet printing and/or flexography and/or electrophotography and/or decorative surfaces.
[000188] Another application is the coating of tree leaves and/or plant leaves to reduce exposure to sunlight and UV of the leaf surface.
[000189] According to another aspect of the present invention, a paper product comprising the inventive self-binding pigment particles is provided, wherein the pigment particles comprise calcium carbonate-containing material particles that are at least partially coated with a water-insoluble calcium salt formed from an acid or acid salt, an anionic polymeric binder comprising at least one modified polysaccharide, and at least one cationic polymer.
[000190] According to an embodiment the paper comprising the inventive self-binding pigment particles has a higher tensile index compared to a paper product, in which the inventive self-binding pigment particles are replaced by the same amount of self-binding pigment particles. material containing calcium carbonate. According to an embodiment of the present invention, preferably the stress index is at least 5% higher, more preferably at least 7% higher, and more preferably at least 10% higher compared to the stress index of a paper product, in which the inventive self-binding pigment particles are replaced by the same amount of material particles containing calcium carbonate, and in which the stress index has been back extracted in accordance with ISO 1924-2:2008. In a preferred embodiment the inventive self-bonding pigment particles as filler material have a tensile index of at least 20 Nm/g, preferably at least 22 Nm/g at a filler load of 20% by weight, based on total weight of the paper product.
[000191] It should be understood that the advantageous embodiments described above with respect to the inventive method for manufacturing the self-binding pigment particles can also be used to prepare or define the inventive suspension and its use. In other words, the preferred embodiments described above and any combinations of these embodiments can also be applied to the inventive suspension and its use.
[000192] The scope and interest of the invention will be better understood based on the figures and examples that follow which are intended to illustrate certain embodiments of the invention and are not limiting. Description of the figures:
[000193] Figure 1 shows a diagram in which the rupture dimension of the tested paper samples is plotted against the filler content.
[000194] Figure 2 shows a diagram in which the tension index of the tested paper samples is plotted against the filler content.
[000195] Figure 3 shows a diagram in which the tensile energy absorption of the tested paper samples is plotted against the filler content.
[000196] Figure 4 shows a diagram in which the Scott bond, also referred to as internal bond in the z-direction of the paper samples tested, is plotted against the filler content. Examples 1. Measurement methods
[000197] In what follows, materials and measurement methods implemented in the examples are described. BET surface area
[000198] Specific surface area was measured by the BET method (Brunauer, St., Emmett, PH, Teller, E. (1938): Adsorption of Gases in Multimolecular Layers, J. Am. Chem. Soc., 60 , 309.) in accordance with ISO 9277:2010 using nitrogen, followed by conditioning the sample by heating to 250°C for a period of 30 minutes. Before such measurements, the sample was filtered inside a Büchner funnel, rinsed with deionized water and dried overnight at 90 to 100°C in an oven. Subsequently the dried cake was completely ground in a mortar and the resulting powder placed on a moisture balance at 130°C until a constant weight was reached. Particle Size
[000199] The particle distribution of the calcium carbonate containing material particles was measured using a Sedigraph 5120 from the company Micromeritics, USA. The method and instrument are known to the skilled person and are commonly used to determine the grain size of fillers and pigments. The measurement was carried out in an aqueous solution comprising 0.1% by weight of Na4P2O7. The samples were dispersed using a high speed and supersonic stirrer. Solid content of an aqueous suspension
[000200] The solid content of the suspension (also known as “dry weight”) was back extracted using an HR73 Moisture Analyzer from the company Mettler-Toledo, Switzerland, with the following settings: temperature 120°C, automatic shut-off 3, standard drying, 5 to 20 g of suspension. intrinsic viscosity
[000201] The intrinsic viscosity was back extracted by a Schott AVS 370 system. The samples were dissolved in a 0.2 M solution of NaCl, and subsequently the pH was adjusted to 10 with NaOH. Measurements were taken at 25°C with a type 0a capillary and corrected using Hagenbach's correction. carboxylation degree
[000202] The degree of carboxylation was back extracted by conductometric titration according to Katz ET AL. "The determination of strong and weak acidic groups in sulphite pulps" (Svensk Paperstidn., 1984, 6, pp. 48-53). 2. Examples Example 1 - Comparative Example
[000203] A precipitated scalenohedral calcium carbonate (S-PCC) (commercially available as a slurry with a solid content of 13 % by weight from Omya, Switzerland) having a fineness corresponding to a d50 value of 2.5 µm, a d95 of 5 μm, a d30 of 2 μm and a specific surface area of 3.4 m2g-1 was used as the calcium carbonate-containing material. Example 2 - Comparative Example
[000204] A precipitated scalenohedral calcium carbonate (S-PCC) (commercially available as a slurry with a solid content of 13 % by weight from Omya, Switzerland) having a fineness corresponding to a d50 value of 2.5 µm, a 5 μm D95, a 2 μm D30 and a specific surface area of 3.4 m2g-1 was used as the calcium carbonate-containing material. Trisodium citrate (commercially available from Sigma Aldrich) was used as the acid, and two different carboxymethylcelluloses (CMC) (commercially available from Mare Austria GmbH) having a molecular weight of 60,000 g/mol (Niklacell T10G) and 200,000 g /mol (Niklacell CH90F) were used as an anionic binder. The intrinsic viscosity of the CMCs was 168 ml/g (Niklacell T10G) and 298 ml/g (Niklacell CH90F), and the degree of substitution was 0.8 for both.
[000205] PCC was used in the form of a suspension having a solid content of 13 % by weight. 0.09% by weight of trisodium citrate, based on the total amount of dry PCC, was added to said slurry in a first step and thereafter 0.2% by weight of Niklacell T10G and 0.28% in weight of Niklacell CH90F, based on the total amount of dry PCC, were added to said slurry in a second step, in which sodium citrate was added as a solution in water having a concentration of 35% by weight of citrate of sodium, based on the total weight of the solution, and the CMC was added as an aqueous solution containing 6% by weight of CMC, based on the total amount of the solution. Example 3 - Inventive Example
[000206] 2 wt% cationic starch (C*Bond HR 35845, commercially available from Cargill Deutschland GmbH, Germany), based on the total amount of dry PCC, was added as cationic polymer to the suspension obtained in Example 2 in the form of a powder and thereafter the suspension was heated to 100°C and stirred for 60 min. During treatment, the solids content was maintained at 50% by weight, based on the total weight of the suspension. The suspension was cooled to room temperature. Example 4 - Inventive Example
[000207] 2 wt% cationic starch (C*Bond HR 35845, commercially available from Cargill Deutschland GmbH, Germany), based on the total amount of dry PCC in the fibrous suspension, was added to a Eucalyptus Pulp fiber suspension (Jarilyptus) and thereafter the suspension obtained in Example 2 was added. Starch was prepared by cooking the starch at 100°C in water having a concentration of 1.5% by weight, based on the total weight of the suspension. Sheets formed and tested as described below. Test of mechanical strength properties of uncoated wood paper containing the surface modified precipitated calcium carbonate particles of Examples 3 and 4 as fillers
[000208] Eucalyptus (Jarilyptus) pulp refined to 30°SR was used as pulp. The surface-modified precipitated calcium carbonate particles of Examples 3 and 4 were used as fillers. In addition, a precipitated scalenohedral calcium carbonate (S-PCC) (commercially available as a slurry with a solids content of 13 wt% from Omya, Switzerland) was used having a fineness corresponding to a d50 value of 2.5 µm, a d95 of 5 µm, a d30 of 2 µm and a specific surface area of 3.4 m2g-1 and examples 1 and 2 were used as Comparative Examples. The fillers were diluted with water to a concentration of 10% by weight, based on the total amount of suspension, and de-agglomerated with a high speed stirrer (Kinematica, Switzerland).
[000209] 60 g (dry) pulp was diluted in 10 dm3 of tap water, and then the filler to be tested was added in an amount so as to obtain the overall filler content based on the final paper weight. The suspension was stirred for 30 minutes. Subsequently, 0.06% (based on dry weight) of a polyacrylamide (Polimin 1530, commercially available from BASF, Ludwigshafen, Germany) was added as a retention aid and 78 g/m2 sheets were formed using the sampler of Rapid-Kothen paper. Each sheet was dried using a Rapid-Kothen dryer.
[000210] The filler content in the paper samples was back extracted by burning a quarter of a dry paper sample in a muffle furnace heated to 570°C. After combustion was complete, the residue was transferred into a desiccator and allowed to cool. When room temperature was reached, the weight of the residue was measured and the mass was related to the initially measured weight of the fourth part of the dry paper sample. The filler content in the examples was 18% to 32%.
[000211] The mechanical strength properties of the paper samples were characterized after drying of the paper samples by the crack dimension according to ISO 1924-2:2008, the tensile index according to ISO 1924-2:2008 , the voltage energy absorption according to ISO 1924-2:2008, and the internal bonding (z direction), also referred to as scott bonding, according to SCAN-P80:98 / TAPPI T541.
[000212] Figures 1 to 4 show the mechanical properties of the tested paper samples. The data show that the use of the surface-modified particles of the present invention enables an increase in filler loading from about 20% to about 27% i.e. by about 7% without affecting the strength properties of the paper. In the case of internal bonding (Fig. 4), the effect is even stronger, such that even higher filler contents would be possible.

权利要求:
Claims (25)
[0001]
1. Process for preparing self-binding pigment particles, the process characterized in that it comprises the following steps: a) providing an aqueous suspension comprising at least one calcium carbonate-containing material, b) providing at least one acid or acid salt in an amount of 0.001 to 40% by weight based on the total weight of the dry calcium carbonate-containing material, wherein the acid anion or acid salt is capable of forming water-insoluble calcium salts, c) providing an anionic polymeric binder in an amount of 0.001 to 20% by weight based on the total weight of the dry calcium carbonate-containing material, said binder comprising at least one modified polysaccharide, d) providing at least one cationic polymer in an amount of 0.001 to 20% by weight based on the total weight of the dry calcium carbonate-containing material, e) mixing the aqueous suspension of step a) with the at least one acid or acid salt of step b), and f) mixing the suspension from step e), the anionic polymeric binder from step c) and the at least one cationic polymer from step d).
[0002]
2. Process according to claim 1, characterized in that in step f) the suspension obtained by step e) is, in a first step, mixed with the anionic polymeric binder of step c), and then, in a second step step, is mixed with the at least one cationic polymer from step d).
[0003]
3. Process according to claim 1, characterized in that in step f) the suspension obtained by step e) is mixed with the anionic polymeric binder from step c) and the at least one cationic polymer from step d) in a stage.
[0004]
4. Process according to claim 1, characterized in that in step f) the suspension obtained by step e) is, in a first step, mixed with the at least one cationic polymer from step d), and then, in a second step is mixed with the anionic polymeric binder of step c).
[0005]
5. Process according to any of the preceding claims, characterized in that the suspension obtained by step e) is concentrated before step f).
[0006]
6. Process according to any of the preceding claims, characterized in that the at least one calcium carbonate-containing material is selected from calcium carbonate, calcium carbonate-containing minerals, calcium carbonate-based fillers mixed, or mixtures thereof, preferably the calcium carbonate containing material is calcium carbonate, more preferably precipitated calcium carbonate (PCC) and most preferably is scalenohedral PCC (S-PCC), rhombohedral PCC (R-PCC ), prismatic PCC (P-PCC), cubic PCC (C-PCC), or a mixture thereof.
[0007]
7. Process according to any one of the preceding claims, characterized in that the at least one calcium carbonate-containing material of step a) is supplied in the form of particles having a d50 value of the weighted average particle diameter of 0. 1 to 100 µm, preferably from 0.2 to 50 µm, more preferably from 0.5 to 25 µm, and most preferably from 1.0 to 10 µm.
[0008]
8. Process according to any one of the preceding claims, characterized in that the at least one calcium carbonate-containing material of step a) is supplied in the form of particles having a specific surface area of 0.1 to 200 m2 µg, preferably from 0.5 to 100 m2/g, more preferably from 1.0 to 50 m2/g, and most preferably from 2.0 to 10 m2/g.
[0009]
9. Process according to any one of the preceding claims, characterized in that the aqueous suspension of step a) has a solid content of 1 to 99% by weight, preferably 15 to 70% by weight, more preferably 10 to 50% by weight, and more preferably from 12 to 40% by weight, based on the total weight of the suspension.
[0010]
10. Process according to any of the preceding claims, characterized in that the suspension of step a) further comprises minerals such as talc, kaolin, TiO2, bentonite and their mixtures.
[0011]
11. Process according to any one of the preceding claims, characterized in that the at least one acid or acid salt of step b) is added in an amount from 0.005 to 20% by weight and more preferably from 0.01 to 10% by weight, and more preferably from 0.05 to 5% by weight, based on the total weight of the dry calcium carbonate containing material.
[0012]
12. Process according to any one of the preceding claims, characterized in that the at least one acid or acid salt of step b) is selected from the group comprising citric acid, oxalic acid, phosphoric acid, sulfuric acid, arsenic acid and iodic acid or salts thereof, and mixtures thereof.
[0013]
13. Process according to any one of the preceding claims, characterized in that the suspension obtained by step e) has a solid content of 2 to 99% by weight, preferably 10 to 60% by weight, more preferably 15 to 45% by weight, and more preferably from 20 to 30% by weight, based on the total weight of the suspension.
[0014]
14. Process according to any one of the preceding claims, characterized in that the at least one modified polysaccharide is a carboxymethyl derivative and/or a carboxymethyl hydroxypropyl derivative and/or a carboxymethyl hydroxyethyl derivative of a polysaccharide, preferably a carboxymethylcellulose, an anionic guar, an anionic starch, or xanthan gum.
[0015]
15. Process according to any one of the preceding claims, characterized in that the at least one modified polysaccharide has a degree of substitution of hydroxyl groups in the range from 0.4 to 2.0, preferably from 0.5 to 1, 8, more preferably from 0.6 to 1.6, and more preferably from 0.7 to 1.5.
[0016]
16. Process according to any one of the preceding claims, characterized in that the intrinsic viscosity of the at least one modified polysaccharide is in the range from 5 to 500 ml/g, preferably from 10 to 450 ml/g, more preferably from 50 to 350 ml/g, and more preferably from 100 to 200 ml/g.
[0017]
17. Process according to any one of the preceding claims, characterized in that the binder of step c) is in the form of an aqueous solution or dry material, preferably in the form of a solution having a binder concentration of 1 to 70% by weight, preferably from 2 to 55% by weight, more preferably from 5 to 50% by weight, and most preferably from 30 to 50% by weight, based on the total weight of the solution.
[0018]
18. Process according to any one of the preceding claims, characterized in that the binder of step c) is added in an amount of 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight, and more preferably from 0.05 to 5% by weight, based on the total weight of the dry calcium carbonate containing material.
[0019]
19. Process according to any of the preceding claims, characterized in that the at least one cationic polymer of step d) is selected from the group comprising polyethyleneimines, polyacrylamides, cationic epichlorohydrin resins, cationic starch, cationic guar, and mixtures of the same.
[0020]
20. Process according to any one of the preceding claims, characterized in that the at least one cationic polymer of step d) is in the form of a solution or dry material, preferably in the form of a solution having a concentration of 0.5 to 70% by weight, preferably from 1 to 25% by weight, more preferably from 1.5 to 20% by weight, and most preferably from 2 to 10% by weight, based on the total weight of the solution.
[0021]
21. Process according to any one of the preceding claims, characterized in that the at least one cationic polymer of step d) is added in an amount of 0.005 to 15% by weight, more preferably from 0.01 to 10% by weight weight, and more preferably from 0.05 to 5% by weight, based on the total weight of the dry calcium carbonate containing material.
[0022]
22. Self-bonding pigment particle suspension, characterized in that it is obtainable by a process as defined in any one of claims 1 to 21, wherein the self-bonding pigment particles have a specific surface area from 0.1 to 200 m2/g, measured using nitrogen and the BET method according to ISO 9277:2010.
[0023]
23. Use of a self-binding pigment particle suspension as defined in claim 22, characterized in that it is in paper, plastics, paint, coatings, concrete and/or agricultural applications, wherein preferably the self-binding pigment particle suspension is used in the final wet process of a paper machine, in cigarette paper, cardboard, and/or coating applications, or as a support for rotogravure and/or offset and/or inkjet and/or inkjet printing. continuous ink and/or flexography and/or electrophotography and/or decorative surfaces, or the self-bonding pigment particle suspension is used to reduce the exposure to sunlight and UV of plant leaves.
[0024]
24. Paper product, characterized in that it comprises self-binding pigment particles, wherein the pigment particles comprise particles of calcium carbonate-containing material that are at least partially coated with a water-insoluble calcium salt formed from of an acid or acid salt, an anionic binder comprising at least one modified polysaccharide, and at least one cationic polymer.
[0025]
25. The paper product of claim 24, characterized in that the paper product has a higher tensile index compared to a paper product, in which the inventive self-binding pigment particles are replaced by the same amount of particles of calcium carbonate-containing material, preferably the tensile index is at least 5% higher, more preferably at least 7% higher, and more preferably at least 10% higher compared to the tensile index of a paper product , wherein the inventive self-bonding pigment particles are replaced by the same amount of calcium carbonate containing material particles.

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CN104284945B|2017-03-01|

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EP2662416B1|2015-07-22|

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CO7141472A2|2014-12-12|

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CA2871097C|2017-11-07|

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AR091005A1|2014-12-30|

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DK2662416T3|2015-10-05|

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AU2013258201A1|2014-11-13|

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MX2014013222A|2015-02-18|

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US20170369695A1|2017-12-28|

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CN104284945A|2015-01-14|

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US20150096698A1|2015-04-09|

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EP2850135A1|2015-03-25|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-02-23| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP12167650.6|2012-05-11|

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EP12167650.6A|EP2662416B1|2012-05-11|2012-05-11|Treatment of calcium carbonate containing materials for increased filler load in paper|

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US201261648642P| true| 2012-05-18|2012-05-18|

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US61/648,642|2012-05-18|

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PCT/EP2013/059197|WO2013167473A1|2012-05-11|2013-05-02|Treatment of calcium carbonate containing materials for increased filler load in paper|

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