CN1898439A - Filler for papermaking process - Google Patents

Abstract

The present invention relates to a filler comprising a calcium salt and a cellulose derivative having a degree of substitution of net ionic groups up to about 0.65, wherein the filler is substantially free of cellulose or lignocellulose fibres or fibrils. The invention also relates to a filler comprising a calcium salt and a cellulose derivative having a degree of substitution of net ionic groups up to about 0.65, wherein the cellulose derivative contains cationic groups. The invention further relates to a method for preparing a filler, comprising: the calcium salt-containing material is admixed with a cellulose derivative having a degree of substitution of net ionic groups of up to about 0.65 in the substantial absence of cellulose or lignocellulosic fibres or fibrils. The invention also relates to a method for preparing a filler, comprising: a calcium salt-containing material is mixed with a cellulose derivative having a degree of substitution of net ionic groups of up to about 0.65, wherein the cellulose derivative contains cationic groups. The invention further relates to a filler obtainable by these methods. The invention further relates to a process for making paper comprising: providing an aqueous suspension containing cellulosic fibres, introducing into the suspension a filler comprising a calcium salt and a cellulose derivative having a degree of substitution of net ionic groups up to about 0.65, wherein the filler is substantially free of fibres or fibrils of cellulose or lignocellulose, and dewatering the suspension to form a paper web or sheet. The invention also relates to a process for making paper comprising: providing an aqueous suspension containing cellulosic fibres, introducing into the suspension a filler comprising a calcium salt and a cellulose derivative having a degree of substitution of net ionic groups up to about 0.65, wherein the cellulose derivative contains cationic groups, and dewatering the suspension to form a web or sheet of paper.

Description

Translated fromChinese

用于造纸方法的填料Fillers for papermaking processes

本发明涉及一种包含钙盐和纤维素衍生物的填料。本发明进一步涉及一种制备该填料的方法、该填料在造纸中的应用、一种其中将该填料用作添加剂的造纸方法以及包含该填料的纸。The present invention relates to a filler comprising a calcium salt and a cellulose derivative. The invention further relates to a process for preparing the filler, the use of the filler in papermaking, a papermaking process in which the filler is used as an additive, and paper comprising the filler.

                    发明背景Background of the Invention

在造纸工业中高度填充的纸是一种既定趋势，这不仅是因为减少使用纤维的节省而且还因为改进的产品质量，例如更高的不透明性和更好的可印刷性。基于碳酸钙的填料由于它们优良的光散射性能而被普遍使用。在高度填充的、特别含有高表面积的填料的纸的制备中的主要缺陷是上胶剂的高消耗。从而，随着纸中的填料含量增加，为了获得相应的上胶结果而需要较大量的上胶剂。因此，当填料的量增加时更难以将纤维素悬浮液上胶。Highly filled papers are an established trend in the paper industry, not only because of savings from reduced use of fibers but also because of improved product qualities such as higher opacity and better printability. Calcium carbonate based fillers are commonly used due to their excellent light scattering properties. A major drawback in the production of highly filled papers, especially those containing fillers of high surface area, is the high consumption of sizing agents. Thus, as the filler content in the paper increases, a larger amount of sizing agent is required to obtain a corresponding sizing result. Therefore, it is more difficult to size the cellulosic suspension when the amount of filler is increased.

为了实现纸或纸板的防水性和减少边缘起芯(wicking)，主要进行上胶。其还将影响纸和纸板的机械性能，例如尺寸稳定性、摩擦系数、柔韧性和耐折强度。另外，上胶可以通过控制油墨扩散和粘合而特别地提高可印刷性。In order to achieve water repellency and reduce edge wicking of the paper or board, sizing is mainly carried out. It will also affect the mechanical properties of paper and board, such as dimensional stability, coefficient of friction, flexibility and folding strength. In addition, sizing can specifically improve printability by controlling ink spreading and adhesion.

上胶方法涉及到使憎水性物质-通常被称作上胶剂沉积在纤维表面上。普遍采用的上胶剂是非纤维素活性的上胶剂例如基于松香的上胶剂，和纤维素活性的上胶剂，例如烷基烯酮二聚物(“AKD”)和酸酐例如链烯基琥珀酸酐(“ASA”)。然而，公知的是纤维素活性的上胶剂-即AKD和ASA经历了水解，这与所希望的和纤维的反应相竞争。此外，由于胶料倒置或迁移、胶料蒸发、产品的机械磨损等，可能出现最终产品的上胶损失。The sizing process involves depositing a hydrophobic substance, commonly referred to as a sizing agent, on the fiber surface. Commonly used sizing agents are non-cellulosic reactive sizing agents such as rosin-based sizing agents, and cellulosic reactive sizing agents such as alkyl ketene dimers ("AKD") and anhydrides such as alkenyl Succinic anhydride ("ASA"). However, it is well known that cellulose active sizing agents - ie AKD and ASA - undergo hydrolysis which competes with the desired reaction with the fibers. In addition, loss of sizing on the final product may occur due to inversion or migration of the sizing material, evaporation of the sizing material, mechanical wear of the product, etc.

Bartz和同事已经观察到在AKD蜡的流动性增加期间，一些AKD可能渗透并且此后被捕集在填料的孔隙结构中(Bartz，W.；Darroch，M.E.；Kurrle，F.L.，“碳酸钙填充的纸中的烷基烯酮二聚物上胶效率和倒置”，Tappi Journal，77卷，12期，1994)。对于具有多孔瓣状体结构和高表面积的偏三角面体形状的PCC而言，特别出现了这种现象。Voutllainen指出具有高表面积的填料吸附AKD甚至比纤维更好(Voutilainen，P.，“烷基烯酮二聚物在纸浆纤维和CaCO3填料上的竞争吸附”，Proceedings from International Paper andCoating Chemistry Symposium，1996)。填料表面上铝氧化物和硅氧化物的存在可以另外吸附含于AKD颗粒中的阳离子淀粉。还提出了在AKD与碳酸钙填料之间存在强的相互作用，或者可能甚至是结合。这些所提出的填料机理自然是不希望的，并且应作出努力以使这些相互作用减少到最小。Bartz and co-workers have observed that during the increased mobility of AKD wax, some AKD may permeate and thereafter become trapped in the pore structure of the filler (Bartz, W.; Darroch, M.E.; Kurrle, F.L., "Calcium carbonate-filled paper Sizing efficiency and inversion of alkylketene dimers in ", Tappi Journal, Vol. 77, Issue 12, 1994). This phenomenon was particularly observed for scalenohedral-shaped PCCs with a porous petaloid structure and high surface area. Voutllainen pointed out that fillers with high surface area adsorb AKD even better than fibers (Voutilainen, P., "Competitive adsorption of alkyl ketene dimers on pulp fibers and CaCO3 fillers", Proceedings from International Paper and Coating Chemistry Symposium, 1996) . The presence of aluminum oxides and silicon oxides on the filler surface can additionally adsorb the cationic starch contained in the AKD granules. It has also been suggested that there is a strong interaction, or possibly even binding, between AKD and the calcium carbonate filler. These proposed filler mechanisms are naturally undesirable and efforts should be made to minimize these interactions.

为了提高上胶效率，在美国专利No.5,514,212中提出可以用阴离子淀粉-皂复合物将颜料的表面改性。得自于玉米或马铃薯的蒸煮淀粉与脂肪酸盐复合并且当与沉淀的钙浆液或者含有高含量的钙离子的造纸配料混合时沉淀在颜料表面上。In order to improve the sizing efficiency, it is proposed in US Patent No. 5,514,212 that an anionic starch-soap complex can be used to modify the surface of the pigment. Cooked starch derived from corn or potatoes is complexed with fatty acid salts and precipitates on the pigment surface when mixed with precipitated calcium slurries or papermaking furnishes containing high levels of calcium ions.

美国专利No.5,972,100提出了一种由纤维素活性的浆料(例如AKD)、阳离子分散剂(例如阳离子淀粉或聚酰胺)和填料组成的体系。除了改进的上胶之外，该发明使得能够分别独立地控制填料装填量和上胶。US Patent No. 5,972,100 proposes a system consisting of a cellulosic active size such as AKD, a cationic dispersant such as cationic starch or polyamide, and a filler. In addition to improved sizing, this invention enables independent control of filler loading and sizing, respectively.

此外，WO95/13324涉及到用纤维素衍生物例如取代度为0.7的羧甲基纤维素钠(“CMC”)处理的碳酸钙。所述处理的碳酸钙被用作碱性造纸悬浮液中的填料，由此提高了纸的亮度。Furthermore, WO95/13324 relates to calcium carbonate treated with a cellulose derivative such as sodium carboxymethylcellulose ("CMC") having a degree of substitution of 0.7. The treated calcium carbonate is used as a filler in alkaline papermaking suspensions, thereby increasing the brightness of the paper.

美国专利No.3,730,830披露了一种制备纸，特别是像纸的方法，其包括使用合成聚合物纤维。在将合成纤维加入纤维悬浮液之前，将无机颜料或碳加入含有羧甲基纤维素和合成纤维的浆液中，由此实现了聚合物纤维在造纸原料中的纤维素纤维之间均匀分散。US Patent No. 3,730,830 discloses a method of making paper, especially paper like paper, which involves the use of synthetic polymer fibers. Before the synthetic fibers are added to the fiber suspension, inorganic pigments or carbon are added to the slurry containing carboxymethylcellulose and synthetic fibers, thereby achieving uniform dispersion of the polymer fibers among the cellulose fibers in the papermaking stock.

仍然需要一种提供改进的造纸方法和更好性能的所制备的纸的填料。将希望的是提供一种使得可以制备表现出优良的印刷性能和机械性能的高度填充的纸的填料。还将希望的是提供一种减少了上胶需求并且由此导致改进的上胶效率的填料。还将希望的是提供一种可与助滤剂和助留剂相容并且由此导致优良的排水性、保持性和造纸机运行能力的填料。还将希望的是提供一种简单和有效的用于制备表现出以上特性的填料的方法。There remains a need for a filler that provides improved papermaking processes and better properties of the paper produced. It would be desirable to provide a filler that would allow the preparation of highly filled papers exhibiting excellent printing and mechanical properties. It would also be desirable to provide a filler that reduces sizing requirements and thereby results in improved sizing efficiency. It would also be desirable to provide a filler that is compatible with drainage and retention aids and thereby results in good drainage, retention and paper machine runnability. It would also be desirable to provide a simple and efficient method for preparing fillers exhibiting the above properties.

                    发明概述Invention Summary

总的来说，本发明涉及一种包含钙盐和纤维素衍生物的填料。总的来说，本发明进一步涉及一种包含钙盐和羧烷基纤维素衍生物的填料。总的来说，本发明还涉及一种通过将含有钙盐的材料与纤维素衍生物混合而制备填料的方法、该填料在造纸中用作添加剂的应用以及包含该填料的纸。总的来说，本发明进一步涉及一种其中将该填料引入含水的纤维素悬浮液的造纸方法。In general, the present invention relates to a filler comprising a calcium salt and a cellulose derivative. In general, the present invention further relates to a filler comprising a calcium salt and a carboxyalkylcellulose derivative. In general, the present invention also relates to a process for preparing a filler by mixing a calcium salt-containing material with a cellulose derivative, the use of the filler as an additive in papermaking and paper comprising the filler. In general, the invention further relates to a papermaking process in which the filler is introduced into an aqueous cellulosic suspension.

更特别地，本发明涉及一种包含钙盐和净离子基团取代度至多约0.65的纤维素衍生物的填料。本发明还涉及一种包含钙盐和羧烷基取代度至多约0.65的纤维素衍生物的填料。本发明进一步涉及一种制备填料的方法，其包括：将含有钙盐的材料与净离子基团取代度至多约0.65的纤维素衍生物混合。本发明还涉及一种制备填料的方法，其包括：将含有钙盐的材料与羧烷基取代度至多约0.65的纤维素衍生物混合。本发明进一步涉及一种可通过这些方法获得的填料。本发明进一步涉及一种造纸方法，其包括：提供含有纤维素纤维的含水悬浮液、将包含钙盐和净离子基团取代度至多约0.65的纤维素衍生物的填料引入悬浮液，和将悬浮液脱水以形成纸幅或纸片。本发明还涉及一种造纸方法，其包括：提供含有纤维素纤维的含水悬浮液、将包含钙盐和羧烷基取代度至多约0.65的纤维素衍生物的填料引入悬浮液，和将悬浮液脱水以形成纸幅或纸片。在该造纸方法中，可以通过将钙盐和纤维素衍生物一起作为单一组合物加入而将填料引入纤维素悬浮液。More particularly, the present invention relates to a filler comprising a calcium salt and a cellulose derivative having a degree of substitution of net ionic groups of at most about 0.65. The present invention also relates to a filler comprising a calcium salt and a cellulose derivative having a degree of carboxyalkyl substitution of up to about 0.65. The invention further relates to a method of preparing a filler comprising: mixing a calcium salt-containing material with a cellulose derivative having a degree of substitution of net ionic groups of at most about 0.65. The present invention also relates to a method of preparing a filler comprising: mixing a calcium salt-containing material with a cellulose derivative having a degree of carboxyalkyl substitution of at most about 0.65. The invention further relates to a filler obtainable by these methods. The present invention further relates to a process for making paper comprising: providing an aqueous suspension containing cellulose fibers, introducing a filler comprising a calcium salt and a cellulose derivative having a degree of substitution of net ionic groups of up to about 0.65 into the suspension, and adding the suspended The liquid is dewatered to form a paper web or sheet. The present invention also relates to a process for making paper comprising: providing an aqueous suspension containing cellulose fibers, introducing a filler comprising a calcium salt and a cellulose derivative having a degree of carboxyalkyl substitution of up to about 0.65 into the suspension, and introducing the suspension into Dewatering to form a web or sheet. In this papermaking process, fillers can be introduced into the cellulosic suspension by adding the calcium salt and the cellulose derivative together as a single composition.

                    发明详述                    Invention Details

本发明提供一种适用于造纸的新的填料。已经令人惊奇地发现，根据本发明的填料使得可以减少与在造纸中普遍使用并且被掺入纸中的填料相关的一些问题。更特别地，通过将本发明的填料用于造纸方法，可以提供具有优良的印刷性能例如高的光滑度、高的不透明度和洁白度，改进的机械性能例如干强度、拉伸强度、Scott结合性和抗弯刚度，和改进的上胶效果的纸。由本发明所表现出的另一些优点包括优良的和/或改进的脱水性和细粒保持性，这导致了就造纸机的运行性能而言的优点。The present invention provides a new filler suitable for papermaking. It has surprisingly been found that the filler according to the invention makes it possible to reduce some of the problems associated with fillers commonly used in papermaking and incorporated into paper. More particularly, by using the filler of the present invention in a papermaking process, it is possible to provide paper having excellent printing properties such as high smoothness, high opacity and whiteness, improved mechanical properties such as dry strength, tensile strength, Scott bond and bending stiffness, and improved sizing effect of the paper. Further advantages exhibited by the present invention include good and/or improved dewatering and fines retention, which lead to advantages in terms of paper machine runnability.

当将该填料与上胶剂结合使用时，已经观察到本发明使得可以减少上胶需求并且因此通常提高了上胶效率。对于不同类型的上胶剂，包括非纤维素和纤维素活性的上胶剂，特别是纤维素活性的上胶剂例如烯酮二聚物和酸酐而言，均展现出提高的上胶效率。特别地，本发明提供了尤其是具有高的填料装填量和/或当使用具有高表面积的填料时的填充纸的提高的上胶效率和上胶稳定性。When this filler is used in combination with a sizing agent, it has been observed that the present invention makes it possible to reduce sizing requirements and thus generally increase sizing efficiency. Improved sizing efficiency was exhibited for different types of sizing agents, including non-cellulosic and cellulose-reactive sizing agents, especially cellulose-reactive sizing agents such as ketene dimers and anhydrides. In particular, the invention provides increased sizing efficiency and sizing stability for filled papers, especially with high filler loadings and/or when fillers with high surface areas are used.

根据本发明，还不能预期地观察到在简单的加工期间可以使纤维素衍生物与含有钙盐的材料混合并且更有效地吸附在或者粘附在含有钙盐的材料上。可以将本发明的填料看作是改性的填料，或者纤维素衍生物处理的填料。According to the present invention, it has also been unexpectedly observed that cellulose derivatives can be mixed with calcium salt-containing materials and more effectively adsorbed or adhered to calcium salt-containing materials during simple processing. The fillers of the present invention may be considered modified fillers, or cellulose derivative treated fillers.

根据本发明，已经发现可以通过将含有钙盐的材料和纤维素衍生物以预混合或预处理的形式一起加入纤维素悬浮液中而获得非常优良的结果。用纤维素衍生物将含有钙盐的材料预处理提供了一种单独加工纤维素悬浮液的仅仅一种组分以制得改性的填料的便利方式，可以使用该改性的填料代替或者部分代替常规的填料。没有受任何理论的束缚，认为当将这些组分混合时纤维素衍生物吸附在含有钙盐的材料上。According to the present invention, it has been found that very good results can be obtained by adding the calcium salt-containing material and the cellulose derivative together in premixed or pretreated form to the cellulose suspension. Pretreatment of calcium salt-containing material with cellulose derivatives provides a convenient way of processing only one component of the cellulosic suspension separately to produce modified fillers which can be used instead or in part In place of regular fillers. Without being bound by any theory, it is believed that the cellulose derivative adsorbs on the calcium salt-containing material when these components are mixed.

根据本发明的填料包含钙盐和纤维素衍生物。合适的钙盐的例子包括：碳酸钙、硫酸钙和草酸钙，优选碳酸钙，和其混合物。碳酸钙是石灰石、大理石、白垩和白云石中的主要成分。可以直接由上述天然形成的石头种类得到碳酸钙，并且于是将其称作为重质碳酸钙(“GCC”)。也可以合成制备碳酸钙，通常将其称作为沉淀碳酸钙(“PCC”)。优选由氢氧化钙和在水相中产生碳酸根离子的材料例如碱金属碳酸盐或二氧化碳获得碳酸钙。GCC和PCC均可用于本发明，优选PCC，包括存在的各种结晶形式或形态的任何一种例如菱形、棱柱形、板状、立方形和偏三角面体形状的方解石和针状的霰石。PCC通常具有约2-约20m²/g，适宜地约为7-约12m²/g的比表面积。The fillers according to the invention comprise calcium salts and cellulose derivatives. Examples of suitable calcium salts include: calcium carbonate, calcium sulfate and calcium oxalate, preferably calcium carbonate, and mixtures thereof. Calcium carbonate is the main constituent in limestone, marble, chalk and dolomite. Calcium carbonate can be obtained directly from the aforementioned naturally occurring stone species, and is then referred to as ground calcium carbonate ("GCC"). Calcium carbonate can also be prepared synthetically and is commonly referred to as precipitated calcium carbonate ("PCC"). Calcium carbonate is preferably obtained from calcium hydroxide and a material which generates carbonate ions in the aqueous phase, such as alkali metal carbonates or carbon dioxide. Both GCC and PCC can be used in the present invention, PCC is preferred, including any of the various crystalline forms or morphologies that exist such as rhombohedral, prismatic, plate, cubic and scalenohedral calcite and acicular aragonite. PCC generally has a specific surface area of from about 2 to about 20 m² /g, suitably from about 7 to about 12 m² /g.

钙盐可以作为基本纯的钙盐，包括一种或多种钙盐的混合物而存在。其还可以与一种或多种其他组分一起的混合物形式存在。本文中使用的术语“含有钙盐的材料”是指一种包含钙盐和任选的一种或多种其他组分的材料。合适的这类其他组分的例子包括：纤维素、木质纤维素或类似的植物材料的纤维或原纤维、无机粘土、高岭土、滑石、二氧化钛、氢化的铝氧化物、硫酸钡等。优选地，当使用时，这些其他组分适用于造纸。Calcium salts may be present as substantially pure calcium salts, including mixtures of one or more calcium salts. It may also be present in admixture with one or more other components. As used herein, the term "calcium salt-containing material" refers to a material comprising a calcium salt and optionally one or more other components. Examples of suitable such other components include: fibers or fibrils of cellulose, lignocellulose or similar plant material, inorganic clays, kaolin, talc, titanium dioxide, hydrogenated aluminum oxides, barium sulfate, and the like. Preferably, when used, these other components are suitable for papermaking.

在包含纤维素、木质纤维素或类似的植物材料的纤维或原纤维的含有钙盐的材料中，可以使至少部分钙盐沉积在纤维或原纤维上。原纤维的平均厚度可以约为0.01-约10μm，适宜地至多约5μm，优选至多约1μm。原纤维的平均长度可以约为10μm-约1500μm。合适的含有钙盐的材料的例子包括披露于美国专利Nos.5,731,080；5,824,364；6,251,222；6,375,794和6,599,391中的复合材料，这些专利的披露内容因此被在此引入作为参考。可商购获得的这类复合材料包括M-Real Oy的SuperFill。In calcium salt-containing materials comprising fibers or fibrils of cellulose, lignocellulosic or similar plant material, at least part of the calcium salt may be deposited on the fibers or fibrils. The average thickness of the fibrils may be from about 0.01 to about 10 μm, suitably up to about 5 μm, preferably up to about 1 μm. The average length of the fibrils can range from about 10 μm to about 1500 μm. Examples of suitable calcium salt-containing materials include the composite materials disclosed in US Patent Nos. 5,731,080; 5,824,364; 6,251,222; 6,375,794 and 6,599,391, the disclosures of which are hereby incorporated by reference. Commercially available composites of this type include M-Real Oy's SuperFill(R).

根据本发明的填料进一步包含纤维素衍生物。优选的是该纤维素衍生物是水溶的或者至少部分水溶的或水分散的，优选是水溶的或者至少部分水溶的。优选地，该纤维素衍生物是离子性的。该纤维素衍生物可以是阴离子的、阳离子的或者两性的，优选是阴离子的或两性的。合适的纤维素衍生物的例子包括纤维素醚，例如阴离子和两性的纤维素醚，优选阴离子纤维素醚。纤维素衍生物优选具有离子的或者带电的基团，或取代基。合适的离子基团的例子包括阴离子基团和阳离子基团。合适的阴离子基团的例子包括：羧酸盐例如羧烷基、磺酸盐例如磺烷基、磷酸盐和膦酸盐基团，其中烷基可以是甲基、乙基、丙基和其混合物，适宜地为甲基；适宜地，纤维素衍生物含有阴离子基团，包括羧酸盐基团例如羧烷基。阴离子基团的抗衡离子通常是碱金属或碱土金属，适宜地为钠。The fillers according to the invention further comprise cellulose derivatives. It is preferred that the cellulose derivative is water-soluble or at least partially water-soluble or water-dispersible, preferably water-soluble or at least partially water-soluble. Preferably, the cellulose derivative is ionic. The cellulose derivative may be anionic, cationic or amphoteric, preferably anionic or amphoteric. Examples of suitable cellulose derivatives include cellulose ethers, such as anionic and amphoteric cellulose ethers, preferably anionic cellulose ethers. The cellulose derivative preferably has ionic or charged groups, or substituents. Examples of suitable ionic groups include anionic groups and cationic groups. Examples of suitable anionic groups include: carboxylate such as carboxyalkyl, sulfonate such as sulfoalkyl, phosphate and phosphonate groups where the alkyl group can be methyl, ethyl, propyl and mixtures thereof , suitably a methyl group; suitably, the cellulose derivative contains anionic groups, including carboxylate groups such as carboxyalkyl groups. The counterion of the anionic group is usually an alkali or alkaline earth metal, suitably sodium.

根据本发明的纤维素衍生物的合适阳离子基团的例子包括：胺盐，适宜地为叔胺盐，和季铵基团，优选为季铵基团。连接在胺和季铵基团的氮原子上的取代基可以相同或不同并且可以选自烷基、环烷基和烷氧基烷基，并且一个、两个或多个取代基与氮原子一起可以形成杂环。这些取代基彼此独立地通常包含1-约24个碳原子，优选1-约8个碳原子。阳离子基团的氮可以借助于原子链而与纤维素或其衍生物相连，这些原子适宜地包括碳原子和氢原子以及任选的O和/或N原子。通常，原子链是含有2-18个，适宜地为2-8个碳原子、任选地被一个或多个杂原子例如O或N打断或取代的亚烷基，例如亚烷基氧基或羟亚丙基。优选的含阳离子基团的纤维素衍生物包括通过使纤维素或其衍生物与选自2，3-环氧基丙基三甲基氯化铵、3-氯-2-羟丙基三甲基氯化铵和其混合物的季铵化试剂反应而获得的那些。Examples of suitable cationic groups for the cellulose derivatives according to the invention include: amine salts, suitably tertiary amine salts, and quaternary ammonium groups, preferably quaternary ammonium groups. The substituents attached to the nitrogen atoms of the amine and quaternary ammonium groups may be the same or different and may be selected from alkyl, cycloalkyl and alkoxyalkyl groups, and one, two or more substituents together with the nitrogen atom may form heterocycle. These substituents independently of each other generally contain 1 to about 24 carbon atoms, preferably 1 to about 8 carbon atoms. The nitrogen of the cationic group may be linked to the cellulose or its derivatives by means of a chain of atoms, suitably comprising carbon and hydrogen atoms and optionally O and/or N atoms. Typically, the chain of atoms is an alkylene group containing 2-18, suitably 2-8 carbon atoms, optionally interrupted or substituted by one or more heteroatoms such as O or N, such as alkyleneoxy or hydroxypropylene. Preferred cationic group-containing cellulose derivatives include cellulose or derivatives thereof and selected from 2,3-epoxypropyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl Those obtained by reacting quaternizing agents with ammonium chloride and mixtures thereof.

本发明的纤维素衍生物可以含有非离子基团，例如烷基或羟烷基如羟甲基、羟乙基、羟丙基、羟丁基和其混合物，例如羟乙基甲基、羟丙基甲基、羟丁基甲基、羟乙基乙基、羟丙基等。在本发明的一个优选实施方案中，纤维素衍生物含有离子基团和非离子基团。The cellulose derivatives of the present invention may contain nonionic groups such as alkyl or hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl and mixtures thereof, such as hydroxyethylmethyl, hydroxypropyl hydroxymethyl, hydroxybutylmethyl, hydroxyethylethyl, hydroxypropyl, etc. In a preferred embodiment of the present invention, the cellulose derivative contains ionic groups and non-ionic groups.

根据本发明的合适纤维素衍生物的例子包括：羧烷基纤维素例如羧甲基纤维素、羧乙基纤维素、羧丙基纤维素、磺乙基羧甲基纤维素、羧甲基羟乙基纤维素(“CM-HEC”)、其中纤维素被一个或多个非离子取代基取代的羧甲基纤维素，优选为羧甲基纤维素(“CMC”)。合适的纤维素衍生物的例子和它们的制备方法包括披露于美国专利No.4,940,785中的那些，该专利因此被在此引入作为参考。Examples of suitable cellulose derivatives according to the invention include: carboxyalkyl celluloses such as carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, sulfoethyl carboxymethyl cellulose, carboxymethyl hydroxy Ethyl cellulose ("CM-HEC"), carboxymethyl cellulose in which the cellulose is substituted with one or more nonionic substituents, preferably carboxymethyl cellulose ("CMC"). Examples of suitable cellulose derivatives and methods for their preparation include those disclosed in US Patent No. 4,940,785, which is hereby incorporated by reference.

根据本发明的一个优选实施方案，填料包含：含有纤维素或木质纤维素的纤维或原纤维的钙盐和含有阳离子基团的纤维素衍生物。该阳离子基团可以是在本申请中所列举的那些的任何一种。According to a preferred embodiment of the present invention, the filler comprises: a calcium salt of cellulose or lignocellulose-containing fibers or fibrils and a cellulose derivative containing cationic groups. The cationic group may be any of those listed in this application.

在本发明的另一个优选实施方案中，填料包含：基本不含纤维素或木质纤维素的纤维或原纤维的钙盐和可以是阴离子、阳离子或两性的纤维素衍生物。In another preferred embodiment of the present invention, the filler comprises: a calcium salt of fibers or fibrils substantially free of cellulose or lignocellulose and a cellulose derivative which may be anionic, cationic or amphoteric.

本文中使用的术语“取代度”或“DS”是指纤维素衍生物的β-葡萄糖酐环的取代环位点的数目。由于在纤维素的每个葡萄糖酐环上有三个羟基可用于取代，因此DS的最大值为3.0。根据本发明的一个优选实施方案，纤维素衍生物的净离子基团的取代度(“DS_NI”)至多约0.65，即纤维素衍生物具有至多约0.65的净离子平均取代度/每个葡萄糖单元。该净离子取代可以是净阴离子的、净阳离子的或者净中性的。当净离子取代是净阴离子的时，有净余过量的阴离子基团(净阴离子基团＝每个葡萄糖单元的阴离子基团的平均数-阳离子基团的平均数，如果有的话)并且DS_NI与净阴离子基团的取代度(“DS_NA”)相同。当净离子取代是净阳离子的时，有净余过量的阳离子基团(净阳离子基团＝每个葡萄糖单元的阳离子基团的平均数-阴离子基团的平均数，如果有的话)并且DS_NI与净阳离子基团的取代度(“DS_NC”)相同。当净离子取代是净中性的时，如果有的话，每个葡萄糖单元的阴离子基团和阳离子基团的平均数目相同，并且DS_NI以及DS_NA和DS_NC为0。根据本发明的另一个优选实施方案，纤维素衍生物的羧烷基取代度(“DS_CA”)至多约0.65，即纤维素衍生物具有至多约0.65的羧烷基平均取代度/每个葡萄糖单元。羧烷基适宜地为羧甲基，于是本文中所指的DS_CA与羧甲基的取代度(“DS_CM”)相同。根据本发明的这些实施方案，DS_NI、DS_NA、DS_NC和DS_CA彼此独立地通常为至多约0.60，适宜地至多约0.50，优选至多约0.45，更优选至多约0.40，而DS_NI、DS_NA、DS_NC和DS_CA彼此独立地通常为至少0.01，适宜地至少约0.05，优选至少约0.10，更优选至少约0.15。DS_NI、DS_NA、DS_NC和DS_CA的范围彼此独立地通常约为0.01-约0.60，适宜地约为0.05-约0.50，优选约为0.10-约0.45，更优选约为0.15-约0.40。The term "degree of substitution" or "DS" as used herein refers to the number of substituted ring sites of the β-anhydroglucose ring of a cellulose derivative. Since there are three hydroxyl groups available for substitution on each anhydroglucose ring of cellulose, the maximum value of DS is 3.0. According to a preferred embodiment of the present invention, the cellulose derivative has a net ionic group substitution ("DS_NI ") of at most about 0.65, i.e. the cellulose derivative has a net ionic average degree of substitution per glucose of at most about 0.65 unit. The net ionic substitution may be net anionic, net cationic or net neutral. When the net ionic substitution is net anionic, there is a net excess of anionic groups (net anionic groups = average number of anionic groups per glucose unit - average number of cationic groups, if any) and DS_NI is the same as the degree of substitution ("_DSNA ") of the net anionic group. When the net ionic substitution is net cationic, there is a net excess of cationic groups (net cationic groups = average number of cationic groups per glucose unit - average number of anionic groups, if any) and DS_NI is the same as the degree of substitution ("DS_NC ") of the net cationic group. When the net ionic substitution is net neutral, the average number of anionic and cationic groups, if any, per glucose unit is the same and DS_NI as well as DS_NA and DS_NC are zero. According to another preferred embodiment of the present invention, the cellulose derivative has a carboxyalkyl degree of substitution ("DS_CA ") of at most about 0.65, i.e. the cellulose derivative has an average degree of carboxyalkyl substitution of at most about 0.65 per glucose unit. The carboxyalkyl group is suitably carboxymethyl, so_DSCA referred to herein is the same as the degree of substitution ("_DSCM ") of carboxymethyl. According to these embodiments of the invention, DS_NI , DS_NA , DS_NC and DS_CA independently of each other are generally at most about 0.60, suitably at most about 0.50, preferably at most about 0.45, more preferably at most about 0.40, and DS_NI , DS_NA , DS_NC and DS_CA independently of each other are generally at least 0.01, suitably at least about 0.05, preferably at least about 0.10, more preferably at least about 0.15. DS_NI , DS_NA , DS_NC and DS_CA independently of each other generally range from about 0.01 to about 0.60, suitably from about 0.05 to about 0.50, preferably from about 0.10 to about 0.45, more preferably from about 0.15 to about 0.40.

阴离子或两性的纤维素衍生物通常具有0.01-约1.0的阴离子取代度(“DS_A”)，只要DS_NI和DS_NA如本文中所定义；适宜地从约0.05，优选从约0.10，更优选从约0.15，并且适宜地到至多约0.75，优选至多约0.5，更优选至多约0.4。阳离子或两性的纤维素衍生物可以具有0.01-约1.0的阳离子取代度(“DS_C”)，只要DS_NI和DS_NC如本文中所定义；适宜地从约0.02，优选从约0.03，更优选从约0.05，并且适宜地到至多约0.75，优选至多约0.5，更优选至多约0.4。阳离子基团适宜地为季铵基团，于是本文中所指的DS_C与季铵基团的取代度相同(“DS_CN”)。对于本发明的两性纤维素衍生物而言，DS_A或DS_C当然可以高于0.65，只要DS_NA和DS_NC分别如本文中所定义。例如，如果DS_A为0.75并且DS_C为0.15，则DS_NA为0.60。Anionic or amphoteric cellulose derivatives generally have an anionic degree of substitution ("DS_A ") of from 0.01 to about 1.0, so long as DS_NI and DS_NA are as defined herein; suitably from about 0.05, preferably from about 0.10, more preferably From about 0.15, and suitably up to about 0.75, preferably up to about 0.5, more preferably up to about 0.4. The cationic or amphoteric cellulose derivatives may have a cationic degree of substitution ("_DSc ") from 0.01 to about 1.0, provided_DSNI and_DSNC are as defined herein; suitably from about 0.02, preferably from about 0.03, more preferably From about 0.05, and suitably up to about 0.75, preferably up to about 0.5, more preferably up to about 0.4. The cationic group is suitably a quaternary ammonium group, so DS_C referred to herein has the same degree of substitution ("DS_CN ") as the quaternary ammonium group. For the amphoteric cellulose derivatives of the invention, DS_A or DS_C may of course be higher than 0.65, provided DS_NA and DS_NC respectively are as defined herein. For example, if DS_A is 0.75 and DS_C is 0.15, then DS_NA is 0.60.

具有如上定义的取代度的合适纤维素衍生物的例子包括在同一日期以Akzo Nobel N.V.的名义提交的共同悬而未决的专利申请中披露的水溶性低DS羧烷基纤维素衍生物。基于干纤维素衍生物的总重量，该水溶性纤维素衍生物在水溶液中适宜地具有至少85wt％的溶解度，优选至少90wt％，更优选至少95wt％，最优选至少98wt％。Examples of suitable cellulose derivatives having a degree of substitution as defined above include the water-soluble low DS carboxyalkyl cellulose derivatives disclosed in a co-pending patent application filed on the same date in the name of Akzo Nobel N.V. The water-soluble cellulose derivative suitably has a solubility in aqueous solution of at least 85 wt%, preferably at least 90 wt%, more preferably at least 95 wt%, most preferably at least 98 wt%, based on the total weight of the dry cellulose derivative.

纤维素衍生物通常具有至少20,000道尔顿，优选至少50,000道尔顿的平均分子量，并且平均分子量通常至多1,000,000道尔顿，优选至多500,000道尔顿。Cellulose derivatives typically have an average molecular weight of at least 20,000 Daltons, preferably at least 50,000 Daltons, and typically have an average molecular weight of at most 1,000,000 Daltons, preferably at most 500,000 Daltons.

优选地，在根据本发明的填料中，纤维素衍生物至少部分吸附在或者连接在存在于含有钙盐的材料中的钙盐或其他组分上。适宜地，至少约10wt％，优选至少约30wt％，更优选至少约45wt％，最优选至少约60wt％的纤维素衍生物吸附在或者连接在存在于含有钙盐的材料中的钙盐或其他组分上。Preferably, in the filler according to the invention, the cellulose derivative is at least partially adsorbed or attached to calcium salts or other components present in the calcium salt-containing material. Suitably, at least about 10 wt%, preferably at least about 30 wt%, more preferably at least about 45 wt%, most preferably at least about 60 wt%, of the cellulose derivative is adsorbed or attached to calcium salts or other calcium salts present in the calcium salt-containing material. on the components.

基于填料的固体重量-即基于填料的干重，根据本发明的填料通常具有至少0.0001wt％的钙盐含量；该钙盐含量可以约为0.0001-约99.5wt％，适宜地约为0.1-约90wt％，优选约为60-约80wt％。基于填料的固体重量，该填料通常具有至少0.01wt％的纤维素衍生物含量；该纤维素衍生物含量可以约为0.01-约30wt％，适宜地约为0.1-约20wt％，优选约为0.3-约10wt％。The filler according to the present invention generally has a calcium salt content of at least 0.0001% by weight based on the solid weight of the filler—that is, based on the dry weight of the filler; 90 wt%, preferably about 60 to about 80 wt%. The filler generally has a cellulose derivative content of at least 0.01 wt%, based on the solid weight of the filler; - about 10% by weight.

可以将根据本发明的填料作为可以基本不含水的固体材料而提供。也可以将其作为含水组合物而提供。取决于制备方法和预期的应用，水相或水的含量可以在宽的范围内变化。The filler according to the invention may be provided as a solid material which may be substantially free of water. It can also be provided as an aqueous composition. Depending on the preparation method and the intended use, the aqueous phase or water content can vary within wide ranges.

本发明还涉及一种制备填料的方法，其包括：将纤维素衍生物例如本文中所定义的任何一种纤维素衍生物与包含钙盐和任选的一种或多种其他组分的含有钙盐的材料，例如本文中所定义的任何一种含有钙盐的材料混合。该纤维素衍生物和含有钙盐的材料适宜地以使得提供根据本发明的具有如本文中所定义的纤维素衍生物和钙盐含量的填料的量使用。The present invention also relates to a method of preparing a filler comprising: combining a cellulose derivative, such as any one of the cellulose derivatives defined herein, with a calcium salt and optionally one or more other components containing A calcium salt material, such as any one of the calcium salt-containing materials as defined herein, is mixed. The cellulose derivative and calcium salt containing material are suitably used in amounts such as to provide a filler according to the invention having a cellulose derivative and calcium salt content as defined herein.

使用的纤维素衍生物和含有钙盐的材料可以作为固体、或以含水组合物和其混合物存在。含有钙盐的材料适宜地作为细碎的材料存在。可以通过以间歇、半间歇或连续的方法将纤维素衍生物加入填料，或者反之亦然而实现混合。根据本发明的一个优选实施方案，将纤维素衍生物作为固体加入含有钙盐的材料的含水组合物中，并且然后使获得的组合物适宜地进行有效的分散以将纤维素衍生物溶解。优选地，通过首先形成纤维素衍生物的中性到碱性水相，适宜地为水溶液，然后将其与含有钙盐的材料的含水组合物混合而进行混合。在与含有钙盐的材料混合之前，可以将纤维素衍生物的水相进行预处理例如均化、离心分离和/或过滤，以例如在如果有的情况下将未溶解的纤维素衍生物从水相中分离。The cellulose derivatives and calcium salt-containing materials used may be present as solids, or as aqueous compositions and mixtures thereof. The calcium salt-containing material is suitably present as finely divided material. Mixing can be achieved by adding the cellulose derivative to the filler in a batch, semi-batch or continuous process, or vice versa. According to a preferred embodiment of the present invention, the cellulose derivative is added as a solid to the aqueous composition of the calcium salt-containing material, and the resulting composition is then suitably dispersed effectively to dissolve the cellulose derivative. Preferably, mixing is carried out by first forming a neutral to basic aqueous phase of the cellulose derivative, suitably an aqueous solution, which is then mixed with the aqueous composition of the calcium salt-containing material. Before mixing with the calcium salt-containing material, the aqueous phase of the cellulose derivative may be pretreated, e.g. homogenized, centrifuged and/or filtered, e.g. to remove undissolved cellulose derivative, if any, from separated in the aqueous phase.

优选地，将纤维素衍生物与含有钙盐的材料混合以使得至少部分纤维素衍生物吸附在或者连接在含有钙盐的材料上，优选以使得通过用水稀释很难将其从该材料上除去。这可以通过在足够长的时间下进行混合以使得能够吸附在附着物上而实现。适宜地，混合时间至少约1分钟，优选至少约5分钟，更优选至少约10分钟，最优选至少约20分钟。如果希望达到高程度的连接，甚至几小时(1-10小时)的混合时间也是可以的。适宜地，将至少约10wt％，优选至少约30wt％，更优选至少约45wt％，最优选至少约60wt％的纤维素衍生物从水相中转移并且吸附在或者连接在存在于含有钙盐的材料中的钙盐或其他组分上。Preferably, the cellulose derivative is mixed with the calcium salt-containing material such that at least part of the cellulose derivative is adsorbed or attached to the calcium salt-containing material, preferably so that it is difficult to remove from the material by dilution with water . This can be achieved by mixing for a time long enough to allow adsorption on the deposits. Suitably, the mixing time is at least about 1 minute, preferably at least about 5 minutes, more preferably at least about 10 minutes, most preferably at least about 20 minutes. Mixing times of even several hours (1-10 hours) are possible if a high degree of bonding is desired. Suitably, at least about 10 wt%, preferably at least about 30 wt%, more preferably at least about 45 wt%, most preferably at least about 60 wt%, of the cellulose derivative is transferred from the aqueous phase and adsorbed or attached to the calcium salt-containing Calcium salts or other components in the material.

通常调节纤维素衍生物的水相的pH以使得在约4-约13，优选约6-约10，更优选约7-约8.5的值下吸附使用的特定纤维素衍生物。可以将合适的碱或酸用于调节pH。合适的碱的例子包括碱金属的碳酸氢盐和碳酸盐以及碱金属氢氧化物，适宜地为碳酸氢钠、碳酸钠和氢氧化钠。合适的酸的例子包括无机酸、有机酸和酸盐，适宜地为硫酸和其酸盐例如明矾。一般而言，在较低的pH-即约4.0至中性的pH下，纤维素衍生物的吸附量较高但溶解度降低，而在较高的pH下吸附量降低但溶解度升高。The pH of the aqueous phase of the cellulose derivative is generally adjusted so that the particular cellulose derivative used is adsorbed at a value of from about 4 to about 13, preferably from about 6 to about 10, more preferably from about 7 to about 8.5. Suitable bases or acids can be used to adjust the pH. Examples of suitable bases include alkali metal bicarbonates and carbonates and alkali metal hydroxides, suitably sodium bicarbonate, sodium carbonate and sodium hydroxide. Examples of suitable acids include mineral acids, organic acids and salts, suitably sulfuric acid and its salts such as alum. In general, at lower pH, ie, about 4.0 to neutral pH, cellulose derivatives have higher adsorption but lower solubility, and at higher pH lower adsorption but higher solubility.

温度并不是关键的；在非加压条件下的操作中温度通常约为10-约100℃，优选约20-约80℃。然而，更高的温度更加有利，在混合期间含水组合物的温度适宜地约为30-约70℃，更优选约40-约60℃。The temperature is not critical; in operation under non-pressurized conditions the temperature is generally from about 10 to about 100°C, preferably from about 20 to about 80°C. However, higher temperatures are more advantageous and the temperature of the aqueous composition during mixing is suitably from about 30 to about 70°C, more preferably from about 40 to about 60°C.

当使用除了钙盐之外还含有其他组分例如纤维素或木质纤维素的纤维或原纤维的含有钙盐的材料时，纤维素衍生物的混合和连接可以与钙盐沉淀在原纤维或纤维上同时进行，或者在沉淀之后进行。还可以在沉淀之前加入纤维素衍生物。在该情况下，在打浆期间或者在打浆之后以单独的吸附加入纤维素衍生物。纤维素衍生物可以吸附在或者连接在含有钙盐的材料或者纤维或原纤维表面上和/或吸收到纤维或原纤维中。将类似的纤维素衍生物吸附在类似的填料材料上的方法披露于美国专利Nos.5,731,080；5,824,364；6,251,222；6,375,794和6,599,391中，这些专利的披露内容在此引入作为参考。When using calcium salt-containing materials that contain other components such as fibers or fibrils of cellulose or lignocellulose in addition to calcium salts, the mixing and bonding of cellulose derivatives can be precipitated with calcium salts on the fibrils or fibrils at the same time, or after precipitation. It is also possible to add cellulose derivatives prior to precipitation. In this case, the cellulose derivative is added in a separate adsorption during or after beating. Cellulose derivatives may be adsorbed or attached to calcium salt-containing materials or to the surface of fibers or fibrils and/or absorbed into fibers or fibrils. Methods for adsorbing similar cellulose derivatives onto similar filler materials are disclosed in US Patent Nos. 5,731,080; 5,824,364; 6,251,222; 6,375,794 and 6,599,391, the disclosures of which are incorporated herein by reference.

通过本发明的方法获得的填料可以原样用于例如造纸中。如果作为含水组合物存在，则可以将其直接使用或者在需要时可以将其干燥例如以简化运输。The fillers obtained by the process of the invention can be used as such, for example in papermaking. If present as an aqueous composition, it can be used as such or it can be dried if desired, for example to simplify transport.

本发明还涉及一种造纸方法，其包括：提供含有纤维素纤维的含水悬浮液(“纤维素悬浮液”)、将填料例如本文中所定义的任何一种填料引入纤维素悬浮液，和将纤维素悬浮液脱水以形成纸幅或纸片。优选地，通过将其作为单一组合物加入而将填料引入纤维素悬浮液。作为选择，可以将钙盐或者含有钙盐的材料(例如本文中所定义的任何一种含有钙盐的材料)和纤维素衍生物(例如本文中所定义的任何一种纤维素衍生物)单独加入纤维素悬浮液中并且在纤维素悬浮液中原位形成填料。The present invention also relates to a process for making paper comprising: providing an aqueous suspension containing cellulosic fibers ("cellulosic suspension"), introducing a filler, such as any one of the fillers defined herein, into the cellulosic suspension, and adding The cellulosic suspension is dewatered to form a paper web or sheet. Preferably, the filler is introduced into the cellulosic suspension by adding it as a single composition. Alternatively, calcium salts or calcium salt-containing materials (such as any of the calcium salt-containing materials defined herein) and cellulose derivatives (such as any of the cellulose derivatives defined herein) can be separately Added to the cellulosic suspension and formed the filler in situ in the cellulosic suspension.

在该方法中，当然可以将其他组分引入纤维素悬浮液。这些组分的例子包括：常规填料、荧光增白剂、上胶剂、助滤剂和助留剂、干强度试剂、湿强度试剂等。合适的常规填料的例子包括：高岭土、瓷土、二氧化钛、石膏、滑石、天然和合成的碳酸钙例如白垩、磨碎大理石和沉淀碳酸钙，氢化的铝氧化物(三氢氧化铝)、硫酸钙、硫酸钡、草酸钙等。当将根据本发明的填料与常规填料一起使用时，基于全部填料的干重，根据本发明的填料可以至少1wt％，适宜地至少5wt％，优选至少10wt％，更优选至少约20wt％，适宜地至多约99wt％的量存在。合适的上胶剂的例子包括：非纤维素活性的上胶剂例如基于松香的上胶剂，比如基于松香的皂，基于松香的乳液/分散液；和纤维素活性的上胶剂例如酸酐比如琥珀酸酐(ASA)、链烯基和烷基烯酮二聚物(AKD)和多聚物的乳液/分散液。合适的助滤剂和助留剂的例子包括：有机聚合物产品例如阳离子、阴离子和非离子聚合物，包括阳离子聚乙烯亚胺、阳离子、阴离子和非离子聚丙烯酰胺、阳离子聚胺、阳离子淀粉和阳离子瓜尔胶；无机材料，例如铝化合物、阴离子微粒材料比如硅胶基颗粒、蒙脱石类粘土例如斑脱土、蒙脱土；胶体氧化铝，和其组合。合适的助滤剂和助留剂组合的例子包括阳离子聚合物和阴离子微粒材料，例如阳离子淀粉和阴离子硅胶基颗粒、阳离子聚丙烯酰胺和阴离子硅胶基颗粒以及阳离子聚丙烯酰胺和斑脱土或蒙脱土。合适的湿强度试剂的例子包括聚胺和聚氨基酰胺。含有根据本发明的填料和阳离子淀粉的纸表现出非常优良的强度性能。In this method, it is of course possible to introduce further components into the cellulosic suspension. Examples of such components include: conventional fillers, optical brighteners, sizing agents, drainage and retention aids, dry strength agents, wet strength agents, and the like. Examples of suitable conventional fillers include: kaolin, china clay, titanium dioxide, gypsum, talc, natural and synthetic calcium carbonates such as chalk, ground marble and precipitated calcium carbonate, hydrogenated aluminum oxide (aluminum trihydroxide), calcium sulfate, Barium sulfate, calcium oxalate, etc. When fillers according to the invention are used together with conventional fillers, the fillers according to the invention may be at least 1 wt%, suitably at least 5 wt%, preferably at least 10 wt%, more preferably at least about 20 wt%, based on the dry weight of the total filler, suitably It is present in an amount up to about 99% by weight. Examples of suitable sizing agents include: non-cellulosic reactive sizing agents such as rosin-based sizing agents, such as rosin-based soaps, rosin-based emulsions/dispersions; and cellulose-reactive sizing agents such as anhydrides such as Emulsions/dispersions of succinic anhydride (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers. Examples of suitable drainage and retention aids include: organic polymer products such as cationic, anionic and nonionic polymers, including cationic polyethyleneimines, cationic, anionic and nonionic polyacrylamides, cationic polyamines, cationic starches and cationic guar gum; inorganic materials such as aluminum compounds, anionic particulate materials such as silica-based particles, smectite-type clays such as bentonite, montmorillonite; colloidal alumina, and combinations thereof. Examples of suitable combinations of drainage and retention aids include cationic polymers and anionic particulate materials such as cationic starch and anionic silica-based particles, cationic polyacrylamide and anionic silica-based particles, and cationic polyacrylamide and bentonite or montmorillonite. off the soil. Examples of suitable wet strength agents include polyamines and polyaminoamides. Papers containing fillers according to the invention and cationic starch exhibit very good strength properties.

根据本发明的一个优选实施方案，将至少一种上胶剂引入纤维素悬浮液以制得含有填料的上胶纸。优选地，该上胶剂是本文中所提及的类型的纤维素活性上胶剂。合适的烯酮二聚物具有下面的通式(I)，其中R¹和R²表示饱和或不饱和的烃基，通常为饱和烃，这些烃基适宜地含有8-36个碳原子，通常为含有12-20个碳原子的直链或支链烷基例如十六烷基和十八烷基。烯酮二聚物在环境温度下-即在25℃下，适宜地在20℃下可以为液体。通常，酸酐可以由下面的通式(II)表征，其中R³和R⁴可以相同或不同并且表示适宜地含有8-30个碳原子的饱和或不饱和的烃基，或者R³和R⁴与-C-O-C-部分一起可以形成5至6元环，该环任选地进一步被含有至多30个碳原子的烃基取代。商业上使用的酸酐的例子包括烷基和链烯基琥珀酸酐，特别为异十八烯基琥珀酸酐。According to a preferred embodiment of the invention, at least one sizing agent is introduced into the cellulosic suspension to produce a sized paper containing fillers. Preferably, the sizing agent is a cellulose reactive sizing agent of the type mentioned herein. Suitable ketene dimers have the general formula (I) below, wherein R and^R represent saturated or unsaturated hydrocarbon groups, usually^saturated hydrocarbons, which suitably contain 8 to 36 carbon atoms, usually containing Straight-chain or branched-chain alkyl groups of 12 to 20 carbon atoms such as hexadecyl and octadecyl. The ketene dimer may be liquid at ambient temperature - ie at 25°C, conveniently at 20°C. Generally, the acid anhydride can be characterized by the following general formula (II), wherein R and^R can^be the same or different and represent a saturated or unsaturated hydrocarbon group suitably containing 8-30 carbon atoms, or R^andR can be combined with The -COC- moieties together can form a 5 to 6 membered ring which is optionally further substituted with a hydrocarbyl group containing up to 30 carbon atoms. Examples of commercially used anhydrides include alkyl and alkenyl succinic anhydrides, especially isoctadecenyl succinic anhydride.

合适的烯酮二聚物、酸酐和有机异氰酸酯包括披露于美国专利No.4,522,686中的化合物，该专利因此被在此引入作为参考。Suitable ketene dimers, anhydrides and organic isocyanates include those disclosed in US Patent No. 4,522,686, which is hereby incorporated by reference.

可以将根据本发明的填料以可以在宽的范围内变化的量加入纤维素悬浮液，这尤其取决于纤维素悬浮液的类型、所制得的纸的类型、加入点等。基于干纤维的重量，通常以1-约50wt％，适宜地约5-约40wt％，通常约10-约30wt％的量加入填料。因此，基于干纤维的重量，根据本发明的纸通常具有1-约50wt％，适宜地约5-约40wt％，通常约10-约30wt％的本发明的填料含量。The fillers according to the invention can be added to the cellulosic suspension in amounts which can vary within wide ranges, depending inter alia on the type of cellulosic suspension, the type of paper produced, the point of addition, etc. Fillers are typically added in amounts of 1 to about 50 wt%, suitably about 5 to about 40 wt%, usually about 10 to about 30 wt%, based on dry fiber weight. Thus, papers according to the invention generally have a filler content of the invention of from 1 to about 50 wt%, suitably from about 5 to about 40 wt%, usually from about 10 to about 30 wt%, based on dry fiber weight.

当在该方法中使用其他组分时，可以将这些组分以可以在宽的范围内变化的量加入纤维素悬浮液，这尤其取决于这些组分的类型和数量、纤维素悬浮液的类型、填料含量、所制得的纸的类型、加入点等。通常以基于干纤维的重量为至少约0.01wt％，适宜地至少约0.1wt％的量将上胶剂引入纤维素悬浮液，并且上限通常约为2wt％，适宜地约0.5wt％。一般而言，将助滤剂和助留剂以与当不使用这些助剂时获得的相比产生更好的排水性和/或保持性的量引入纤维素悬浮液。通常将助滤剂和助留剂、干强度试剂和湿强度试剂彼此独立地以基于干纤维为至少约0.001wt％，通常至少约0.005wt％的量引入，并且上限通常约为5wt％，适宜地约1.5wt％。When other components are used in the process, these components can be added to the cellulosic suspension in amounts which can vary within wide ranges, depending inter alia on the type and amount of these components, the type of cellulosic suspension , filler content, type of paper produced, point of addition, etc. The sizing agent is generally introduced into the cellulosic suspension in an amount of at least about 0.01 wt%, suitably at least about 0.1 wt%, and the upper limit is usually about 2 wt%, suitably about 0.5 wt%, based on the weight of dry fibers. In general, drainage and retention aids are introduced into the cellulosic suspension in amounts that result in better drainage and/or retention than is obtained when these aids are not used. Drainage and retention aids, dry strength agents and wet strength agents are generally introduced independently of each other in an amount of at least about 0.001 wt%, usually at least about 0.005 wt%, and the upper limit is usually about 5 wt%, suitably Ground about 1.5wt%.

本文中使用的术语“纸”不仅包括纸和其产品，而且包括其他含有纤维素纤维的片状或网状产品，例如纸和纸板及其产品。该方法可用于由不同种类的纤维素(含纤维素的)纤维的含水悬浮液制备纸，并且这些悬浮液将适宜地含有基于干物为至少25wt％，优选至少50wt％的这类纤维。纤维素纤维可以基于原纤维和/或再生纤维，包括木材或者一年生植物或多年生植物的纤维。纤维素悬浮液可以含有木材或者不含木材，并且其可以基于得自于以下物质的纤维：化学纸浆例如硫酸盐、亚硫酸盐和有机溶剂纸浆，机械纸浆例如热-机械纸浆、化学-热-机械纸浆、精炼纸浆和磨木纸浆，硬木和软木，并且还可以基于任选地得自于脱墨纸浆的再生纤维，和其混合物。纤维素悬浮液适宜地具有中性至碱性范围的pH，例如约6-约10，优选约6.5-约8.0。The term "paper" as used herein includes not only paper and products thereof, but also other sheet or web products containing cellulose fibers, such as paper and board and products thereof. The process can be used to prepare paper from aqueous suspensions of cellulosic (cellulose-containing) fibers of different kinds and these suspensions will suitably contain at least 25 wt%, preferably at least 50 wt% of such fibers on a dry matter basis. Cellulosic fibers may be based on virgin and/or regenerated fibers, including fibers of wood or annual or perennial plants. The cellulosic suspension may or may not contain wood and it may be based on fibers derived from chemical pulps such as sulfate, sulfite and organic solvent pulps, mechanical pulps such as thermo-mechanical pulps, chemical-thermal- Mechanical, refiner and groundwood pulps, hardwoods and softwoods, and may also be based on recycled fibers optionally obtained from deinked pulp, and mixtures thereof. The cellulosic suspension suitably has a pH in the neutral to alkaline range, for example from about 6 to about 10, preferably from about 6.5 to about 8.0.

可以将制得的纸干燥、涂覆和压延。可以用例如以下物质涂覆纸：碳酸钙、石膏、硅酸铝、高岭土、氢氧化铝、硅酸镁、滑石、二氧化钛、硫酸钡、氧化锌、合成颜料，和其混合物。The produced paper can be dried, coated and calendered. Paper may be coated with, for example, calcium carbonate, gypsum, aluminum silicate, kaolin, aluminum hydroxide, magnesium silicate, talc, titanium dioxide, barium sulfate, zinc oxide, synthetic pigments, and mixtures thereof.

制得的纸的克重可以在宽的范围内变化，这取决于制得的纸的类型；通常，克重约为20-约500g/m²，适宜地约30-约450g/m²，优选30-约110g/m²。优选地，将本发明用于制备未涂覆和涂覆的胶版纸、电子照相纸、任选地含有机械纸浆的未涂覆和涂覆的高级纸张，以及书写纸和晒图纸。一种尤其优选的产品是其中结合了高光泽度和高不透明度以及容积的涂覆的胶版纸。The grammage of the paper produced can vary within wide ranges, depending on the type of paper produced; generally, the grammage is from about 20 to about 500 g/m² , suitably from about 30 to about 450 g/m² , Preferably 30 to about 110 g/m² . Preferably, the invention is used for the production of uncoated and coated offset papers, electrophotographic papers, uncoated and coated fine papers optionally containing mechanical pulp, and writing and printing papers. A particularly preferred product is coated offset paper in which high gloss is combined with high opacity and volume.

在以下实施例中进一步阐述本发明，然而这些实施例并不意在限制本发明。份和％分别涉及重量份和wt％，除非另外说明。The invention is further illustrated in the following examples, which, however, are not intended to limit the invention. Parts and % relate to parts by weight and % by weight, respectively, unless otherwise stated.

                    实施例1Example 1

通过用纤维素衍生物将含有钙盐的材料处理而制备根据本发明的填料和用于比较的填料。使用的纤维素衍生物是DS_NI(DS_CA＝DS_CM＝DS_A＝DS_NA＝DS_NI)分别为0.3、0.32和0.7的羧甲基纤维素(“CMC”)。使用的另一种CMC是DS_CA＝DS_CM＝DS_A＝0.4；DS_C＝DS_QN＝0.17；和DS_NI＝DS_NA＝0.4-0.17＝0.23的季铵羧甲基纤维素(“QN-CMC”)。使用的纤维素衍生物的平均分子量为100,000-400,000。使用的含有钙盐的材料是表面积分别为5.7和10.0m²/g的不同的沉淀碳酸钙(“PCC”)。使用的另一种含有钙盐的材料是SuperFill(纸浆细粒上的PCC)。Fillers according to the invention and fillers for comparison were prepared by treating a material containing calcium salts with a cellulose derivative. The cellulose derivative used was carboxymethylcellulose ("CMC") with DS_NI (DS_CA =DS_CM =DS_A =DS_NA =DS_NI ) of 0.3, 0.32 and 0.7, respectively._{AnotherCMCusedis} quaternary ammonium carboxymethylcellulose_("QN- CMC"). The average molecular weight of the cellulose derivative used is 100,000-400,000. The calcium salt-containing materials used were different precipitated calcium carbonates ("PCC") with surface areas of 5.7 and 10.0^m2 /g, respectively. Another calcium salt-containing material used is SuperFill(R) (PCC on pulp fines).

通过将CMC溶解于水中至0.5wt％的浓度而制备填料。此后，将得到的CMC组合物加入PCC填料浆液中并且在25-45分钟在约50℃的温度下混合。根据本发明的填料(“本发明产品”)和用于比较的填料(“比较产品”)如下：Fillers were prepared by dissolving CMC in water to a concentration of 0.5 wt%. Thereafter, the resulting CMC composition was added to the PCC filler slurry and mixed at a temperature of about 50°C for 25-45 minutes. The filler according to the invention ("invention product") and the filler used for comparison ("comparison product") are as follows:

本发明产品1(“IP1”)：CMC(DS_NI0.3)处理的PCC(5.7m²/g)Inventive Product 1 ("IP1"): CMC (DS_NI 0.3) treated PCC (5.7 m² /g)

本发明产品2(“IP2”)：CMC(DS_NI0.3)处理的PCC(10m²/g)Inventive Product 2 ("IP2"): CMC (DS_NI 0.3) treated PCC (10 m² /g)

本发明产品3(“IP3”)：CMC(DS_NI0.32)处理的SuperFillInventive Product 3 ("IP3"): CMC (DS_NI 0.32) Treated SuperFill(R)

本发明产品4(“IP4”)：QN-CMC(DS_NI0.23)处理的SuperFillInventive Product 4 ("IP4"): SuperFill(R) treated by QN-CMC (DS_NI 0.23)

比较产品1(“CP1”)：CMC(DS_NI0.7)处理的PCC(5.7m²/g)Comparative Product 1 ("CP1"): CMC (DS_NI 0.7) treated PCC (5.7 m² /g)

比较产品2(“CP2”)：SuperFillComparative Product 2 ("CP2"): SuperFill(R)

                    实施例2Example 2

对根据本发明制备的纸的上胶进行评价并且与出于比较的目的使用的纸比较。使用根据实施例1的IP1制备根据本发明的纸。使用根据实施例1的CP1并且使用不含纤维素衍生物的填料制备用于比较的纸。The sizing of the papers prepared according to the invention was evaluated and compared with the papers used for comparative purposes. Paper according to the invention was prepared using IP1 according to Example 1. Papers for comparison were prepared using CP1 according to Example 1 and using fillers without cellulose derivatives.

由化学纸浆组成的并且含有如表1中所示的变化数量(wt％，基于干纸)的未处理的PCC的纸浆制备纸片。向纸浆悬浮液中加入2.0kg/吨干纤维的根据实施例1的填料和不含纤维素衍生物的填料；3.0kg/吨干纤维的AKD(含水分散液Eka Keydime C223)，和包含阳离子淀粉(Eka PL 1510)和二氧化硅颗粒(Eka NP 780)的保持体系。阳离子淀粉和二氧化硅颗粒以0.15kg/吨干纤维的量加入。加入顺序如下：Sheets were prepared from pulp consisting of chemical pulp and containing varying amounts (wt% on dry paper) of untreated PCC as shown in Table 1 . 2.0 kg/ton of dry fibers of the filler according to Example 1 and fillers without cellulose derivatives; 3.0 kg/ton of dry fibers of AKD (aqueous dispersion Eka Keydime C223), and cationic starch containing (Eka PL 1510) and silica granules (Eka NP 780) retention system. Cationic starch and silica particles were added in an amount of 0.15 kg/ton dry fiber. The order of joining is as follows:

CMC处理的PCC的加入：0秒Addition of PCC processed by CMC: 0 seconds

AKD分散液的加入：30秒Addition of AKD dispersion: 30 seconds

阳离子淀粉的加入：45秒Addition of cationic starch: 45 seconds

二氧化硅颗粒的加入：60秒Addition of silica particles: 60 seconds

纸片成型：75秒Sheet molding: 75 seconds

使用动态纸片成型机(“Formette”，CTP Grenoble)根据标准方法制备纸片。为了建立上胶结果，使用Cobb₆₀(SCAN-P 12：64)方法。表1示出了获得的结果。Sheets were prepared according to standard methods using a dynamic sheet former ("Formette", CTP Grenoble). To establish the gumming results, the Cobb₆₀ (SCAN-P 12:64) method was used. Table 1 shows the results obtained.

                    表1   测试号  纸的PCC含量   填料   Cobb₆₀   1  18％   CP1   45   2  19％   IP1   25Table 1 test number PCC content of paper filler Cobb₆₀ 1 18% CP1 45 2 19% IP1 25

                    实施例3Example 3

在该实施例中，评价其中(i)将CMC处理的PCC加入纸浆悬浮液和(ii)将CMC和PCC(未处理)单独加入纸浆悬浮液的根据本发明的造纸方法。In this example, a papermaking process according to the invention was evaluated wherein (i) CMC-treated PCC was added to the pulp suspension and (ii) CMC and PCC (untreated) were added separately to the pulp suspension.

由实施例2中使用的并且含有基于干纸为30wt％未处理的PCC(表面积10m²/g)或CMC(DS_NI0.3)处理的PCC(10m²/g)(根据实施例1的IP2)的相同类型的纸浆制备纸片。向纸浆悬浮液中加入4kg/吨干纤维的阳离子淀粉(PB 970)、3.0kg/吨干纤维的AKD(含水上胶分散液Eka Keydime C223)，和包含阳离子聚丙烯酰胺(Eka PL 1310)和二氧化硅颗粒(Eka NP 780)的保持体系。阳离子聚丙烯酰胺和二氧化硅颗粒均以0.20kg/吨干纸的量加入。当使用未处理的PCC时，单独加入1.0kg/吨的DS_NI为0.3的CMC。当加入CMC处理的PCC时，不单独加入CMC。加入顺序如下：PCC (10 m 2 /g) treated with PCC (10 m² /g) or CMC (DS NI 0.3) containing 30 wt % untreated PCC (surface area 10 m² /g) or CMC (DS_NI 0.3) on a dry paper basis (IP2 according to example 1) Paper sheets are prepared from the same type of pulp. To the pulp suspension was added 4 kg/ton dry fiber of cationic starch (PB 970), 3.0 kg/ton dry fiber of AKD (containing water size dispersion Eka Keydime C223), and containing cationic polyacrylamide (Eka PL 1310) and Retention system of silica particles (Eka NP 780). Both cationic polyacrylamide and silica particles are added in an amount of 0.20 kg/ton of dry paper. When using untreated PCC, add 1.0 kg/ton of CMC with a DS_NI of 0.3 alone. When CMC-treated PCC was added, CMC was not added alone. The order of joining is as follows:

阳离子淀粉的加入：0秒Addition of cationic starch: 0 seconds

CMC处理的PCC/未处理的PCC的加入：30秒Addition of CMC treated PCC/untreated PCC: 30 seconds

CMC的单独加入：35秒Single join of CMC: 35 seconds

AKD的加入：45秒Addition of AKD: 45 seconds

阳离子聚丙烯酰胺的加入：60秒Addition of cationic polyacrylamide: 60 seconds

二氧化硅颗粒的加入：75秒Addition of silica particles: 75 seconds

纸片成型：90秒Sheet molding: 90 seconds

如实施例2中那样评价纸片。结果示于表2中。Sheets were evaluated as in Example 2. The results are shown in Table 2.

                            表2   测试号   加入方式  填料   Cobb₆₀   1   单独加入  未处理的PCC+CMC   65   2   加入CMC处理的PCC  IP2   35Table 2 test number How to join filler Cobb₆₀ 1 join alone Untreated PCC+CMC 65 2 Added PCC treated by CMC IP2 35

                    实施例4Example 4

在造纸方法中使用并且评价实施例1的产品。以类似于实施例3的方法由含有70wt％混合的硬木纸浆和30wt％分别在22°和25°SR下精炼的软木纸浆的纤维配料制备纸片，除了不使用阳离子淀粉和使用未处理的SuperFill填料(CP2)或CMC处理的SuperFill填料(IP3和IP4)之外，这些填料以使得得到含有30wt％SuperFill填料的纸片的量加入。加入顺序如下：The product of Example 1 was used and evaluated in a papermaking process. Sheets were prepared from a fiber furnish containing 70% by weight mixed hardwood pulp and 30% by weight softwood pulp refined at 22° and 25° SR in a similar manner to Example 3, except that no cationic starch was used and untreated SuperFill was used In addition to <RTI ID=0.0>(R)</RTI> filler (CP2) or CMC-treated SuperFill(R) filler (IP3 and IP4), these fillers were added in such an amount that a sheet containing 30 wt% SuperFill(R) filler was obtained. The order of joining is as follows:

SuperFill填料的加入：0秒Addition of SuperFill(R): 0 seconds

阳离子聚丙烯酰胺的加入：45秒Addition of cationic polyacrylamide: 45 seconds

二氧化硅颗粒的加入：75秒Addition of silica particles: 75 seconds

AKD的加入：90秒AKD join: 90 seconds

结果描述于表3中。The results are described in Table 3.

              表3   测试号   填料   Cobb₆₀   1   CP2   80   2   IP3   50   3   IP4   21table 3 test number filler Cobb₆₀ 1 CP2 80 2 IP3 50 3 IP4 twenty one

Claims (25)

Translated fromChinese

1.一种填料，其包含钙盐和净离子基团的取代度至多约0.65的纤维素衍生物，其中该填料基本不含纤维素或木质纤维素的纤维或原纤维。CLAIMS 1. A filler comprising a calcium salt and a cellulose derivative having a degree of substitution of net ionic groups of up to about 0.65, wherein the filler is substantially free of fibers or fibrils of cellulose or lignocellulose.2.一种填料，其包含钙盐和净离子基团的取代度至多约0.65的纤维素衍生物，其中该纤维素衍生物含有阳离子基团。2. A filler comprising a calcium salt and a cellulose derivative having a degree of substitution of net ionic groups of at most about 0.65, wherein the cellulose derivative contains cationic groups.3.根据权利要求1或2的填料，特征在于取代度至少为0.05。3. Filler according to claim 1 or 2, characterized in that the degree of substitution is at least 0.05.4.根据权利要求1或2的填料，特征在于取代度约为0.15-约0.40。4. Filler according to claim 1 or 2, characterized in that the degree of substitution is from about 0.15 to about 0.40.5.根据权利要求1、2或3的填料，特征在于纤维素衍生物是纤维素醚。5. Filler according to claim 1, 2 or 3, characterized in that the cellulose derivative is a cellulose ether.6.根据前述权利要求任一项的填料，特征在于纤维素衍生物含有羧甲基。6. Filler according to any one of the preceding claims, characterized in that the cellulose derivative contains carboxymethyl groups.7.根据前述权利要求任一项的填料，特征在于纤维素衍生物含有季铵基团。7. Filler according to any one of the preceding claims, characterized in that the cellulose derivative contains quaternary ammonium groups.8.根据权利要求1，3-7任一项的填料，特征在于纤维素衍生物是阴离子的。8. Filler according to any one of claims 1, 3-7, characterized in that the cellulose derivative is anionic.9.根据权利要求1-7任一项的填料，特征在于纤维素衍生物是两性的。9. Filler according to any one of claims 1-7, characterized in that the cellulose derivative is amphoteric.10.根据前述权利要求任一项的填料，特征在于纤维素衍生物是至少部分水溶的。10. Filler according to any one of the preceding claims, characterized in that the cellulose derivative is at least partially water-soluble.11.根据前述权利要求任一项的填料，特征在于基于填料的固体重量，该填料的纤维素衍生物含量为0.3-10wt％。11. Filler according to any one of the preceding claims, characterized in that the filler has a cellulose derivative content of 0.3-10% by weight, based on the weight of solids of the filler.12.根据前述权利要求任一项的填料，特征在于基于填料的固体重量，该填料的钙盐含量为60-约80wt％。12. Filler according to any one of the preceding claims, characterized in that the filler has a calcium salt content of 60 to about 80% by weight, based on the solid weight of the filler.13.根据前述权利要求任一项的填料，特征在于钙盐是碳酸钙。13. Filler according to any one of the preceding claims, characterized in that the calcium salt is calcium carbonate.14.根据前述权利要求任一项的填料，特征在于钙盐是沉淀的碳酸钙。14. Filler according to any one of the preceding claims, characterized in that the calcium salt is precipitated calcium carbonate.15.根据权利要求2的填料，特征在于该填料进一步包含纤维素或木质纤维素的纤维或原纤维。15. Filler according to claim 2, characterized in that the filler further comprises fibers or fibrils of cellulose or lignocellulose.16.根据权利要求2的填料，特征在于该填料基本不含纤维素或木质纤维素的纤维或原纤维。16. Filler according to claim 2, characterized in that the filler is substantially free of cellulose or lignocellulosic fibers or fibrils.17.包含根据权利要求1-16任一项的填料的纸。17. Paper comprising a filler according to any one of claims 1-16.18.根据权利要求17的纸，特征在于基于干纸，该纸的总填料含量为5-40wt％。18. Paper according to claim 17, characterized in that the paper has a total filler content of 5-40% by weight, based on dry paper.19.一种制备填料的方法，其包括：在基本没有纤维素或木质纤维素的纤维或原纤维的存在下将含有钙盐的材料与净离子基团取代度至多约0.65的纤维素衍生物混合。19. A method of preparing a filler comprising: combining a calcium salt-containing material with a cellulose derivative having a net degree of substitution of ionic groups of at most about 0.65 in the presence of substantially free of cellulose or lignocellulosic fibers or fibrils mix.20.一种制备填料的方法，其包括：将含有钙盐的材料与羧烷基取代度至多约0.65的纤维素衍生物混合，其中该纤维素衍生物含有阳离子基团。20. A method of preparing a filler comprising: mixing a calcium salt-containing material with a cellulose derivative having a degree of carboxyalkyl substitution of up to about 0.65, wherein the cellulose derivative contains cationic groups.21.一种可通过根据权利要求19或20的方法获得的填料。21. A filler obtainable by a method according to claim 19 or 20.22.一种造纸方法，其包括：提供含有纤维素纤维的含水悬浮液、将根据权利要求1-16和21任一项的填料引入悬浮液，和将悬浮液脱水以形成纸幅或纸片。22. A process for the manufacture of paper comprising: providing an aqueous suspension containing cellulose fibres, introducing a filler according to any one of claims 1 to 16 and 21 into the suspension, and dewatering the suspension to form a paper web or sheet .23.根据权利要求22的方法，特征在于通过将含有钙盐和纤维素衍生物的单一组合物加入悬浮液而将填料引入悬浮液。23. A method according to claim 22, characterized in that the filler is introduced into the suspension by adding a single composition comprising a calcium salt and a cellulose derivative to the suspension.24.根据权利要求22或23任一项的方法，特征在于基于干纤维，将填料以5-30wt％的量加入。24. A method according to any one of claims 22 or 23, characterized in that the filler is added in an amount of 5-30% by weight, based on dry fibres.25.根据权利要求22或23的方法，特征在于其进一步包括将纤维素活性的上胶剂加入悬浮液。25. The method according to claim 22 or 23, characterized in that it further comprises adding a cellulosic active sizing agent to the suspension.