TWI356862B - Filler for papermaking process - Google Patents

Description

r r\ 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種含有鈣鹽及纖維素 ^ v I何生物之填料》 本發明進一步關於一種製備填料之方 、 6亥填料在製紙中 的用途’填料作為添加劑的製紙方法八 久3有填料的紙。 【先前技術】 在紙張工業中高填料的紙張是一種已經確定的趨勢， 不只是因為減少纖維使用的成本，也是因為改良的產品品 質（較高的明度及較佳的適印性）所致。普遍使用基於碳酸 鈣7填料，乃因為彼等較優的光散射性質。在高填料紙張（尤 其是具有高表面積之填料）的生產中，主要缺點是在於高消 耗量的上膠劑。因此，因為在紙張中的填料含量增加為 了要獲得相對應上膠結果而需要較大量的上膠劑。因此， 當填料量增加時’纖維素懸浮液是難以上膠的。 進行上膠主要是為了在紙張或紙板中達成斥水性及降 低紙邊毛蕊（wicking)。同時將影響紙及紙板的機械性質， 例如尺寸安定性、摩擦性數、揉曲性及耐折度。另外，可 精由特定地控制墨水的散佈及黏著性改良上膠的適印性。 上膠方法是涉及在纖維表面上沉積疏水性物質，通常 稱作上膠劑。慣常使用的上膠劑為非纖維素-反應性的上膠 劑（例如基於松香的上膠劑），及纖維素·反應性的上膠劑， 例如烷基乙烯酮二聚物（“AKD”），及酸酐，例如烯基號轴 酸野（“ASA”）。然而，習知纖維素·反應性的上膠劑，亦即 AKD及ASA會經歷與纖維所欲反應競爭的水解。再者， 1356862 在最後產品中上膠的損失可以是因為上膠劑的轉化或遷 移，上膠劑蒸發，產品的機械磨損等緣故而發生。Rr\ IX. Description of the invention: [Technical field of the invention] The present invention relates to a filler containing calcium salt and cellulose, and the invention further relates to a method for preparing a filler and a 6 liter filler in papermaking. Use 'filler as an additive paper making method eight long 3 filled paper. [Prior Art] High filler paper in the paper industry is an established trend, not only because of the reduced cost of fiber use, but also because of improved product quality (higher brightness and better printability). Calcium carbonate based fillers are commonly used because of their superior light scattering properties. In the production of high filler papers, especially those with high surface area, the main disadvantage is the high consumption of sizing agents. Therefore, a larger amount of sizing agent is required because the amount of filler in the paper is increased in order to obtain a corresponding sizing result. Therefore, the cellulose suspension is difficult to sizing when the amount of filler is increased. Gluing is primarily done to achieve water repellency in paper or paperboard and to reduce wicking on the paper side. At the same time, it will affect the mechanical properties of paper and paperboard, such as dimensional stability, friction, flexibility and folding resistance. In addition, the fineness can be controlled by specifically controlling the dispersion and adhesion of the ink to improve the printability of the sizing. The sizing process involves depositing a hydrophobic material on the surface of the fiber, commonly referred to as a sizing agent. The commonly used sizing agents are non-cellulosic-reactive sizing agents (for example rosin-based sizing agents), and cellulose-reactive sizing agents, such as alkyl ketene dimers ("AKD"). And an anhydride such as an alkenyl acid ("ASA"). However, conventional cellulose-reactive sizing agents, i.e., AKD and ASA, undergo hydrolysis which competes with the desired reaction of the fiber. Furthermore, the loss of sizing in the final product of 1356862 may occur due to conversion or migration of the sizing agent, evaporation of the sizing agent, mechanical wear of the product, and the like.

Bartz及其同事已經發現在AKD蠟增加流動性的期 間，有一些AKD可以穿透及此後被捕捉在填料的孔隙結 構中（Bartz，W.; Darroch，M.E·，Kurrie，F.L.，“燒基乙稀綱 二聚物在填充碳酸鈣的紙張中的上膠及轉化”， Journal，Vol. 77, 12, 1994)。這尤其是在使用具有多孔玫^ 化型結構及高表面積之PCC之偏三角面體形式時發生。 Voutilainen已經顯示具有高表面積之填料比起纖維能較佳 地吸收AKD(V0utilainen，P.，“烷基乙烯酮二聚物在紙漿纖 維及CaC〇3填料上競爭性吸收作用”，得自Bartz and colleagues have found that during the increased mobility of AKD waxes, some AKDs can penetrate and are subsequently captured in the pore structure of the filler (Bartz, W.; Darroch, ME, Kurrie, FL, "Burning B Sizing and conversion of rare dimers in paper filled with calcium carbonate", Journal, Vol. 77, 12, 1994). This occurs especially when using a scalenohedral form of PCC having a porous rose structure and a high surface area. Voutilainen has shown that fillers with a high surface area absorb AKD better than fibers (V0utilainen, P., "The competitive absorption of alkyl ketene dimers on pulp fibers and CaC〇3 fillers",

Paper and Coating Chemistry Symposium，1996)。在填料 表面上Al-及Si-氧化物的存在可另外吸收包含在AKd粒 子中的陽離子澱粉。也己經建議在AKD及碳酸鈣填料之 間存在強的父互作用或者鍵結。這些建議的使用填料時的 機制是不欲的，因此應該努力來使這些交互作用降到最 ，J、。 為了改良上膠率，在美國專利第5514212號建議可以 使用陰離子澱粉-皂錯合物來改性。來自玉米或馬鈴薯的蒸 煮澱粉與脂族酸鹽混合並當與沉澱鈣漿液或含高含量鈣離 子之製紙漿料混合時沉澱到顏料表面。 美國專利第5972100建議一種由纖維素反應性上膠劑 (例如AKD) ’陽離子分散劑（例如陽離子澱粉或聚醯胺類） 及填料所組成之系統。除了改良上膠劑之外，本發明亦容 丄妁6862 5午獨立地分開控制填料裝載及上膠兩者。 ，再者，W0 95/13324提到以纖維素衍生物（例如具有取 2度為0.7之纖維素羧甲基鈉（“CMC”)）處理的碳酸鈣。該 .經處理的碳酸鈣被用來作為鹼性製紙懸浮液中的填料，^ 此增加紙張的明度。 、 錯 美國專利第3730830號揭示一種製造紙（特定指照相紙） :法’其包括使用合成聚合纖維。在添加合成纖維到纖 :1孚液中之則，將無機顏料或碳添加到含缓甲基纖維素 之游聚及合成纖維中，藉此達成聚合物纖維在紙張原料 纖維素纖維中均一的分散。 ;=然存在一種提供製紙方法及所得紙張較佳性質的填 ，提供種導致可能生產出顯示極佳印染及機械性質之 间填料紙張的填料是令人合意的。提供一種降低所需上膠 並藉此改良上膠率之填料是令人合意的。提供—種與排出 及保留助劑相容並因此導致良好的排水、保留及紙張機械 運轉性之填料是令人合意的。提供一種製備顯示前述特性 之填料的簡單及有效方法是令人合意的。 【發明内容】 本發明一般關於一種包括鈣鹽及纖維素衍生物之 料。本發明推—丰H 、 進步關於一種包括鈣鹽及羧烷基纖維素衍生 之〃料本發明亦關於藉由混合含鈣鹽之物質和纖維素 丁生物以1&填料之方法，關於填料作為製紙中添加劑的 途乂及關於含填料的紙。本發明進一步關於一種製造紙 的方法’其中填料被併人水性纖維素懸浮液中。 1356862 更特定言之，本發明關於一種包括鈣鹽及具有淨離子 基取代度為高至約0.65的纖维素衍生物的填料。本發明亦 關於包括鈣鹽及具有羧烷基取代度為高至約0.65之纖维素 何生物的填料。本發明亦關於一種製備填料之方法，其包 括混合#5鹽之物質與具有淨離子基取代度為高至約㈣: 纖維素衍生物。本發明亦關於一種製備填料的方法其包 括混合約鹽之物質與具有叛烧基取代度為高至約〇.65 ^ 維素何生物。本發明進一步關於由這些方法獲得的填料。 本發明進—步關於—種製造紙的方法，其包括提供一、種: 纖維素纖維之水性懸浮液、導人含㈣及具有淨離子基: 代度為高至約〇.65的纖維素衍生物的填料到懸浮液中，及 使懸浮液脫水’以形成紙片抄網。本發明進一步關於—種 製造紙的方法，其包括提供一種含纖維素纖維之水性懸浮 液、導入含辦鹽及具有㈣基取代度為高至約0.65的纖维 素衍生物的填料到懸浮液中’及使懸浮液脫水，以形成紙 =網。在製紙方法中’可藉由將辦鹽及纖維素衍生物以 早一組成方式—起添加來使填料導人到纖維素懸浮液中。 【發明内容】 發明詳細說明 已 中 製Paper and Coating Chemistry Symposium, 1996). The presence of Al- and Si-oxide on the surface of the filler can additionally absorb the cationic starch contained in the AKd particles. It has also been suggested that there is a strong parental interaction or bonding between the AKD and the calcium carbonate filler. These suggested mechanisms for using fillers are undesirable, so efforts should be made to minimize these interactions, J. In order to improve the sizing rate, it is suggested in U.S. Patent No. 5,512,212 that an anionic starch-soap complex can be used for modification. The cooked starch from corn or potato is mixed with an aliphatic acid salt and precipitated onto the surface of the pigment when mixed with a precipitated calcium slurry or a paper pulp containing a high content of calcium ions. U.S. Patent No. 5,792,100 teaches a system consisting of a cellulose reactive sizing agent (e.g., AKD) ' a cationic dispersing agent (e.g., cationic starch or polyamidamide) and a filler. In addition to the improved sizing agent, the present invention also allows for independent control of both filler loading and sizing, independently at 6862. Further, W0 95/13324 refers to a calcium carbonate treated with a cellulose derivative such as cellulose carboxymethyl sodium ("CMC") having a degree of 0.7. The treated calcium carbonate is used as a filler in an alkaline paper suspension, which increases the brightness of the paper. U.S. Patent No. 3,730,830 discloses a method of making paper (specifically referred to as photographic paper): a method comprising the use of synthetic polymeric fibers. In the addition of synthetic fiber to the fiber:1, the inorganic pigment or carbon is added to the agglomerated and synthetic fibers containing the slow methyl cellulose, thereby achieving uniformity of the polymer fiber in the paper raw material cellulose fiber. dispersion. There is a filling which provides a paper making method and a preferred property of the resulting paper, and it is desirable to provide a filler which results in the possibility of producing a filler paper which exhibits excellent printing and mechanical properties. It would be desirable to provide a filler that reduces the amount of sizing required and thereby improves the rate of sizing. It is desirable to provide a filler that is compatible with the effluent and retention aids and thus results in good drainage, retention, and mechanical mechanical continuity of the paper. It would be desirable to provide a simple and efficient method of preparing a filler that exhibits the foregoing characteristics. SUMMARY OF THE INVENTION The present invention generally relates to a material comprising a calcium salt and a cellulose derivative. The present invention also relates to a method for mixing a calcium salt-containing material and a cellulose butyl material by a 1& filler, with respect to a filler as a filler. The route of additives in papermaking and papers containing fillers. The invention further relates to a method of making paper wherein the filler is in a suspension of an aqueous cellulose. More specifically, the present invention relates to a filler comprising a calcium salt and a cellulose derivative having a net ionic group substitution of up to about 0.65. The invention also relates to fillers comprising a calcium salt and a cellulose having a degree of carboxyalkyl substitution of up to about 0.65. The invention also relates to a method of preparing a filler comprising a material of a mixed #5 salt having a degree of substitution with a net ionic group of up to about (4): a cellulose derivative. The present invention also relates to a method of preparing a filler which comprises mixing a salt of a substance with a degree of substitution with a repressive group of up to about 〇.65^. The invention further relates to fillers obtained by these methods. The invention further relates to a method for producing paper comprising the steps of: providing an aqueous suspension of cellulose fibers, introducing a human (4), and having a net ionic group: a cellulose having a degree of generation of up to about 〇.65 The filler of the derivative is suspended into the suspension and the suspension is dehydrated to form a paper dip net. The invention further relates to a method of making a paper comprising providing an aqueous suspension comprising cellulose fibers, introducing a salt comprising a salt, and a cellulose derivative having a (4) degree of substitution of up to about 0.65 to the suspension Medium' and dewatering the suspension to form a paper = net. In the paper making process, the filler can be introduced into the cellulosic suspension by adding the salt and the cellulose derivative in an early composition. SUMMARY OF THE INVENTION Detailed Description of the Invention

/發明提供—種適於製造紙的新穎填料。令人驚言牙的 經發現根據本發明之填料使得通常於製紙時及併入紙張 的填料所遭遇到的-些問題得以降低。更特；t言之，在 、’氏方法中’藉由本發明之填料可以提供具有極佳印刷性 (例如高平滑度、高不透明度及白度）、改良的機械性 1356862 貝（乾強度、抗張強度' Scott鍵及抗曲勁度）&改良的上 勝效果。由本發明顯示的額外優點包括從紙張機器運轉性 觀點=為益處的良好及/或改良的脫水與微粒子留存性。 當一起使用填料與上膠劑時，已經發現本發明可以降 低上膠需求及因此改良上膠效率。對於不同類型的上膠劑 顯示出了改良的上勝效率，這些上滕劑包括非·纖維素及纖 維素-反應性上㈣，特定為纖維素·反應性上㈣，例如 乙烯酮二聚物及酸酐類。尤其是，本發明提供改良加填料 紙，之上膠效率及上膠安定性（尤其是具有高填料量者及/ 或當具有高表面積之填料被使用時）。 一根據本發明已經發現出I意料地，纖維素衍生物可以 在間易處理期間與含鈣鹽之物質混合，且更有效地吸附於 含鈣鹽之物質上或結合於含鈣鹽之物質上。本發明之填料 可視為經改性的填料，或經纖維素衍生物處理的填料。 根據本發明，已經發現藉由將含鈣鹽之物質及纖維素 /亍生物以預1此合或預先處理形式一起添力口到纖維素懸浮 液中可以獲得非；^良好的結果。含辦鹽之物質與纖維素衍 生物的預先處理提供一種個別地處理只有一種成分之纖維 素懸浮液來產生經改性填料的方便方式，這可以用來取代 或部分取代傳統填料。在不被任何理論限制下，傾相信當 混合成分（等）時，纖維素衍生物被吸附到含鈣鹽之物質上Υ 根據本發明之填料包括鈣鹽及纖維素衍生物。合適鈣 鹽之例子包括碳酸鈣，硫酸鈣及草酸鈣，較佳為碳酸鈣， 以及彼等的混合物。碳酸鈣為灰石、大理石、白堊及白雲 1356862 石中的主要成分。碳酸鈣可以從前述天然產生的石頭種類 直接獲得，而後稱作重質碳酸鈣（“GCC”）。碳酸弼亦可以 合成產生，通常稱作沉澱碳酸鈣（“PCC”）。碳酸飼較佳是從 氫氧化鈣及能在水相中產生碳酸根離子之物質（如鹼金屬 石厌酸鹽或一戰化碳）中獲得。在本發明.中，可使用gcc及 PCC兩者，較佳為PCC，包括任何各式各樣的結晶形式戒 存在的表面型態形式，例如菱形、稜形、扁平狀立方狀 及偏三角面體形式之方解石及針狀形式之文石epcc通常 具有比表面積是從約2到約20m2/g，合適為從約7到約 12m2/g。 舞鹽可以為實質上純約鹽（包括一或多種約鹽之混合 物）來存在。亦可以混合物與一或多種其他成分形式來存 在。在此處使用的術語”含鈣鹽之物質”是指含鈣鹽之物 質及視情況需要的一或多種其他成分。合適其他成分的例 子包括纖維素、木質纖維素或似植物性物質的纖維或原纖 維，無機黏土，高嶺土，滑石，二氧化鈦，氫化氧化鋁， 硫酸鋇等。較佳地，其他成分是當使用時適合用於製紙的。 在包括纖維素、木質纖維素或似植物性物質之纖維或 原纖維的含鈣物質中，至少部份鈣鹽可被沉積在纖維或短 纖維上。短纖維之平均厚度可從約〇〇1到高至1〇μιη，合 適地為尚至約5μηι且較佳地高至約丨μπι。原纖維的平均長 度了伙1 Ομηι到咼至約1 5〇〇ym。合適含約物質之例子包 括揭不於美國專利第 5731〇8〇，5824364，6251222，6375794 及6599391中的複合材料，彼等揭示皆併入圍參考。這種 13!)050Ζ 類型之市售 仔複合材料包括Μ-Real Oy的SuperFill®。 根據本發明之填料進一步包括纖維素衍生物。較佳的 纖j素何生物為水溶性或至少部份水溶性或水可分散性， + 良'合眭或至少部分水溶性。較佳地，纖維素衍生物 為離子的。纖維素衍生物可為陰離子、陽離子或兩性的， 車乂佳地為陰離子或兩性的◊合適纖維素衍生物之例子包括 隹素醚類，例如陰離子及兩性的纖維素醚類，較佳地為 陰離子纖維素喊類。纖維素衍生物較佳地具有陰離子或帶 電的基團或取代基。合適離子基團之例子包括陰離子及陽 土團σ適陰離子基團之例子包括羧酸根，例如羧烷 基’ ％酸根，如磺烷基，磷酸根及膦酸根基團，其中烷基 可為甲基、乙基、丙基及其混合物，合適地為甲基·合適 也.截.，隹素何生物包含陰離子基團，包括羧酸根基團，例如 羧烷基。陰離子基團之反離子通常是鹼金屬或鹼土金屬， 合適地為鈉。 根據本發明之纖維素衍生物的合適陽離子基團之例子 包括胺鹽、合適地為三級胺及四級銨基團之鹽類，較佳地 為四級錄基®。連接到胺及四㈣基團之氮原子上的取代 基可為相同或不同且可為選自烷基、環烷基及烷氧基及 一、兩個或多個取代基可與氮原子一起形成雜環基。取代 基通常各別包括從i到約24個碳原子.，較佳& i到約8 個碳原子。陽離子機團的氮可藉由合適包括碳及氫原子及 視需要的0及/或N原子之原子鏈而被連接到纖維素或其 衍生物上。通常原子鏈為具有從2到丨8個碳原子（合適 12 1356862 為2到8個碳原子）之伸垸基，其視情況需要可被-或多 個雜原子（例如〇 4晴打斷或取代，例如為稀氧基或經 基伸丙基。較佳含陽離子基團之纖维素街生物包括藉由使 纖維素或其衍生物與季銨化試劑反應所得者，季錢化試劑 為選自2,3-環氧丙基三甲基氯化録，3·氣·2· 氯化銨及其混合物。 —土 本發明之纖維素衍生物可包含非離子性基團，例如烧 基或經烧基，如經甲基，經乙基，經丙基，經丁基，及其 混合物，如經乙基甲基，經丙基甲基，經丁基甲 基乙基’經丙基及其類似物。在本發明之較佳具體實例中， 纖維素衍生物包含離子性基圏及非離子性基團兩者。 根據本發明之合適纖維素衍生物的例子包括敌 料，如W基纖維素乙基纖維素1丙基纖維素·，/Invention provides a novel filler suitable for making paper. It has been found that the fillers according to the present invention reduce the problems encountered with the fillers typically found in papermaking and incorporation into paper. More specifically; in other words, in the 'Method', the filler of the present invention can provide excellent printability (for example, high smoothness, high opacity and whiteness), improved mechanical properties of 1356862 shells (dry strength, Tensile strength 'Scott key and resistance to stiffness' & improved superior effect. Additional advantages exhibited by the present invention include good and/or improved dewatering and microparticle retention from the viewpoint of paper machine runnability. When fillers and sizing agents are used together, it has been found that the present invention can reduce sizing requirements and thus improve sizing efficiency. Improved superior efficiencies for different types of sizing agents, including non-cellulosic and cellulose-reactive (4), specifically cellulose·reactive (iv), such as ketene dimers and Anhydrides. In particular, the present invention provides improved filler paper, sizing efficiency and sizing stability (especially when having a high filler content and/or when a filler having a high surface area is used). According to the present invention, it has been found that, i.e., the cellulose derivative can be mixed with a substance containing a calcium salt during easy handling, and adsorbed more efficiently on a substance containing a calcium salt or on a substance containing a calcium salt. . The filler of the present invention can be regarded as a modified filler or a filler treated with a cellulose derivative. In accordance with the present invention, it has been found that good results can be obtained by adding a calcium salt-containing material and a cellulose/亍 organism together in a pre-treated or pre-treated form to the cellulosic suspension. Pretreatment of the salt-containing material with the cellulose derivative provides a convenient means of individually treating the cellulosic suspension with only one component to produce a modified filler which can be used to replace or partially replace the conventional filler. Without being bound by any theory, it is believed that when a component (etc.) is mixed, the cellulose derivative is adsorbed onto the substance containing the calcium salt. The filler according to the present invention includes a calcium salt and a cellulose derivative. Examples of suitable calcium salts include calcium carbonate, calcium sulfate and calcium oxalate, preferably calcium carbonate, and mixtures thereof. Calcium carbonate is the main component of limestone, marble, chalk and white clouds. Calcium carbonate can be obtained directly from the aforementioned naturally occurring stone species and is hereinafter referred to as heavy calcium carbonate ("GCC"). Barium carbonate can also be produced synthetically, commonly referred to as precipitated calcium carbonate ("PCC"). The carbonic acid feed is preferably obtained from calcium hydroxide and a substance capable of producing carbonate ions in the aqueous phase (e.g., alkali metal anoate or mono-warmed carbon). In the present invention, both gcc and PCC, preferably PCC, may be used, including any of a wide variety of crystalline forms or surface forms, such as diamonds, prisms, flat cubes, and triangular faces. The calcite and acicular form of the aragonite epcc typically have a specific surface area of from about 2 to about 20 m2/g, suitably from about 7 to about 12 m2/g. The dance salt can be present as a substantially pure salt (including a mixture of one or more about salts). Mixtures may also be present in one or more other forms. The term "calcium salt-containing material" as used herein refers to a substance containing a calcium salt and one or more other ingredients as may be required. Examples of suitable other ingredients include cellulose, lignocellulose or plant-like fibers or fibrils, inorganic clay, kaolin, talc, titanium dioxide, aluminum hydride, barium sulfate and the like. Preferably, the other ingredients are suitable for papermaking when used. In the calcium-containing material comprising cellulose, lignocellulose or a plant-like material of fibers or fibrils, at least a portion of the calcium salt may be deposited on the fibers or staple fibers. The average thickness of the staple fibers can range from about 〇〇1 up to 1 〇μηη, suitably from about 5 μηιη and preferably up to about 丨μπι. The average length of the fibrils is from 1 Ομηι to 1 to about 15 〇〇 ym. Examples of suitable inclusions include composite materials which are disclosed in U.S. Patent Nos. 5,731,8, 5,824,364, 6,,,,,,,,,,,,,,,,,,,, This 13!) 050 Ζ type of commercially available composite material includes Μ-Real Oy's SuperFill®. The filler according to the invention further comprises a cellulose derivative. Preferably, the organism is water soluble or at least partially water soluble or water dispersible, + good or at least partially water soluble. Preferably, the cellulose derivative is ionic. The cellulose derivative may be anionic, cationic or amphoteric, and the ruthenium is preferably an anionic or amphoteric oxime. Examples of suitable cellulose derivatives include alizarin ethers, such as anionic and amphoteric cellulose ethers, preferably Anionic cellulose shouts. The cellulose derivative preferably has an anionic or charged group or substituent. Examples of suitable ionic groups include anionic and cation groups. Examples of sigma-containing anionic groups include carboxylates such as carboxyalkyl '% acid groups, such as sulfoalkyl, phosphate and phosphonate groups, wherein the alkyl group can be a The base, the ethyl group, the propyl group, and mixtures thereof, suitably a methyl group, are also suitable. The alkaloids include an anionic group, including a carboxylate group, such as a carboxyalkyl group. The counterion of the anionic group is typically an alkali or alkaline earth metal, suitably sodium. Examples of suitable cationic groups of the cellulose derivatives according to the invention include amine salts, suitably salts of tertiary amines and quaternary ammonium groups, preferably quaternary bases®. The substituents attached to the nitrogen atom of the amine and the tetra(tetra) group may be the same or different and may be selected from the group consisting of an alkyl group, a cycloalkyl group, and an alkoxy group, and one or two or more substituents may be bonded together with the nitrogen atom. A heterocyclic group is formed. Substituents typically each include from i to about 24 carbon atoms. Preferred & i to about 8 carbon atoms. The nitrogen of the cationic group can be attached to the cellulose or its derivative by a suitable atomic chain comprising carbon and hydrogen atoms and optionally 0 and/or N atoms. Usually the atomic chain is a thiol group having from 2 to 8 carbon atoms (suitably 2 to 8 carbon atoms for 12 1356862), which may optionally be interrupted by - or a plurality of heteroatoms (eg 〇4 或 or Substituting, for example, a dilute oxy group or a propyl group. Preferably, the cationic group-containing cellulosic street organism comprises a cellulose acid or a derivative thereof and a quaternizing agent, and the quaternary reagent is selected. From 2,3-epoxypropyltrimethyl chloride, 3·gas·2·ammonium chloride and mixtures thereof. - The cellulose derivative of the present invention may contain a nonionic group such as a burn group or By alkyl group, such as methyl, ethyl, propyl, butyl, and mixtures thereof, such as ethylmethyl, propylmethyl, butylmethylethyl propyl and the like In a preferred embodiment of the invention, the cellulose derivative comprises both ionic ruthenium and nonionic groups. Examples of suitable cellulose derivatives according to the invention include hostile materials such as W-based cellulose. Ethyl cellulose 1 propyl cellulose·,

石寅酸乙基缓甲基纖維辛，韃甲A 竣甲基m纖維素（“cm· )，竣甲基纖維素’其中纖維素被—或多個非離子性 取代基取代，較佳為缓？基纖維素（“CMc”）。 衍…例子及其製備方法包括揭示於美國專= 4940785號者，彼等併入為參考。 根據本發明之-較佳具體實例’填料包括含纖維辛或 木, 質纖維素之纖維或短纖維之辦鹽及含陽離子基團之纖維 素何生物。陽離子基團可為任何列在本申請案中者。’、’· 在本發am較佳具體實例中，填料包括Ethyl sulphate ethyl ketone, lanthanum A 竣 methyl m cellulose ("cm · ), 竣 methyl cellulose 'in which cellulose is replaced by a plurality of nonionic substituents, preferably Examples of slow-based cellulose ("CMc"). Examples of the preparations and methods for their preparation include those disclosed in U.S. Patent No. 4,940,785, the disclosure of which is incorporated herein by reference. Or wood, cellulose or short fiber and cellulose containing cationic groups. The cationic group can be any of those listed in the present application. ', '· In the examples, the filler includes

不含纖維㈣木質纖維素之㈣及可為陰離子、陽離子 兩性的纖維素衍生物。 A 1356862 “此處使㈣術語”取代度，，或”DS，，意指纖維素衍生物之 β-葡萄酐環所具有之取代環位置之數目。因為在每個供取 代之纖維素的㈣野環上有三個㈣，DS的最大值為3〇。 根據本發明之-較佳具體實施例，纖維素衍生物具有高至 約0.65之淨離子基團的取代度（‘I”），亦即，纖維素衍 生物在每-個葡萄糖單位具有高至約〇 65之平均淨離子取 代度。淨離子取代可為淨.陰料性、淨㈣子性或淨中性。 當淨離子取代為淨陰離子時，將具有淨過量陰離子基（淨 陰離子基畴個葡萄糖單位上之平均陰離子基·每個葡萄糖 單位上之平均陽離子基(若有的話））一“與淨陰 離子基(“DSna，，)之取代度相同。當淨離子取代為淨陽陰離 :時’將具有淨過量陽離子基（淨陽離子基=每個葡萄糖 早位上之平均陽離子基·每個葡萄糖單位上之平均陽離子基 (若有的話）），且〇5们會與淨陽離子基（π%〆，）之取代产 相同。當淨離子取代為淨中性時’每葡萄糖單位上之平^ 的陰離子及陽離子基團之數目會㈣，且^及I和(4) which is free of fiber (4) lignocellulose and a cellulose derivative which can be anionic or cationic. A 1356862 "The term "fourth" in this case, or "DS," means the number of substitution ring positions of the β-glucosamine ring of the cellulose derivative. Because of the (four) in each of the substituted celluloses There are three (four) on the wild ring, and the maximum value of DS is 3 〇. According to a preferred embodiment of the present invention, the cellulose derivative has a degree of substitution ('I") of a net ionic group of up to about 0.65, That is, the cellulose derivative has an average net ion substitution of up to about 65 in each glucose unit. The net ion substitution can be net, feminine, net (tetra) or net neutral. When the net ion is replaced by a net anion, it will have a net excess of anionic groups (the average anionic group on the glucose unit of the net anion domain · the average cationic group per glucose unit (if any)) - a net anion The base ("DSna,") has the same degree of substitution. When the net ion is replaced by a net cation: 'will have a net excess of cationic groups (net cation = average cation group per glucose in the early position · average cation group per glucose unit (if any)) And 〇5 will be the same as the replacement of the net cationic group (π% 〆,). When the net ion is replaced by a net neutrality, the number of anions and cationic groups per unit of glucose will be (4), and ^ and I and

We為〇。根據本發明之另—較佳具體實例，纖維素衍生 物具有㈣基取代度（“DSca，，）為高至、約〇.65，亦即纖維素 何生物在每個葡萄糖單元上具有平均幾院基取代度為高至 約0.65。繞烧基係合適地為竣甲基，且然後此處所指之恥“ 與羧甲基(“DSCM”)取代度相同。根據本發明之具體實例， DSm ' DSNA 、DSnc和DSca分別為高至約〇 6〇，合適 地為高至約0.50,較佳地為高至約0·45且更佳地高至〇 4〇， 然而dsn丨、DSna 、DSnc和DSca分別為至少〇 〇丨合 1356862 適地為至少約0.50,較佳地為至少約〇 ι〇且更佳地為至少 約〇.l5eDSN1、DSNA、DSnc和DSca之範圍分別為從 約〇.(H至約0.60’合適地為從約Q G5至約q 5g，較佳地 為從約0.10至約0.45,且更佳地為從約〇15至約〇 4〇。 陰離子或兩十生纖維素衍生物通常具有陰離子取代声 (DSA)是在從（ΜΠ到約U的範圍内，只要DSjDs^ 此處所定義，適當地是從約〇·〇5，較佳地從約〇 ι〇，且更 佳地從約（Μ5而適當地高至約Q 75，較佳地高至約〇 5, 且更佳地高至約0.40。陽離子或兩性纖維素衍生物可以具 有陽離子取代度（“DSc”）是在從〇·〇1到'約1.0的範圍内，只 要DSNI和DSnC如此處所定義，適當地是從、約0.02,較佳 地從約G.03,且更佳地從約⑽而適當地高至約〇 75,較 佳地高至約0.5，且更祛认古E▲ 更佳地间至約0,40。陽離子基團合適 地為季胺基，且然後此處所提之叫則與季胺基之取代度We are 〇. According to another preferred embodiment of the present invention, the cellulose derivative has a (iv) group degree of substitution ("DSca,") of up to about 6565, that is, cellulose has an average of a few on each glucose unit. The degree of substitution of the base is up to about 0.65. The cyclization is suitably a fluorenylmethyl group, and then the shame "referred to herein is the same as the carboxymethyl ("DSCM") degree of substitution. According to a specific embodiment of the invention, DSm 'DSNA, DSnc and DSca are respectively up to about 〇6〇, suitably up to about 0.50, preferably up to about 0.45 and more preferably up to 〇4〇. And dsn丨, DSna, DSnc, and DSca are each at least 1356862, suitably at least about 0.50, preferably at least about 〇ι, and more preferably at least about 〇.l5eDSN1, DSNA, DSnc, and DSca. The range is from about 〇. (H to about 0.60' suitably from about Q G5 to about q 5g, preferably from about 0.10 to about 0.45, and more preferably from about 〇15 to about 〇4〇 An anionic or quaternary cellulose derivative typically having an anion-substituted sound (DSA) in the range from (ΜΠ to about U, as long as DSjDs^ is defined herein, suitably from about 〇·〇5, preferably From about 〇ι〇, and more preferably from about Μ5 and suitably up to about Q 75, preferably up to about 〇5, and more preferably up to about 0.40. The cationic or amphoteric cellulose derivative may have The degree of cationic substitution ("DSc") is in the range from 〇·〇1 to 'about 1.0, as long as DSNI and DSnC are as defined herein, suitably from 0.02, preferably from about G.03, and more preferably from about (10), suitably up to about 〇75, preferably up to about 0.5, and more preferably an ancient E ▲ more preferably to about 0, 40. The cationic group is suitably a quaternary amine group, and then the degree of substitution with the quaternary amine group is referred to herein.

(DSQN”）相同°對於本發明之兩性纖維素衍生物而言，DS(DSQN") identical. For the amphoteric cellulose derivative of the present invention, DS

或DSC可以當然為高於〇 A 门於0.65，只要0、及DSNC分別為此 處所疋義。例如，卷n Q各π 田DSA為0.75且DSc為〇 15時然 DSNa 為 〇·60 〇 具有刖述叱義之取代度的合適纖維素衍生物之例子包 括揭示於同申請中w Δ ν 中以Akzo Nobel N.V.為名提申之申請案中 的水溶性低DS羧烷A输雉丰…从此 物合適地在財水溶,㈣維素衍生 纖、准素何生物之總重量為基準時，在水溶 液♦具右曼4、5?« i 重里％溶解度’較佳地至少9 〇重量％， 更佳地至少95重量％’且最佳地至少98重量％。 15 1356862 纖維素衍生物通常具有平均分子量為至少2〇〇〇〇道 吞，較佳至少50〇0〇道爾呑，且平均分子量通常為^至 1000000道爾吞’較佳為高至500000道爾吞。 间至 較佳地，在根據本發明之填料中，纖維素衍生物β 至少吸附到或結合絲鹽上或是在存於含轉鹽之物質:之 其他成份上》合適地，至少約10重量％，較佳地至少約如 重量％’更佳地至少約45重量％’且最佳地至少約的重 量。/0的纖維素衍生物被吸附到或結合在㈣上或在存於人 鈣鹽之物質上之其他成份上。 、3 根據本發明之填料通常具㈣鹽含量為至少重 量。/。，鈣鹽含量可從約0.0001到約99 5重量％，合適地從 約0.1到約90重量％，且較佳地從約6〇到約8〇重量％， 在以填料之ϋ體重量為基礎，亦即以填料之乾重量為基礎 下。填料通常具有纖维素衍生物含量為至少Q()i重量二， 纖維素衍生物含量可從約〇 〇1到約3〇重量％，合適地從 勺〇’ 1到”勺20重篁〇/〇,且較佳地從約〇 3到約工〇重量％， 在以填料之固體重量為基礎下。 根據本發明之填料可以實質上不含水的固態材料來供 。亦可以水性組成物來供應。水相或水的含量可以在取 決於生產方法及所欲用途而在廣範圍内變化。 發月亦關於一種製造填料之方法，其包括混合纖維 、π生物（例如任何此處所定義之纖維素衍生物）和含的鹽 、为貝（例如任何此處所定義之含詞鹽之物質，包括飼鹽）， 以及視情況需要之—或多個其他成分。纖維素衍生物及含 16 1356862 鈣鹽之物質之合適地是以提供具有此處定義之纖維素衍生 物及鈣鹽之含量的根據本發明填料之數量來使用。 所使用之纖維素衍生物及含鈣鹽之物質可以固體或水 性組成物或其混合物存在。含躬鹽之物質適合以細粒物質 存在。混合可以藉由添加纖維素衍生物到填料中來達成， 反之亦然。根據本發明之一具體實施例，纖維素衍生物以 固體方式添加到含鈣鹽之物質之水性組成物中，且所得組 成物然後適合被施以有效的分散以溶解纖維素衍生物。較 佳地，混合是藉由將天然纖維素衍生物形成為鹼性水相， 合適為水溶液來進行，其然後與含鈣鹽之物質之水性組成 物混合。在與含鈣鹽之物質混合之前，纖維素衍生物之水 相可被施以預先處理，例如均質化、離心及/或過濾，例如 用以從水相中分離出未溶解纖維素衍生物。 較佳地，纖維素衍生物與含鈣鹽之物質混合，以容許 至少部份的纖維素衍生物吸收到或結合到含鈣鹽之物質 上，較佳地使得其難以藉由與水稀釋來從該物質中移除。' 此可f由進行混合歷時-段足夠長的在吸附物上吸附的時 間來完成。合適地，混合時間為至”"分鐘，較佳地為 至/、’勺5分鐘，更佳地為至少約1〇分鐘，且最佳地為至少 約20分鐘。甚至激n士 +、日人+ 數小犄之此合時間（1-10小時）是有可能的， 假如達到高度吸附是合意的話。合適地，至少約10重量％， =::3。重量％’更佳至少…量％，且最佳至少 結合_==纖維素衍生物係從水相中轉移出且吸附到或 I或/、他存在於含鈣鹽之物質上的成分。 17 丄妁6862 —纖維素衍生物之水相的pH值通常因為吸著所使用之 特义纖維素衍生物而被調整到從約4到約13之數值，較 ^從約Π)’更佳從約7到約8 5。合適驗或酸可用 調整PH❶合適鹼的例子為鹼金屬之碳酸氫鹽及碳酸鹽及 2金屬氫氧化物’合適為碳酸氫鈉，碳酸鈉及氫氧化鈉。 合適酸的例子包括礦物酸、無機酸及酸鹽’合適地為硫酸 及其酸鹽，例如明礬。一般而言，在較低阳，亦即從約4 〇 到中性的pH下，纖維素衍生物的吸附力會較高，但是溶 解度會下降，然而，在較高pH 了，會降低吸附力;但溶 解度會增加。 溫度不是關鍵的，在非加壓的操作環境中，溫度血型 是^約！0到约丨〇〇。〇：，較佳是從約2〇到約8〇〇c。然而， 較高溫度是更有利地’在混合期間，水性組成物之合適溫 度是從30到高至約70。〇更佳是㈣4〇到高至約 當使用亦含有鈣鹽之外的其他成分的含鈣鹽之物質 時，如纖維素或木質纖維素之纖維或原纖維時，纖維素衍 生物之混合和結合可同時與在纖維或原纖維上沉澱鈣鹽進 行或在沉澱之後才進行。&有可能在沉殿之前添加纖維素 衍生物。在此例中，纖維素衍生物是在打漿期間或在打漿 之後的個別吸著中添加。纖維素衍生物可被吸附或結合到 含鈣鹽之物質上或纖維或原纖維表面上及/或吸著在纖=或 原纖維上。吸附相似纖維素衍生物到相似填料·物質上之方 法係揭示在 USP 5731080，· 5824364 ; 6251222 ; 6375794 · 及6599391，彼等揭示内容係併入本文中為參考。 18 1356862 由本發明方法所得 忒所仔之填科可用於例如 组成物存在時，可以直接使 + 表次右以水性 化運輸。 直接使用，右合意時’可被乾燥以簡 本發明亦騎 纖维素纖維之水性懸浮液（“纖維素懸浮液括=—種含 如此處定義之任何—種填料）到纖維素懸浮導真料（例 素懸浮液脫水以形成紙匹或紙片。較佳地 使纖維 权佳地’填料則蕤λ验 二早-組成物方式添加到纖维素懸浮液令。另外：越 或含辦鹽之物質(此處定義 t 衍生物(例如此處定義之任何纖维素二素 纖維=料_，且额㈣地料於㈣耗浮=;入 在本.方法令，其他成分可春^$ λ _ ’此镟占八…… 田然導入纖維素懸浮液令。 此類成力之例子包括傳統填 > η加— 光學增白劑’上膠劑，排 水及留存助劑，乾強度 排 例子包括-嶺土 h .，，、強度劑專。合適傳統填料之 …嶺土，竞土，二氧化鈦，石膏，滑 合成碳酸鈣等，例如白垄， …、及 ^ 巧微右母及沉澱碳酸鈣，高 化氧化鋁（三氫氧化鋁），硫 馱约虱 •弓，硫S久鋇，草酸鈣等。去 使用根據本發明之填料及值纪枯士 田 夕户―* 具料及傳統填料時，根據本發明之填料 ，存在數量可以是至少1重量％，合適地為至少5重量Γ 較佳地為至少10重量％， 直置/0， ^ 更佳為至少約20重量％，且八 適地為高至約99重量％，,、， σ 下^ 重置/〇’在以所有填料之乾重量為基礎 基於松脂之上勝劑，減^ =素·反應性上膠劑，例如 埒、泣 土 、权月曰的皂，基於松脂的乳液/分 、及纖維-反應性上膠劑，如酸酐的乳液/分散液，如 1356862 烯基琥珀酸酐（ASA) ’烯 聚物。合適排水及留存：：稀綱二聚物⑽D)與多 如含有陽離丄 例子包括有機聚合產物，例 3有％離子聚乙烯亞 性平人铷拉你， 陰離子性及非離子 聚物，％離子性、陰離 m ^ - e f及非離子性聚丙烯醯胺， Μ子性聚胺’陽離切粉’及陽離子瓜爾豆，無機物質， 例如鋁化合物，陰離子 …、 輪士他 粒子& f，#卿體#石為主之 粒子，綠土類型之黏土，如皂土，热 及彼等組合。合適排水及留…豕脫土，膠體氧化紹， 存劑之組合的例子包括陽離 子水合物及陰離子微粒子物 ^ 例如險離子澱粉及陰離子 :夕石為主之粒子，陽離子聚丙烯酿胺及陰離子膠體石夕 =主之粒子，以及陽離子聚丙烯ϋ胺及4土或蒙脫土。 口濕強度劑之粒子包括聚胺及聚胺基酿胺。含有根據本 兔月之填料及陽離子澱粉之紙張顯示非常良好 質。 根據本發明之一具體實例’至少一種上膠劑被導入纖 維素懸浮液中，以產生含有填料之上膠紙張。較佳地，上 膠劑為此處所提之纖維素-反應性上膠劑。合適乙烯酮二聚 物具有下列通式，其中R1與R2係表示飽和或不飽和之烴 基團，通常是飽和烴類，烴基團適當地係具有從8到36 個奴原子，通常是具有12到20個碳原子之直線或支鏈烷 基，例如十六烷基與十八烷基。乙烯酮二聚物在常溫、即 25 C、適當地是2〇〇c下可以是液態。通常，酸酐可以藉 下述之通式（II)以表示其特色，其中R3與R4可以是相同或 不同且代表飽和或不飽和之烴基，適當地係具有從8到3〇 20 1356862 個碳原子，m R4連同-C-O-C半體可以形成5到6元 :環，可以選用地被含有高4 30個碳原子之烴基團所進 :步取代。商業上可以使狀酸酐之例子係、包括貌基與鍵 、基琥珀酸酐且特別是異十八烯基琥珀酸酐。 (I)Or DSC can of course be higher than 〇 A gate at 0.65, as long as 0, and DSNC are respectively derogatory for this location. For example, an example of a suitable cellulose derivative having a degree of substitution of the DN field DSA of 0.75 and a DSc of 〇15 and a DSNa of 〇60 〇 having a degree of substitution is disclosed in the same application as w Δ ν Akzo Nobel NV is the water-soluble low DS carboxy alkane A in the application for the name of the application. From this material, it is suitably dissolved in the water, and (iv) the total weight of the vitamin-derived fiber and the quasi-sugar is based on the aqueous solution. ♦ Having a right-hand 4, 5? «i weight % solubility' is preferably at least 9 〇 wt%, more preferably at least 95 wt% ' and optimally at least 98 wt%. 15 1356862 Cellulose derivatives generally have an average molecular weight of at least 2 guanidines, preferably at least 50 〇 〇 呑 呑, and an average molecular weight of usually from ^ to 1,000,000 dolphines, preferably up to 500,000 channels. Ertun. Preferably, in the filler according to the present invention, the cellulose derivative β is adsorbed or bound to at least the silk salt or on other components of the salt-containing material: suitably, at least about 10 weights. %, preferably at least about, such as % by weight 'more preferably at least about 45% by weight' and most preferably at least about the weight. The cellulose derivative of /0 is adsorbed or bound to (iv) or to other components present on the substance of the human calcium salt. 3, the filler according to the invention generally has a (iv) salt content of at least a weight. /. The calcium salt content may range from about 0.0001 to about 99 5% by weight, suitably from about 0.1 to about 90% by weight, and preferably from about 6 Torr to about 8% by weight, based on the weight of the steroid of the filler. , that is, based on the dry weight of the filler. The filler usually has a cellulose derivative content of at least Q()i by weight two, and the cellulose derivative content may be from about 〇〇1 to about 3% by weight, suitably from the scoop '1 to the spoon 20 篁〇 /〇, and preferably from about 〇3 to about % by weight, based on the solid weight of the filler. The filler according to the present invention may be supplied as a solid material which is substantially free of water. Supply. The aqueous phase or water content can vary widely depending on the method of production and the intended use. The month also relates to a method of making a filler comprising a blend of fibers, π organisms (such as any of the fibers defined herein). a derivative) and a salt thereof, which is a shellfish (such as any of the salts containing a salt as defined herein, including a feed salt), and optionally as needed - or a plurality of other ingredients. Cellulose derivatives and calcium containing 16 1356862 The substance of the salt is suitably used in an amount to provide a content of the cellulose derivative and the calcium salt as defined herein according to the present invention. The cellulose derivative and the calcium salt-containing substance may be solid or The composition or mixture thereof is present. The substance containing the onium salt is suitably present as a fine particulate material. Mixing can be achieved by adding a cellulose derivative to the filler, and vice versa. According to one embodiment of the invention, cellulose The derivative is added to the aqueous composition of the calcium salt-containing material in a solid form, and the resulting composition is then suitably subjected to effective dispersion to dissolve the cellulose derivative. Preferably, the mixing is carried out by deriving natural cellulose. The substance is formed into an alkaline aqueous phase, suitably an aqueous solution, which is then mixed with an aqueous composition of the calcium salt-containing material. The aqueous phase of the cellulose derivative can be applied prior to mixing with the calcium salt-containing material. Processing, for example homogenization, centrifugation and/or filtration, for example to separate undissolved cellulose derivatives from the aqueous phase. Preferably, the cellulose derivative is mixed with a calcium salt-containing material to allow at least a portion of The cellulose derivative is absorbed or bound to the substance containing the calcium salt, preferably such that it is difficult to remove from the substance by dilution with water. 'This can be mixed by the duration-stage The length of time sufficient to adsorb on the adsorbate is completed. Suitably, the mixing time is to "" minutes, preferably to /, 'spoon for 5 minutes, more preferably at least about 1 minute, and optimal. The ground is at least about 20 minutes. Even the combined time (1-10 hours) of the singer +, the Japanese + the number of small squats is possible, if it is desirable to achieve high adsorption. Suitably, at least about 10% by weight, =::3. The % by weight is more preferably at least ... by weight, and optimally at least combined with the _== cellulose derivative is a component which is removed from the aqueous phase and adsorbed to or I or /, which is present on the substance containing the calcium salt. 17 丄妁6862—The pH of the aqueous phase of the cellulose derivative is usually adjusted to a value of from about 4 to about 13 by sorption of the specific cellulose derivative used, preferably from about Π) From about 7 to about 8 5 . Suitable tests or acids can be used to adjust the pH. Suitable examples of bases are alkali metal hydrogencarbonates and carbonates and 2 metal hydroxides. Suitable are sodium hydrogencarbonate, sodium carbonate and sodium hydroxide. Examples of suitable acids include mineral acids, inorganic acids and acid salts, which are suitably sulfuric acid and its acid salts, such as alum. In general, at lower yang, ie from about 4 Torr to neutral pH, the adsorption of cellulose derivatives will be higher, but the solubility will decrease, however, at higher pH, the adsorption will decrease. ; but the solubility will increase. Temperature is not critical, in a non-pressurized operating environment, the temperature blood type is about! 0 to about 丨〇〇. 〇: Preferably, it is from about 2 〇 to about 8 〇〇c. However, higher temperatures are more advantageous' during mixing, the suitable temperature for the aqueous composition is from 30 up to about 70. Preferably, it is (4) up to about 4 minutes up to about when a calcium salt-containing substance other than a calcium salt is used, such as cellulose or lignocellulose fibers or fibrils, a mixture of cellulose derivatives and The bonding can be carried out simultaneously with precipitation of the calcium salt on the fibers or fibrils or after precipitation. & It is possible to add cellulose derivatives before the sink. In this case, the cellulose derivative is added during beating or during individual sorption after beating. The cellulose derivative can be adsorbed or bound to the substance containing the calcium salt or to the surface of the fiber or fibril and/or adsorbed on the fiber = or fibril. Methods for adsorbing similar cellulose derivatives to similar fillers and materials are disclosed in U.S. Patent Nos. 5, 573, 1080, 5,824, 364, 6, 251, 222, 6, 375, 794, and 6, 599, 391, the disclosures of 18 1356862 The fillings obtained by the method of the present invention can be used, for example, in the presence of a composition, and the + table can be directly transported in aqueous form. Directly used, right when desired 'can be dried to simplify the invention also riding an aqueous suspension of cellulosic fibers ("cellulosic suspensions include - all kinds of fillers as defined herein" to cellulose suspension guide The material suspension is dehydrated to form paper or paper. It is preferred to add the fiber right to the 'filler' and then add the composition to the cellulosic suspension. Substance (here defined t derivative (such as any cellulose fibril fiber defined here = material _, and the amount of (4) land in (four) consumption floating =; into the method. Other ingredients can be spring ^ $ λ _ 'This 镟 occupies eight... Tian Ran introduces cellulose suspension. Examples of such strength include traditional filling > η plus - optical brightener 'sizing agent, drainage and retention aids, dry strength row Examples include - ridge soil h.,,, strength agent. Suitable for traditional fillers... ridge soil, competitive soil, titanium dioxide, gypsum, slip synthetic calcium carbonate, etc., such as white ridge, ..., and ^ Qiaowei right mother and precipitated carbonic acid Calcium, high alumina (trihydrogen aluminum oxide), sulphur, sputum, bow, sulfur S Long-term, calcium oxalate, etc. When using the filler according to the invention and the value of the glutinous rice field-* materials and conventional fillers, the filler according to the invention may be present in an amount of at least 1% by weight, suitably at least 5 The weight Γ is preferably at least 10% by weight, straight/0, ^ more preferably at least about 20% by weight, and 8% suitably up to about 99% by weight, and, σ is reset ^ 在The dry weight of all fillers is based on the rosin-based sizing agent, minus the sulphur-reactive sizing agent, such as sputum, weeping earth, saponin, rosin-based emulsion/min, and fiber-reactive sizing. An agent, such as an emulsion/dispersion of an acid anhydride, such as 1356862 alkenyl succinic anhydride (ASA) 'ene polymer. Suitable drainage and retention:: dimer dimer (10) D) and many examples of containing cations, including organic polymerization products, Example 3 has a % ion polyethylene subtropical puller, anionic and nonionic polymers, % ionic, anionic m ^ - ef and nonionic polypropylene decylamine, scorpion polyamine Cut powder 'and cationic guar, inorganic substances, such as aluminum compounds, Yin Sub..., 轮士他颗粒&f,#卿体# Stone-based particles, clay of smectite type, such as bentonite, heat and their combination. Suitable for drainage and retention... 豕 soil removal, colloidal oxidation, Examples of combinations of the present invention include cationic hydrates and anionic fine particles; for example, ionic ion starch and anion: sapphire-based particles, cationic polypropylene-brown amine and anionic colloidal stone = main particles, and cationic polyacrylamide And 4 soil or montmorillonite. The particles of the wet strength agent include polyamine and polyamine-based amine. The paper containing the filler according to the present invention and the cationic starch shows very good quality. According to one embodiment of the present invention, at least A sizing agent is introduced into the cellulosic suspension to produce a sized paper containing the filler. Preferably, the sizing agent is a cellulose-reactive sizing agent as set forth herein. Suitable ketene dimers have the general formula wherein R1 and R2 represent a saturated or unsaturated hydrocarbon group, typically a saturated hydrocarbon, suitably having from 8 to 36 slave atoms, usually having 12 to A straight or branched alkyl group of 20 carbon atoms, such as cetyl and octadecyl. The ketene dimer may be in a liquid state at normal temperature, i.e., 25 C, suitably 2 〇〇c. In general, the acid anhydride may be represented by the following formula (II), wherein R3 and R4 may be the same or different and represent a saturated or unsaturated hydrocarbon group, suitably having from 8 to 3〇20 1356862 carbon atoms. mR4 together with the -COC half may form 5 to 6 members: a ring, optionally substituted with a hydrocarbon group having a height of 4 to 30 carbon atoms. Commercially available examples of pharmaceutically acceptable anhydrides include the phenotypic group and the bond, the succinic anhydride, and especially the isooctadecenyl succinic anhydride. (I)

R-CH=C-CH-R o—c=o (Π) ο ο 3 II II ΛR-CH=C-CH-R o-c=o (Π) ο ο 3 II II Λ

R—C—〇~~c—R 適合之乙烯酮二聚物、酸酐與有機異氰酸酿係包括美 國專利第4,522,686號中所揭示之化合物，其係收錄於此 以作為參考之用。 根據本發明之填料通常可被加入到纖維素懸浮液中， 其數量可在取決於纖維素懸浮液之類型、所製造紙張之類 型’添加點等而定而在廣範圍内變化。以乾纖維之 基礎，填料通常是從重量％，合適是從約5到約 重量％，且通常是從約10到約3〇重量％的範 里内變化。iUb，在以乾纖維之重量為基礎下，根據本發 明之紙張通常具有本發明之填料含量的範圍是&】到約 重量％ ’合適是從約5到約4〇重量％，且通常是從10到 約30重量％。 ~ :在本方法中使用其他成分時，這些成分可被加到纖 維偏液，其數量可在取決於成分之類型及數量 素懸浮液之類型，填料含量，所製造紙張之類型，添加點 等而定’而在廣範圍内變化。在基於乾纖維之重量下..· 膠劑通常被導入纖維素懸浮液之數.量為至少約〇_ 旦 · 重里 21 1356862 % -適地為至少約〇1重量％，且其上限通常為約2重量 二：適地為約〇·5重量％。一般而言排水及留存助劑以 4使用這些助劑時所獲得更好的排水及/留存率的數量 來導入纖維素懸浮液中。排水及留存助劑，乾強度劑及濕 強度劑，可彼此獨立地，在以乾纖維為基準下，以至少約 〇·〇〇ι重田量％’經常為至少約0 005重量％，且上限通常為 約5重量❶/〇,及合適為約i 5重量％的數量來導入。 在此所使用的術語“紙張，，不僅包括紙張及其產物， 也包括含纖維素纖維的紙片或似紙匹產品，例如紙板（board) 及紙板（pa⑽Gan1)，及其產品。本方法可用在從不同類型 的纖維素（含纖維素）之纖維的水性懸浮液來製造紙張，且 在以該物質為基準下，懸浮液合適地包含至少25重量％的 纖維’且較佳地為至少5G f量的纖維。纖維素纖維可為 包括木質或動物或多年生植物的基於原始纖維及/或回收纖 維。纖維素懸浮液可為含木質或不含木質，且其可為基於 化學漿之纖維，例如硫酸酯，亞硫酸酯及有機溶劑木漿 (organosolve pulp)，機械木漿，如熱機械木漿化學-熱_ 機械木漿，精鍊木漿，及磨木漿，彼等可為來自硬質木材 及軟質木材，且亦可基於回收纖維，視情況需要為來自脫 墨紙漿及其混合物。纖維素懸浮液合適地具有在中性到鹼 性範圍的pH，例如從約6到約10，較佳地從約6·5到約8… 所產生紙張可為經乾燥、經塗覆及軋光的。紙張可以 塗覆有例如碳酸鈣，石膏’矽酸鋁，高嶺土，氫氧化結， 矽酸鎂，滑石，二氧化鈦，硫酸鋇，氧化鋅，合成顏料， 22 1356862 及其混合物。 所產生紙張的基重（grammage)可在取決於所產生紙張 之類型而在廣範圍内變化，通常基重是在從約20到約' 500#’合適地從約3〇到約45〇〆，且較佳地從3〇到 約110 g/m2的範圍内。 較佳地，本發明是用於生產未經塗覆及已塗覆之柯色 紙，光電紙，視需要含有機械木漿之未經塗覆及經塗覆之 高級紙’以及筆記用紙及印刷紙。尤其較佳產品為經塗覆 柯色紙，其中組合高光澤及高不透明度與嵩度（ΜΙ"。 鲁 本發明進-步在下列實施例中說明，然而，本發明不 意圖被因此限制。除非有特別指日月，份數及％是指重量份 及重量％。 實施例1 根據本發明及作為比較用的填料是藉由處理含鈣鹽之 物質與、纖維素衍生物來製備的。所使用的纖維素衍生物是 具有 dsni(dsca =DSCM =DSa =DSna =DSni)為 〇 3、〇 32 和 〇·7之缓甲基纖維素（“(^，，卜所使用的另—個⑽^具 · 有 DSca =DScm =DSa =0.4、DSc =DSqn =0.17 ;及 DSn丨=dSna = 0.4-0.17=0.23之季胺羧甲基纖維素（“qn_cmc”）。所使用 的纖維素衍生物之平均分子量為在從1〇〇,〇〇〇到4〇〇,〇⑼ 的範圍中。所使用含鈣鹽之物質為分別具有表面積為57 及l〇.〇m2/g的不同沉澱碳酸鈣（“pcc”）。另一種含释鹽之 物質為SuperFUl ® (在紙漿粉末上的pcc)。 填料是藉由溶解CMC到水中使濃度為〇.5重量％來製 23 1356862 添加經CMC處理的PCC: 0秒 添加AKD分散液： 30秒 添加陽離子澱粉： 45秒 添加石夕石粒子： 60秒 紙片形成： 75秒 紙片是根據使用 Dynamical Sheet Former(“Formette”， CTP Grenoble)之標準方法來製造。使用 Cobb6()(SCAN-P 12:64)方法以得到上膠結果。表1顯示所得結果。 表1 測試號碼 紙張的PCC含量 填料 Cobb60 1 18% CP1 45 2 19% IP1 25 .實施例3 在本實施例中，評估根據本發明之製紙方法，其中（i) 經CMC處理的PCC被加入到紙漿懸浮液中，且（ii)CMC 及PCC(未經處理）被分別加入到紙漿懸浮液中。 紙片是從實施例2中所使用的相同類型之紙漿中產 生，且在以乾紙張為基準下，其含有30重量％未經處理的 PCC(10m2/g 的表面積）或經 CMC(DSN丨 0.3)的 PCC(10 m2/g)(根據實施例1的IP2)。在紙漿懸浮液中，加入4公 斤/噸之乾陽離子澱粉纖維（PB 970)，3.0公斤/噸的乾AKD 纖維（水性上勝分散液，Eka Keydime C223)，及含有陽離 子聚丙烯醯胺（Eka PL 1310)及矽石粒子（Eka NP 780)之留 1356862 存系統。陽離子聚丙烯醯胺及矽石粒子兩者則以0.20公斤 /噸之乾紙張數量來添加。當使用未經處理的PCC時，分 別添加具有DSN1為0.3之1.0公斤/噸。當添加經CMC處 理的PCC時，未進行分開添加的CMC。添加順序係如下 述： 添加陽離子澱粉 0秒 添加經CMC處理/未經處理的PCC: 30秒 分開添加CMC: 35秒 添加AKD: 45秒 添加陽離子聚丙烯醯胺： 60秒 添加矽石粒子： 75秒 紙片形成： 90秒 如貫施例2般評估紙片。結果係顯不在表2中。 表1 測試號碼 添加模式 填料 Cobbfi0 1 分開添加 未經處理的PCO+CMC 65 2 添力口經CMC處理白勺 PCC irz 35 實施例4 使用實施例1之產物並在製紙方法中進行評估。以相 似於實施例3之方法，除了沒有使用陽離子澱粉外，從含 26R-C-〇~~c-R Suitable ketene dimers, anhydrides and organic isocyanic acid systems include the compounds disclosed in U.S. Patent No. 4,522,686, which is incorporated herein by reference. The filler according to the present invention can usually be added to the cellulosic suspension, and the amount thereof can be varied within a wide range depending on the type of the cellulose suspension, the type of addition of the paper to be produced, and the like. On a dry fiber basis, the filler is typically varying from weight percent, suitably from about 5 to about weight percent, and typically from about 10 to about 3 weight percent. iUb, based on the weight of the dry fiber, the paper according to the invention generally has a filler content of the invention in the range of &] to about wt% 'suitably from about 5 to about 4% by weight, and usually From 10 to about 30% by weight. ~ : When other ingredients are used in the method, these ingredients may be added to the fiber eclipse, the amount of which may depend on the type of the component and the type of the susceptor suspension, the filler content, the type of paper produced, the addition point, etc. And it's changing in a wide range. The weight of the gum is usually introduced into the cellulosic suspension based on the weight of the dry fiber. The amount is at least about 〇 重 重 重 21 21 356 862 % - suitably at least about 1% by weight, and the upper limit is usually about 2 weight two: suitably about 〇 5% by weight. In general, the drainage and retention aids are introduced into the cellulosic suspension by the amount of better drainage and/or retention obtained with these auxiliaries. Drainage and retention aids, dry strength agents and wet strength agents, independently of each other, based on dry fiber, at least about 〇·〇〇ι heavy field %' often at least about 0 005 weight percent, and upper limit It is usually introduced in an amount of about 5 weights ❶/〇, and suitably about 5% by weight. The term "paper, as used herein, includes not only paper and its products, but also paper or cellulose-like products containing cellulose fibers, such as cardboard and paperboard (pa(10) Gan1), and products thereof. This method can be used in Paper is produced from an aqueous suspension of different types of cellulose (cellulose-containing) fibers, and the suspension suitably comprises at least 25% by weight of fibers 'and preferably at least 5 Gf based on the substance. Amount of fiber. Cellulose fiber can be based on virgin fiber and/or recycled fiber including wood or animal or perennial. Cellulose suspension can be woody or wood free, and it can be chemical pulp based fiber, for example Sulfate, sulfite and organosolve pulp, mechanical wood pulp, such as thermomechanical pulp chemistry - heat _ mechanical wood pulp, refined wood pulp, and groundwood pulp, which can be from hardwood and Soft wood, and may also be based on recycled fibers, optionally from deinked pulp and mixtures thereof. Cellulosic suspensions suitably have a pH in the neutral to alkaline range, for example from about 6 to about 10, preferably from about 6.5 to about 8... The resulting paper may be dried, coated and calendered. The paper may be coated with, for example, calcium carbonate, gypsum 'aluminum silicate, kaolin, Hydrogenation, magnesium citrate, talc, titanium dioxide, barium sulfate, zinc oxide, synthetic pigments, 22 1356862 and mixtures thereof. The basis weight of the resulting paper can vary widely depending on the type of paper produced. The variation, usually the basis weight, is suitably in the range from about 20 to about '500#', suitably from about 3 Torr to about 45 Å, and preferably from 3 Torr to about 110 g/m2. The invention is for producing uncoated and coated koe paper, photoelectric paper, uncoated and coated fine paper containing mechanical wood pulp as needed, and note paper and printing paper. Especially preferred products For coated Koch paper, where high gloss and high opacity and twist are combined (ΜΙ". The invention is described in the following examples, however, the invention is not intended to be limited thereby unless otherwise specified Months, parts and % refer to parts by weight and % by weight. The filler according to the invention and as a comparative is prepared by treating a calcium salt-containing substance with a cellulose derivative. The cellulose derivative used has dsni (dsca = DSCM = DSa = DSna = DSni)缓3, 〇32 and 〇·7 of slow-methylcellulose (“(^,, another one used in Bu (10)^ have DSca = DScm = DSa = 0.4, DSc = DSqn = 0.17; and DSn丨=dSna = 0.4-0.17 = 0.23 quaternary ammonium carboxymethyl cellulose ("qn_cmc"). The average molecular weight of the cellulose derivative used is from 1 〇〇, 〇〇〇 to 4 〇〇, 〇 (9) In the scope. The calcium salt-containing materials used were different precipitated calcium carbonates ("pcc") having a surface area of 57 and 1 〇m2/g, respectively. Another substance containing a salt release is SuperFUl ® (pcc on pulp powder). The filler was prepared by dissolving CMC in water to a concentration of 〇.5% by weight. 23 1356862 Adding CMC-treated PCC: 0 second adding AKD dispersion: 30 seconds adding cationic starch: 45 seconds adding Shishi stone particles: 60 seconds Paper Sheet Formation: 75 second paper sheets were manufactured according to standard methods using Dynamical Sheet Former ("Formette", CTP Grenoble). The Cobb6() (SCAN-P 12:64) method was used to obtain the sizing result. Table 1 shows the results obtained. Table 1 PCC content of test number paper Filler Cobb60 1 18% CP1 45 2 19% IP1 25 . Example 3 In this example, a paper making method according to the present invention was evaluated, wherein (i) CMC-treated PCC was added to In the pulp suspension, (ii) CMC and PCC (untreated) were separately added to the pulp suspension. The paper sheets were produced from the same type of pulp used in Example 2, and contained 30% by weight of untreated PCC (10 m 2 /g surface area) or CMC (DSN 丨 0.3) on a dry paper basis. PCC (10 m2/g) (IP2 according to Example 1). In the pulp suspension, 4 kg / ton of dry cationic starch fiber (PB 970), 3.0 kg / ton of dry AKD fiber (water-based dispersion, Eka Keydime C223), and cationic polypropylene amide (Eka PL) were added. 1310) and the removal of the meteorite particles (Eka NP 780) 1568862 storage system. Both cationic polypropylene decylamine and vermiculite particles were added in an amount of 0.20 kg/ton dry paper. When untreated PCC was used, 1.0 kg/ton with a DSN1 of 0.3 was added, respectively. When the CMC-treated PCC was added, the separately added CMC was not performed. The order of addition is as follows: Adding cationic starch 0 second Adding CMC treated/untreated PCC: Adding CMC separately for 30 seconds: Adding AKD for 35 seconds: Adding cationic polypropylene decylamine for 45 seconds: Adding vermiculite particles for 60 seconds: 75 Second sheet formation: 90 seconds was evaluated as in Example 2. The results are not shown in Table 2. Table 1 Test No. Addition mode Filler Cobbfi0 1 Separate addition Untreated PCO + CMC 65 2 Addition port CMC treated PCC irz 35 Example 4 The product of Example 1 was used and evaluated in the papermaking process. Similar to the method of Example 3, except that no cationic starch was used,

Claims (1)

13568621356862 100年9月>·〇曰修正替換頁 申請專利範圍： 種填料，其包括鈣鹽及具有從0.01高至〇 65之 序·離子基團的取代度之纖維素衍生物其中填料為實質上 不含纖維素或木質纖維素之纖維或原纖維。 2、 —種填料，其包括鈣鹽及具有從0.01高至〇 65之 淨離子基團的取代度之纖維素衍生物，其中纖維素衍生物 含有陽離子基團。 T生物 其特徵在於 其特徵在於 其特徵在於 其特徵在於 其特徵在於 其特徵在於 3、 根據申請專利範圍第1或2項之填料 取代度為從0.01到〇·6〇。 4、 根據申請專利範圍第1或2項之填料 取代度為從0.5到〇. 5 〇。 5、 根據申請專利範圍第1或2項之填料 取代度為從〇. 15到〇. 4 〇。 6、 根據申請專利範圍第1或2項之填料 纖維素衍生物為纖維素醚。 7、 根據申請專利範圍第1或2項之填料 纖維素衍生物包含羧甲基基團。 8根據申請專利範圍第1或2項之填料 纖維素衍生物包含季銨基。 辛行9生Λ射請專利範圍第1項之填料，其特徵在於纖維 京何生物為陰離子。 於纖=根射請專利範圍第1《2項之填料，其特徵在 於纖維素衍生物為兩性。 11、根據中請專利範圍第！或2項之填料，其特徵在 28 丄咖862 Μ I %lmm\⑽年9月，正麵 於纖維素衍生物為至少部分水溶性。 12、根據中請專利範圍第i或2項之填料，其特徵在 於以填料之固體重量為基準下，填料具有從〇 3到1〇重量 %的纖維素衍生物含量。 U、根攄申請專利範圍第丨或2項之填料，其特徵在 於以填料之固體重量為基準下，填料具有從6〇到8〇重量％ 的鈣鹽含量。 ° 14、 根據申請專利範圍第丨或2項之填料，其特徵在 於名弓鹽為碳酸約。 、 15、 根據申請專利範圍第丨或2項之填料，其特徵在 於鈣鹽為沉澱的碳酸約。 16、 根據申請專利範圍第丨或2項之填料，其特徵在 於鈣鹽為重質碳酸鈣。 〃 ^ 1 7、根據申請專利範圍第2項之填料，其特徵在於填 料進一步包括纖維素或木質纖維素之纖維或原纖維。 :1 8、根據申請專利範圍第2項之填料，其特徵在於填 料為實貝上不含纖維素或木質纖維素之纖維或原纖維。 19、根據申請專利範圍第i或2項之填料，其特徵在 於至；10重量。/。的纖維素衍生物被吸附到或結合在鈣鹽 上。 2〇、根據申請專利範圍第丨或2項之填料，其特徵在 於至少45重量％的纖維素衍生物被吸附到或結合在鈣鹽 上。 21、根據申請專利範圍第工或2項之填料，其特徵在 29 丄JJOOOZ 100年9迅〇日修正替換頁 :至少Μ重量_纖維素衍生物被吸附到或結合在妈 鹽 22、一種紙張，其台 G括根據申請專利範圍第1到21項 T任一項之填料。 β 2 3、根據申請專利簕囹淨 以乾…其·隹 乾園第22項之紙張，其特徵在於在 ^乾紙張為基準下，紙張之 、，心填科含3:疋從5到40重量％。 24、-種製造填料之方法，其包括在實質上纖 木質纖維素之纖維或原纖維 ^ ，、3 偽Β 存在下，合含4弓鹽之物質 與具有從0.01高至〇 65夕免& ^ Μ 生物。 ./於濉子基團的取代度之纖維素衍 2 5、一種製造填料 、封之方法，其包括混合含鈣鹽之 〇具有羧烷基取代度為從〇〇 # , 〇1间至0·65之纖維素衍生物， 其中纖维素衍生物包含陽離子基團。 %、一種製造紙之方法，其包括提供一種含有纖維素 …之水性Μ液，將根據申請專利範圍第i到 —項之填料導入懸浮液中， 、 戋紙片。 便心子液脱水，以形成紙匹 2 7根據申凊專利範圍第2 6頊之太土甘此 固乐項之方法，其特徵在於 由將含有鈣鹽及纖維f衍攻物 s 曰 飒耳京订生物之早—組成物添加到懸浮液 中’以導入填料到懸浮液中。 I根據中請專利範圍第26項之.方法，其特徵在於以 乾纖維為基礎，填料的添加量為從5到40重量％。 2 9、根據申請專利範圍第9 6工音夕七、+ j乾阁弟26項之方法，其特徵在於以 乾纖維為基礎，填料的添加量為從H)到30重量％。 30 1356862 _ Ώ Ο |\ —w' 修正替換頁 30、 根攄中請專利範圍第26項之方法，其特徵在於並 進一步包括添加纖維素-反應性上膠劑到懸浮液中。 31、 根射請專利範圍第26項之方法，其特徵在於其 進一步包括導入排水及留存助劑到纖維素懸浮液令/ 32、 根射請專利範圍第31項之方法，其特徵在於該 排水及留存助劑包括陽離子、陰料或㈣子聚合物。 33、 根據申請專利範圍第31項之方法，其特口徵在於該 排水及留存助劑包括陽離子聚合物及陰離子微粒子物質之 組合。 3:留：據申請專利範圍第31項之方法其特徵在於該 排水及留存助劑包括陽離子澱粉及陰離子膠體石夕石為主之 粒子之、-且合’陽離子聚丙稀酿胺及陰離子膠體石夕石為主之 粒子之組合，以及陽雜：工u 及％離子聚丙烯醯胺及皂土或蒙脫土之組 合0 十一、圖式： 無。 31 VSeptember, 100 > 〇曰 Amendment Replacement Page Patent Application: A filler comprising a calcium salt and a cellulose derivative having a degree of substitution from 0.01 to 〇65, wherein the filler is substantially Fiber or fibrils without cellulose or lignocellulose. 2. A filler comprising a calcium salt and a cellulose derivative having a degree of substitution from 0.01 to a net ionic group of hydrazine 65, wherein the cellulose derivative contains a cationic group. The T organism is characterized in that it is characterized in that it is characterized in that it is characterized in that the degree of substitution of the filler according to the first or second aspect of the patent application is from 0.01 to 〇6〇. 4. The degree of substitution of the filler according to item 1 or 2 of the patent application range is from 0.5 to 〇. 5 〇. 5. The degree of substitution of the filler according to item 1 or 2 of the scope of the patent application is from 〇. 15 to 〇. 4 〇. 6. Filler according to claim 1 or 2 The cellulose derivative is a cellulose ether. 7. Filler according to claim 1 or 2 The cellulose derivative comprises a carboxymethyl group. 8 Filler according to claim 1 or 2 The cellulose derivative comprises a quaternary ammonium group. Xin Xing 9 Λ Λ 请 请 请 请 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利In the case of the fiber, the filler of the first item of the second item is characterized in that the cellulose derivative is amphoteric. 11, according to the scope of the patent scope! Or 2 fillers, characterized by 28 丄 862 Μ I %lmm\(10) September, which is at least partially water soluble in the cellulose derivative. 12. A filler according to item ith or item 2 of the patent application, characterized in that the filler has a cellulose derivative content of from 〇3 to 1% by weight based on the solid weight of the filler. U. The filler of claim No. 2 or 2 of the patent application is characterized in that the filler has a calcium salt content of from 6 〇 to 8 〇 by weight based on the solid weight of the filler. ° 14. A filler according to item 丨 or item 2 of the patent application, characterized in that the name bow salt is carbonic acid. 15. A filler according to item 丨 or item 2 of the patent application, characterized in that the calcium salt is precipitated carbonic acid. 16. A filler according to item bis or item 2 of the patent application, characterized in that the calcium salt is heavy calcium carbonate. 〃 ^ 17. The filler according to item 2 of the patent application, characterized in that the filler further comprises fibers or fibrils of cellulose or lignocellulose. The filler according to item 2 of the patent application is characterized in that the filler is a fiber or fibril containing no cellulose or lignocellulose on the solid shell. 19. A filler according to item i or item 2 of the patent application, characterized in that; 10 weight. /. The cellulose derivative is adsorbed or bound to the calcium salt. 2. A filler according to item bis or item 2 of the patent application, characterized in that at least 45% by weight of the cellulose derivative is adsorbed or bound to the calcium salt. 21, according to the scope of the application for the scope of the patent or two of the filler, its characteristics in the 29 丄 JJOOOZ 100 years 9 Xun Day revised replacement page: at least Μ weight _ cellulose derivatives are adsorbed or combined in the mother salt 22, a paper , the table G includes the filler according to any one of the claims 1 to 21 of the patent application. β 2 3, according to the patent application, the paper is dry... The paper of the 22nd item of the dry garden is characterized by the basis of the dry paper, the paper, and the heart filling section: 3: 疋 from 5 to 40 weight%. 24. A method of making a filler comprising: in the presence of substantially fibrillar cellulose fibers or fibrils, 3, and 3 pseudomonides, comprising 4 bow salts and having a mass from 0.01 to 〇65 ; ^ Μ Creature. / / Cellulose derivative of the degree of substitution of the scorpion group 2, a method for producing a filler, sealing, comprising mixing a calcium-containing salt with a carboxyalkyl group substitution degree from 〇〇#, 〇1 to 0 A cellulose derivative of 65, wherein the cellulose derivative comprises a cationic group. % A method of making paper comprising providing an aqueous mash containing cellulose, introducing a filler according to the scope of claims ii to - into a suspension, and creping a paper. Dehydration of the heart liquid to form a paper 2 7 according to the method of claim 26 of the patent scope of the patent, which is characterized in that it contains a calcium salt and a fiber f. Pre-organizing the organism - the composition is added to the suspension 'to introduce the filler into the suspension. The method according to the invention of claim 26, characterized in that the filler is added in an amount of from 5 to 40% by weight based on the dry fiber. 2 9. According to the method of applying for the patent scope, the method of the ninth, and the gram of the prince, the method is characterized in that the filler is added in an amount of from H) to 30% by weight based on the dry fiber. 30 1356862 _ Ώ Ο |\ —w' Amendment of the replacement page 30. The method of claim 26, characterized in that it further comprises adding a cellulose-reactive sizing agent to the suspension. 31. The method of claim 26, wherein the method further comprises the step of introducing a drainage and retention aid to the cellulosic suspension, or the method of claim 31, wherein the drainage is And retention aids include cationic, negative or (tetra) subpolymers. 33. The method of claim 31, wherein the drainage and retention aid comprises a combination of a cationic polymer and an anionic particulate material. 3: Retaining: According to the method of claim 31, the drainage and retention aids include cationic starch and anionic colloidal stone, which are mainly composed of particles, and - cationic polyacrylamide and anionic colloidal stones. The combination of the particles of the main stone, and the combination of the yang and the ionic polyacrylamide and bentonite or montmorillonite 0. Figure: None. 31 V