200426275 玖、發明說明： 【發明所屬之技術領域】 本發明關於一種製造紙的方法，其中在纖維素原料由 網前箱（headbox)噴射到漉網上以形成紙幅之前，將造紙添 加劑導入該纖維素原料内。 【先前技術】 發明背景 在造紙技藝中，將含有纖維素纖維、視需要選用的填 料及添加劑之水性懸浮液（被稱為原料）送入網前箱内，該 網前箱將原料噴射到一成形漉網上。水由原料排出，俾在 漉網上形成濕紙幅，及更將紙幅脫水及在造紙機的乾燥段 中被乾燥。 通常將滯留劑導入原料中，俾增加粒子如細粒子和填 料粒子到纖維素纖維上的吸附，以便它們被漉網上的纖維 所保留。技藝中已知道各式各樣的滞留劑，其之例子包括 不同分子量的陰離子性、非離子性、兩性及陽離子性有機 聚合物、無機材料及其組合物。由於不完全的滯留，由將 原料和濕紙幅脫水所得到的水，被稱為白水，係含有不保 留在淹網上的細粒子，而該白水通常在不同的流動迴路中 被循環。 在具有稀釋網前箱的造紙機中，白水係用於稀釋網前 相内的原料。藉此，用起源自白水的低稠度流體來稀釋高 稠度流體。網前箱具有一系列的混合段或稀釋線分佈在網 200426275 前箱的寬度上。白水係被注入混合段内以便局部控制原料 的稀釋，藉以形成可變的稠度輪廓，其以固定的體積流速 離開堰板縫隙。該稀釋網前箱設計係提供對紙張特性的較 佳控制；藉由調整稀釋量，即在橫過機器的稀釋網前箱之 數個點的高稠度流體對低稠度流體的比例，則能以改良的 方式來控制紙幅的基重，且在橫機器向中使成本質上均勻 的。然而明顯地，當使用高性能滯留劑時，已經體驗到造 紙方法及所製得的紙張特性係仍未令人完全滿意的，已經 將其歸因於不當的木瀝青（pitch)沈積控制。 在製造各種紙張中，造紙機上的木瀝青積聚及最後紙 中的瀝青球之形成所導致的問題已經在以前被認知了。木 瀝青通常係指經乳化的疏水性有機化合物。木瀝青可被定 義為黏性、樹脂狀材料，其在碎漿程序期間由木材釋放出 。木瀝青亦包括起源於經塗覆的廢紙及經回收的纖維之黏 性物質，如添加劑，且常常被稱為黏物或膠黏物。在造紙 廠製程水中，木瀝青以不穩定、疏水性粒子的膠態懸浮液 存在著。因此，典型的造紙方法條件，如流體動力和機械 剪切力以及溫度和化學環境及平衡的急劇變化，可能導致 膠態木瀝青粒子在纖維素懸浮液中黏聚或沈積在漉網或其 它設備的表面上。此可能導致成品的品質缺陷，如形成點 或孔及品質差的紙表面，及縮短的設備壽命、可運轉的時 間、造紙機停機時間及最後紙廠的利潤損失。在具有高含 篁製程水閉合，如大量的白水循環之造紙廠中，這些問題 係被放大。 200426275 【發明内容】 本發明大體上係針對一種製造紙的方法，其包括： (i)提供一種含纖維素纖維的主水流； (π)將一或多種滯留成分導入該主水流内，以形成一 含有一或多種滯留成分的主水流； (iii) 提供一種稀釋用水流； (iv) 將低分子量陽離子有機聚合物導入該稀釋用水流 内，以形成一含有低分子量陽離子有機聚合物的稀釋用水 流，該低分子量陽離子有機聚合物具有最高5,〇〇〇,〇〇〇的 重量平均分子量； (V)將該含有低分子量陽離子有機聚合物的稀釋用水流 導入該含有一或多種滯留成分的主水流内，以形成一種生 成水流；及然後 (vi)將該生成水流喷射到漉網上及將該生成水流脫水 ’以形成紙幅。 本發明更針對一種在含有稀釋網前箱的造紙機上製造 紙的方法，其包括： (1)將一或多種滯留成分導入一含有纖維素纖維的主水 流内，及將所獲得的主水流送入該稀釋網前箱内； 、（ii)將一具有重量平均分子量最高為5,000,000的低 分子量陽離子有機聚合物導入一稀釋用水流内，及將所獲 得的稀釋用水流送入該稀釋網前箱内； (111)在網前箱内使所獲得的主水流混合所獲得的稀釋 用水流，以形成一種生成水流；及 200426275 (iv)將該生成水流喷射到漉網上及將該生成水流脫水 ’以形成紙幅。 本發明亦針對一種由含有纖維素纖維和視需要選用的 填料之水性懸浮液來製造紙的方法，其包括將一或多種滞 留成分導入懸浮液内，接著將具有重量平均分子量最高為 5, 〇〇〇, 000的低分子量陽離子有機聚合物導入懸浮液内， 及然後在漉網上形成及瀝乾懸浮液。 發明的詳細説明 依本發明，已經發現藉由在將原料於漉網上脫水以形 成紙巾田之刚’以特定的方式將添加劑導入該原料則可減少 木遞青問題。此發現亦特別有用於造紙方法，其中在具有 稀釋網則箱的造紙機上製造紙。亦已經發現依本發明可較 佳地控制造紙系統中木瀝青的沈積。更已經發現本發明的 方法係能製造具有改良特性的紙。 稀釋網前箱（di lution headbox)大體上可被敘述成一 種裝置，其包括至少一個第一部分體積流用入口、至少一 個第二部分體積流用入口、至少一個供混合該些部分體積 /爪以形成混合體積流的段、及至少一個供喷射該混合體積 流之出口。較宜地，該稀釋網前箱在橫過其之工作寬度上 包括數個該入口、段及出口。適合的稀釋網前箱之例子包 括美國專利號數 4, 909, 904、5, 196, 091、5, 316, 383、 5, 545, 293 及 5, 549, 793 中所揭示者。 本文中所用的術語「主水流」係指含纖維素纖維及視 需要選用的填料之主流，其在進入網前箱，具有高稠度（ 200426275 以下稱為HC)，即高固體含量，HC原料，因此代表高桐度 流（以下稱為HC流）。HC流的稠度範圍可為〇· 1至3· 5重 量％，適合地為〇· 3至2· 2重量％，且較佳為〇· 4至1· 9重 量％。本文中所用的術語「稀釋用水流」係指一種用於稀 釋HC流的水流，且其與HC流有關，係具有低稠度（lc)， 即低固體含量，LC原料，因此代表低稠度流（以下稱為Lc 流）。LC流的稠度範圍可為04.5重量％，適宜地為〇 〇〇2一 0.9重量％，且較佳為0.005-0· 8重量％，限制條件為Lc流 的稠度係低於HC流。較宜地，在網前箱内，jjc流係被Lc 流所混合及稀釋，例如在緊鄰擾流產生器之前，以形成一 種生成流，其排放到漉網上以便脫水。HC流對LC流的體 積比在99:1至50:50的範圍内，適宜地在97:3至6〇:4〇 的範圍内，較佳為在95: 5至75 :25的範圍内，且典型上約 85:15。如稀釋網前箱中所習知者，hc流和LC流的體積比 較佳係在橫過網前箱的寬度之數個點作變化，以便調整稀 釋量’俾能較佳的所形成的紙幅之基重截面。較宜地，部 分體積流，即HC流和LC流，係在網前箱中混合，以形成 一種生成HC/LC混合物體積流，其由網前箱被喷射出，且 其在橫機器方向係本質上恒定的。 稀釋用的LC水流可選自於新鮮水、白水及其它在製程 中循環的水流。該稀釋用的Lc流可能含有纖維細物及填料 ，且在將其送入網前箱之前可用任何純化步驟來處理它。 可用於純化或澄清這些類型水流的適合步驟之例子包括過 濾、浮選、沈降、厭氣及好氣處理。較宜地，L(：流係白水 200426275 ’其含有例如纖維素細⑯、萃取物&其它在碎漿過程中自. 木材所釋放出的材料，以及導人He流内但不保留在漉網上 的填料和添加劑。所用的白水較佳為藉由在漉網上將原料 及/或紙幅脫水而得到者’且其在送入稀釋網前箱之前可 如上述地被澄清。IX流通常具有不同於He流的組成。當 製程中使用填料時，LC流的填料含量通常不同於Hc流. LC流通常具有較高的填料含量，以該流而非以hc流的乾 物質百分率來表示。 除了如上述進入網前箱内的Hc流及Lc流，依本發明 籲 亦可至少一個進入網前箱的額外流。該額外流較佳為一種 含單獨水的流。該額外流亦為一種原料或紙漿流，其之稍 度及/或組成係不同於HC流。 依本發明所要導入HC流内的滯留成分為單一滞留劑或 一種滯留系統，例如任何以下所定義者。單一成分可為任 何具有滯留劑功能的成分，較佳為陽離子聚合物，例如本 文中所定義者。在此具體態樣中，導入主水流内的成分量 應足以得到一種滯留，其優於不添該成分者。 鲁 在本發明-較佳具體態樣中，使用一種滯留系統。本 文中所用的術語「滯留系統」係指二或多種成分或劑，其 當加到原料時’會得到優於不添該二或多種成分或劑者。 =留系統的成分較佳係選自於二或多種有機聚合物及一或 多種聚合物與鋁化合物及/或無機微粒子的組合。 在本發明的一較佳具體態樣中，使用一種微粒子滯留 系統。本文中所用的術語「微粒子滞留系統」係指一種滞 12 200426275 =統，其包括微粒狀材料，或微粒子，例如本文中所定 義的陰離子無機粒子、陽 .雕卞無機粒子及有機微粒子。料 1材料係與至少-種其它成分組合使用，通常至少一種 =合物’本文中亦稱為主聚合物，較佳為陽離子、兩 :二陰離子聚合物。陰離子微粒子較佳係與至少一種兩性 :或陽離子聚合物組合使用，但是陽離子微粒子較佳為 :至少-種兩性及/或陰離子聚合物組合使用。較宜地： U粒子係陰離子無機粒子。200426275 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for manufacturing paper, in which a papermaking additive is introduced into the fiber before a cellulose raw material is sprayed from a headbox onto a gauze to form a paper web. Vegetarian ingredients inside. [Prior art] In the papermaking technology, an aqueous suspension (called a raw material) containing cellulose fibers, optional fillers and additives is sent into a net front box, which sprays the raw materials to a Forming cymbals online. Water is discharged from the raw materials, and the paper web is formed on the web, and the paper web is dewatered and dried in the drying section of the paper machine. Retentive agents are usually introduced into the raw materials to increase the adsorption of particles such as fine particles and filler particles to the cellulose fibers so that they are retained by the fibers on the gauze. A wide variety of retention agents are known in the art, and examples thereof include anionic, nonionic, amphoteric, and cationic organic polymers, inorganic materials, and combinations thereof of different molecular weights. Due to incomplete retention, the water obtained by dewatering the raw material and the wet paper web is called white water, which contains fine particles that do not remain on the flooding net, and this white water is usually circulated in different flow circuits. In a paper machine having a dilute screen front box, white water is used to dilute the raw materials in the front stage of the screen. Thereby, a high-consistency fluid is diluted with a low-consistency fluid originating from white water. The net front box has a series of mixing sections or dilution lines distributed across the width of the net 200426275 front box. The white water system is injected into the mixing section to locally control the dilution of the raw materials, thereby forming a variable consistency profile, which leaves the weir plate gap at a fixed volume flow rate. The dilution net front box design provides better control of the paper characteristics; by adjusting the dilution amount, that is, the ratio of high consistency fluid to low consistency fluid at several points across the dilution net front box of the machine, the Improved way to control the basis weight of the paper web and make the cost uniform in quality in the cross machine direction. However, it is clear that when using high-performance retention agents, the papermaking method and the properties of the paper produced have not been fully satisfactory and have been attributed to improper pitch deposition control of the wood. The problems caused by the accumulation of wood pitch on paper machines and the formation of pitch balls in the final paper in the manufacture of various papers have been previously recognized. Wood pitch usually refers to emulsified hydrophobic organic compounds. Wood pitch can be defined as a sticky, resinous material that is released from the wood during the pulping process. Wood pitch also includes sticky substances, such as additives, that originate from coated waste paper and recycled fibers, and are often referred to as stickies or stickies. In the paper mill process water, wood pitch exists as a colloidal suspension of unstable, hydrophobic particles. As a result, typical papermaking process conditions, such as hydrodynamic and mechanical shear forces, and rapid changes in temperature and chemical environment and balance, can cause colloidal wood pitch particles to coalesce in cellulose suspensions or deposit on a gauze or other equipment on the surface. This can lead to quality defects in the finished product, such as formation of dots or holes and poor-quality paper surfaces, as well as shortened equipment life, operational time, paper machine downtime, and ultimately lost profit at the paper mill. These problems are magnified in paper mills with high tritium-containing process water closures, such as a large number of white water cycles. 200426275 [Summary of the Invention] The present invention is generally directed to a method for manufacturing paper, which includes: (i) providing a main stream containing cellulose fibers; (π) introducing one or more retention components into the main stream to form A main water stream containing one or more retention ingredients; (iii) providing a dilution water stream; (iv) introducing a low molecular weight cationic organic polymer into the dilution water stream to form a low molecular weight cationic organic polymer for dilution Water flow, the low molecular weight cationic organic polymer has a weight average molecular weight of up to 5,000, 000; (V) introducing the dilute water flow containing the low molecular weight cationic organic polymer into the one or more retention components Within the main water stream to form a generated water stream; and (vi) spraying the generated water stream onto a grate and dewatering the generated water stream to form a paper web. The present invention is further directed to a method for manufacturing paper on a paper machine including a dilute net front box, which comprises: (1) introducing one or more retention components into a main stream containing cellulose fibers, and introducing the main stream obtained Sent into the box before the dilution net; (ii) introducing a low molecular weight cationic organic polymer having a weight average molecular weight of up to 5,000,000 into a dilution water stream, and sending the obtained dilution water stream before the dilution net Inside the box; (111) mixing the obtained main water stream in the net box to obtain the diluted water stream to form a generated water stream; and 200426275 (iv) spraying the generated water stream onto the grate and the generated water stream Dewatering 'to form a paper web. The present invention is also directed to a method for making paper from an aqueous suspension containing cellulose fibers and optional fillers, which comprises introducing one or more retention ingredients into the suspension, and then introducing a weight average molecular weight of up to 5,0. A low molecular weight cationic organic polymer of 0.000 is introduced into the suspension, and then the suspension is formed and drained on a gauze screen. DETAILED DESCRIPTION OF THE INVENTION According to the present invention, it has been found that the problem of wood greening can be reduced by introducing additives into the material in a specific manner by dehydrating the material on a gauze net to form a paper towel field. This finding is also particularly useful in papermaking processes where paper is made on a paper machine with a dilute mesh box. It has also been found that the deposition of wood pitch in papermaking systems can be better controlled according to the present invention. It has further been found that the method of the present invention is capable of producing paper with improved characteristics. The dilution headbox can be generally described as a device that includes at least one inlet for first partial volume flow, at least one inlet for second partial volume flow, and at least one partial volume / claw for mixing to form a mixture A section of the volume flow and at least one outlet for spraying the mixed volume flow. Preferably, the dilution net front box includes a plurality of the inlets, sections and outlets across its working width. Examples of suitable dilution net front boxes include those disclosed in U.S. Patent Nos. 4,909,904, 5,196,091,5,316,383, 5,545,293, and 5,549,793. The term "main stream" as used herein refers to the mainstream of cellulose fibers and optional fillers, which have high consistency (200426275 hereinafter referred to as HC) when they enter the front net box, that is, high solid content, HC raw materials, Therefore, it represents a high degree flow (hereinafter referred to as HC flow). The consistency of the HC stream may range from 0.3 to 3.5% by weight, suitably from 0.3 to 2.2% by weight, and preferably from 0.4 to 1.9% by weight. As used herein, the term "diluted water stream" refers to a water stream used to dilute the HC stream, and it is related to the HC stream and has a low consistency (lc), that is, a low solid content, LC raw material, and therefore represents a low consistency stream ( Hereinafter referred to as Lc flow). The consistency of the LC stream can range from 0.45% by weight, suitably from 0.002 to 0.9% by weight, and preferably from 0.005 to 0.8% by weight. The limitation is that the consistency of the Lc stream is lower than the HC stream. Preferably, in the net box, the jjc stream is mixed and diluted by the Lc stream, for example, immediately before the turbulence generator to form a generated stream, which is discharged onto the grate net for dehydration. The volume ratio of HC stream to LC stream is in the range of 99: 1 to 50:50, suitably in the range of 97: 3 to 60:40, preferably in the range of 95: 5 to 75:25. , And typically about 85:15. As is known in the dilution net front box, the volume of the hc stream and the LC stream is better because the number of points across the width of the net box is changed in order to adjust the dilution amount to better form the paper web. The basis weight section. Preferably, part of the volume flow, that is, HC flow and LC flow, is mixed in the front net box to form a volume flow generating HC / LC mixture, which is ejected from the front net box, and it is in the transverse machine direction. Essentially constant. The LC water stream for dilution can be selected from fresh water, white water, and other water streams circulating in the process. The diluted Lc stream may contain fiber fines and fillers, and it can be processed by any purification step before sending it to the pre-net box. Examples of suitable procedures that can be used to purify or clarify these types of streams include filtration, flotation, sedimentation, anaerobic, and aerobic treatment. More suitably, L (: streamlined white water 200426275 'contains, for example, cellulose fines, extracts & other materials released from wood during the pulping process, and leads into the flow of He but does not remain in the water. Fillers and additives on the web. The white water used is preferably obtained by dewatering the raw materials and / or paper web on the web, and it can be clarified as described above before being sent to the dilution net front box. The IX stream is usually Has a composition different from the He stream. When fillers are used in the process, the filler content of the LC stream is usually different from the Hc stream. The LC stream usually has a higher filler content, expressed as the dry matter percentage of the stream rather than the hc stream In addition to the Hc flow and Lc flow entering the net front box as described above, according to the present invention, at least one additional stream entering the net front box is also possible. The additional stream is preferably a stream containing separate water. The additional stream is also A raw material or pulp stream having a slightly different and / or composition different from the HC stream. The retention component to be introduced into the HC stream according to the present invention is a single retention agent or a retention system, such as any of the following definitions. A single component may For anyone with a lag The component of the agent function is preferably a cationic polymer, such as defined herein. In this specific aspect, the amount of the component introduced into the main stream should be sufficient to obtain a retention, which is better than those without the component. Lu Zai In the present invention-a preferred embodiment, a retention system is used. As used herein, the term "retention system" refers to two or more ingredients or agents that, when added to a raw material, will be better than no two or more Ingredients or agents. = The components of the retention system are preferably selected from the group consisting of two or more organic polymers and one or more polymers with aluminum compounds and / or inorganic microparticles. In a preferred embodiment of the present invention A microparticle retention system is used. The term "microparticle retention system" as used herein refers to a type of retention 12 200426275 = system, which includes particulate materials, or microparticles, such as anionic inorganic particles, yang.carved inorganic as defined herein. Particles and organic microparticles. Material 1 is used in combination with at least one other component, usually at least one compound. Also referred to herein as the main polymer, preferably cationic Two: two anionic polymers. Anionic fine particles are preferably used in combination with at least one amphoteric: or cationic polymer, but cationic fine particles are preferably used in combination with at least one amphoteric and / or anionic polymer. More suitably: U The particles are anionic inorganic particles.
態範圍"留系統，係在粒度的膠 尺认 ，、了為二_或四-成分滞留系統。該適 :的額外成分例如包括銘化合物及低分子量陽離子有機聚 °物。通常’滯留系統’包含微粒子滞留系統，亦得到比 不添加該成分時較佳的脫水，而且該系統—般被稱為滞留 及脫水系統。The state range " retention system is tied to the size of the rubber scale, which is a two- or four-component retention system. The suitable additional components include, for example, compounds and low molecular weight cationic organic polymers. Often the 'retention system' contains a particulate retention system, which also results in better dehydration than when this component is not added, and this system is commonly referred to as a retention and dehydration system.
在本發明的另-較佳具體態樣中，使用一種滞留系统 ’其包括-或多種陽離子有機聚合物及一或多種陰離子有 機聚合物。適宜地，該滯留系統包括一具有一或多個芳基 的陽離子有機聚合物及/或—具有—或多個芳基的陰離二 有機聚合物，如本文中所定義。 依本發明所用的陰離子無機粒子包括陰離子石夕石系粒 子及綠土型黏土。較宜使㈣離切^粒子，即基於 Si〇2或輕的粒子，包括膠詩石及*同_的聚石夕酸和 聚矽酸鹽。陰離子矽石系粒子通常係以水性膠態分散液來 供應，即所謂的溶膠。依本發明適合的⑦石系溶膠亦可含 13 200426275 有其它元素，例如氮、鋁及硼。該元素可以使用分別含氮 有機化合物、含鋁化合物及含硼化合物的改質形式存在著 。這些化合物可存在水性溶膠及/或矽石系粒子中。含適 當陰離子石夕石粒子的滯留及脫水系統係揭示於美國專利號 數 4, 388, 150、4, 927, 498、4, 954, 220、4, 961，825、 4,980,025、5，127,994、5，176,891、5,368,833、 5,447,604、5,470,435、5,543,014、5,571,494、 5’ 584’ 966、5’ 603, 805 及 6, 379, 500 中，它們以引用方式 納入本文中。 適合的陰離子石夕石系粒子具有平均粒度低於約50nm， 較佳為低於約2〇nm，且更佳為在約！至約1()nm的範圍内 。如_石化學中所習知者’粒度係、指初級粒子的平均大小 其可為聚集的或非聚集的。矽石系粒子的比表面積適宜 地係50m /g以上，較佳1〇〇m2/g以上。通常，比表面積最 高為約n_vg，讀佳最高$ 1〇〇〇m2/g。以已知的方式 用Na〇H滴疋的方式，例如Se㈣在Analytic Chemistry (1 956).12, 1981-1983 及美國專利第 5，176,891 號中所 =在適*地移除或調整樣品中所存在的之可能干擾滴 ”任何疋素或化合物如鋁和硼物後，測量比表面積。所 付到的面積因此代表粒子的平均比表面積。 在本發明的一較佳且 〃體態樣中，陰離子無機粒子係矽 石糸粒子，其具有比表 鲈杜1nn 積在5〇至100〇m2/g的範圍内， 較佳100至950m2/g。輕眘认认 ^ ^ ^ m # ，陰離子無機粒子係存在於矽 石糸洛膠中，其之s值係 ’、 至45/0的範圍内，較佳1〇至 200426275 35%，含有比表面積在3〇〇至1〇〇〇mVg範圍内的矽石系粒 子，適宜地在500至950mVg的範圍，該粒子可為非經鋁 改質或經鋁改質者，適合地為表面經鋁改質者。s值的測 量及計算係如 Iler & J· Phys· Chem· 60(1956)，955-957 中所述。s值表示聚集或微凝膠形成程度，且較低的s值 係表示較高的聚集度。 在本發明又另一較佳具體態樣中，陰離子無機粒子係 選自於聚矽酸，視需要與鋁反應，具有高的比表面積，適 合地為在約l〇〇〇mVg以上。比表面積在1〇〇〇至17〇〇m2/g · 的範圍内，較佳為1〇50至1 600mvg。在技藝中，聚矽酸亦 稱為聚合矽酸、聚矽酸微凝膠、聚矽酸鹽及聚矽酸鹽微凝 膠’它們皆涵蓋在本文中所用的術語聚矽酸之内。含紹的 聚矽酸通常稱為聚矽酸鋁及聚矽酸鋁微凝膠，它們皆涵蓋 在本文中所用的術語聚矽酸之内。 本發明之方法中所可用的綠土型黏土係技藝中已知者 且包括天然發生、合成及經化學處理的材料。適合的綠土 黏土之例子包括蒙脫土 /膨土、水輝石、貝得石、囊脫石 馨 及滑石粉，較佳為膨土，尤其是在潤脹後較佳為具有表面 積為400至800m2/g者。適合的黏土係揭示於美國專利號 數 4, 753, 710、5, 071，512 及 5, 607, 552 中，它們以引用方 式納入本文中，後者專利揭示陰離子矽石系粒子及綠土黏 土的，較佳為天然膨土。可用的陽離子無機粒子包括陽離 子石夕石系粒子、陽離子氧化鋁及陽離子氧化锆。 依本發明適用當作滯留劑或滞留系統的一部分之有機 15 200426275 聚合物為陰離子性、非離子性、兩性或陽離子性，它們可 得自天然或合成源，且它們可為線型、分枝或交聯，例如 微粒子形式。較宜地，聚合物係水溶性或水可分散性。 適合的陽離子聚合物之例子包括陽離子多醣，例如澱 粉、瓜耳膠、纖維素、幾丁質、幾丁聚糖、聚醣、聚半^ 糖、聚葡萄糖、黃原酸膠、果膠、聚甘露糖、糊精，較佳 為澱粉及瓜耳膠，適合的澱粉包括馬鈴薯、玉米、小麥、 ^薯、稻米、糯玉米、大麥等；陽離子合成有機聚合物如 陽離子鏈生長聚合物，例如陽離子乙烯系加成聚合物，如 丙烯酸酯-、丙烯醯胺-、乙烯胺―、乙烯醯胺—及烯丙基胺 系聚合物，及陽離子逐步生長聚合物，例如陽離子聚醯胺 基胺、聚乙烯醯亞胺、聚胺及聚胺甲酸酯。陽離子澱粉及 陽離子丙烯醯胺系聚合物係特佳的陽離子聚合物，兩者當 作單一滯留成分以及在滯留系統中，有或無陰離子無機粒 子。適合的具有一或多個芳基的陽離子有機聚合物之例子 包括W0 02/12626中揭示者。陽離子有機聚合物的重量平 均分子量在寬廣範圍内變化，尤其取決於所用的聚合物類 型’且其通常在2,0〇〇,〇〇〇以上，更常為在3 〇〇〇 00〇以 上’適合地為在5, 000, 〇〇〇以上。上限係未嚴格要求的； 其可為約600,〇〇〇,〇〇〇，通常15〇,〇〇〇 〇〇〇，且適合地為 1〇〇, 000, 000 〇 依本發明可導入HC流内的更適合陽離子聚合物之例子 包括具有低分子量的陽離子有機聚合物。該陽離子有機聚 合物包括通常稱為陽離子廢物補捉劑（以下稱為atc)〇atc 200426275 陽離子有機聚合物的重量平均分子量通常為至少2, 〇〇〇， 適合地為至少10,000，且較佳至少50,000，且其通常為最 高2,000,000，及常常最高1，500,000。適合的ATC包括線 型、分枝及交聯聚合物，通常係高度帶電的，其可得自天 然及合成源。適合的ATC例子包括低分子量降解之多醣， 例如基於澱粉、瓜耳膠、纖維素、幾丁質、幾丁聚糖、聚 醣、聚半乳糖、聚葡萄糖、黃原酸膠、果膠、聚甘露糖、 糊精，較佳為殿粉及瓜耳膠，適合的澱粉包括馬鈴薯、玉 米、小麥、木薯、稻米、糯玉米、大麥等；陽離子合成有 機聚合物如陽離子鏈生長聚合物，例如陽離子乙烯系加成 聚合物，如丙烯酸酯-、丙烯醯胺_、乙烯胺_、乙烯醯胺— 及稀丙基胺系聚合物，例如基於二稀丙基二烧基齒化敍的 均-和共聚物，例如基於二烯丙基二甲基氣化銨者，以及（ 曱基）丙浠醯胺及（甲基）丙稀酸醋；及陽離子逐步生長聚合 物，例如陽離子聚醯胺基胺、聚乙稀亞胺、聚胺，例如二 甲基胺-¾氧氣丙烷共聚物及聚胺甲酸酯。 依本發明適合的陰離子有機聚合物之例子選自於逐步 生長聚口#、鏈生長聚合物、聚醣、天然發生芳族聚合物 及其改質物。適合的陰離子逐步生長聚合物之例子包括降 及基於萘的縮合聚合物，較佳為基於萘-料 二：一鹽的縮合聚合物；及加成聚合物，即藉由逐 ' :加成聚合所得到的聚合物，例如陰離子聚胺甲酸醋 成ίίΓ離子鍵生長聚合物之例子包括陰離子乙烯系加 物，例如丙埽酸醋'及丙婦酿胺系聚合物，並包括 17 200426275 陰離子或潛在陰離子單體，如（甲基）丙烯酸及對乙烯基酚（ 經基苯乙烯）。依本發明，適合的天然發生芳族聚合物及 其改質之例子，即經改質的天然發生芳族陰離子聚合物， 係包括基於木質素的聚合物，較佳為磺化木質素，例如木 貝素％酸鹽、牛皮紙木質素、磺化牛皮紙木質素及單寧萃 取物。其它適合的具有-或多個芳基的陰離子有機聚合物 之例子係包括W〇〇2/12626中所揭示者。陰離子聚合物的 重量平均分子量在寬廣制内變化，《其取決於所用的聚 合物類型，且其通常至少約5〇〇，適合地在約2 〇〇〇以上 ，且較佳為在約5, 000以上。上限係未嚴格要求的丨其可 為約600’000, 〇〇〇，通常150, 〇〇〇, 〇〇〇，適合地為 100，〇〇〇,〇〇〇，且較佳為 10，〇〇〇,〇〇〇。 本文中所用的術語「逐步生長聚合物」係指一種由逐 步生長聚合所得到的聚合物，亦分別稱為逐步反應聚合物 及逐步反應聚合。本文中所用的術語「鍵生長聚合物」係 指-種由鏈生長聚合所得到㈣合物，亦分別稱為鍵反應 聚合物及鏈反應聚合。 依本發明所可用的紹化合物係包括明装、紹酸鹽、氣 化銘、硝酸I呂及聚氯化銘、聚硫酸銘、含氣和硫酸=離子 的聚鋁化合物、聚鋁矽酸鹽_硫酸鹽，及其混合物。聚鋁 化合物亦可含有其它陰離子，例如來自磷酸、硫酸、有機 酸如檸檬酸和草酸的陰離子。 依本發明較佳的滞留系統包括·· (1)陰離切石系粒子與陽離子殿粉、陽離子瓜耳膠或 18 視需要可與ATC及/或|呂 陽離子丙烯醯胺系聚合物的組合 化合物組合； (i i )陰離子石夕石系粒子 較佳為陰離子丙烯醯胺系 /或ATC的組合； 與陰離子鏈生長聚合物的組合 聚合物與陽離子有機聚合物及 ATC=)膨土與陽離子丙婦酿胺系聚合物，視需要可盘 ATC及/或鋁化合物組合； 一 :)陽離子聚醣，較佳陽離子殿粉，與陰離子逐步生 的組合，較佳為與陰離子萘系縮合聚合物 要可與ATC及/或鋁化合物組合； (V) 陽離子㈣’較佳陽離切粉，與天然發生芳族陰 離子聚合物及其改質物的組合，較佳料 要可與ATC及/或紹化合物組合； (VI) 陽離子鏈生長聚合物，較佳陽離子丙烯醯胺系聚 :物’與陰離子逐步生長聚合物的組合，較佳為與陰離子 奈糸縮合聚合物"見需要可與ATC及/或銘化合物組合； (vii)陽離子鏈生長聚合物’較佳陽離子丙稀酿胺系聚 口物與天然、發生芳族陰離子聚合物及其改質物的組合， 較佳與續化木質素，視需要可與ATC及化合物組合； (..i)陽離子鏈生I聚合&，較4圭陽離I丙稀醯胺系 聚合物，與ATC的組合。 在本發明的方法中，滯留成分係被導入Η。流内，該流 將要與LC流混合，較佳為在網前箱内，藉以將成分導入稀 釋私序中的生成水流。當使用含有多於—種成分的滞留系 200426275 統時’可以傳統方式將該成分加到原#，較佳為在不同點 及以任何順序。當使用-含陰離子無機粒子和陽離子聚合 物的滯留系統時，較佳為在添加微粒狀材料之前，將陽離 子聚合物加到HC原料流’縱使可使用相反的添加順序。當 使用含有陽離子及陰離子有機聚合物的滞留系統時，較佳 為在添加陰離子聚合物之前’將陽離子聚合物加到HC原料 流，縱使可使用相反的添加順序。更佳為在剪切階段之前 ，其可選自於泵打、混合、清洗# ’添加第一成分，例如 陽離子聚合物，及在剪切階段之後’添加第二成分，例如 陰離子無機微粒子或有機聚合物。當使用低分子量陽離子 有機聚合物當# ATC時，較佳為在其它滞留成分之前或同 時地’導入HC原料流内。當使用鋁化合物時 它滯留成分之前或同時地，導人Hc原料流内。為在^、 曰滯留系統的成分係被導入原料内，其將被脫水 !可在寬廣的範圍内，尤其取決於成分的類型 料類型’填料類型，填料含量，添加點，等等。通常，$ 分的添加量係能得到比不添加成分時較佳的滞留。 ΓΤ無機聚合物當作微粒狀材料時，所添加的總：通： ‘D G.GG1重量％，常f至少請5重量％，此係 的乾物質重為基準。上限通常為h 〇· 6重量％。舍栋田^7 且適合地為 田使用陰離子矽石系粒子時，總量適人地仫+ 0.005至〇·5重量％内，此係 °係在 為基準，較佳為在二？ 2…係以乾原料物質 物，例如陽離子及阶 人重1%的範圍内。有機聚合 子及陰離子聚合物，通常的添加總量係至少 20 200426275 0.001重量％，常常至少n 為Α準。上"Λ ’此係以乾原料物質 為基卓上限通常為3重量％，且適合地為U重量％_ 使用低分子量陽離子有機聚合物當作ATC時，^ 料流内的量，以乾原料物質Λ 取 的量係在㈣至。5% :=係至少°.。1%，適合 田使用鋁化合物於製程時， 將要脫水的原料内之總㈣取決於所用的域合物 及其它來自彼的所欲效果。例如，技藝中眾所周知利用铭 化合物當作松香系施膠劑的沈殺劑。所添加的總 至少0.05%，此係以Al2〇3計算且係以乾原料物質為基準。 適合的量為在〇·〇8至2 8%的鉻1¥!如 * 的範糊乾圍内’較佳在^至⑽ 依本發明，低分子量陽離子有機聚合物係導入 HC流混合的LC流内’較佳為在稀釋網前箱中。適合的： 分子1(以下稱為LMW)陽離子有機聚合物包括線型、分枝 及交聯聚合物，通常為高度帶電#，其可衍生自天秋及人 成源。適合的LMW陽離子有機聚合物包括_降解聚醣： 例如基於殿粉、瓜耳膠、纖維素、幾丁質、幾丁聚糖、聚 酿、聚半乳糖、聚葡萄糖、黃原酸膠、果膠、聚甘露糖、 糊精’較佳為殿粉及瓜耳膠’適合的殿粉包括馬铃著、王 米：小麥、木薯、稻米、糯玉米、大麥等；㈣陽離子乙 烯糸加成聚合物，如丙烯酸酷_、丙烯酿胺_、乙稀胺_、乙 烯醯胺-及稀丙基胺系聚合物，例如基於二烯丙基二烷基 南化敍的均-和共聚物，例如基於二稀丙基二甲基氣化二 者，以及（甲基）丙稀醯胺及（甲基）丙稀酸酿；及陽離 21 200426275 子逐步生長聚合物，例如陽離子聚醯胺基胺、聚乙浠亞胺 、聚胺，例如二甲基胺-環氧氣丙烷共聚物及聚胺甲酸酯 。LMW陽離子有機聚合物的重量平均分子量通常為至少 100,000，適合地為至少500,〇〇〇,及較佳至少1〇〇〇 〇〇〇 ，且其通常最高5, 000, 000，適合地最高3, 〇〇〇〇〇〇，且較 佳最高2, 〇〇〇, 000。通常，在將陽離子有機聚合物加到HC 流中當作滞留劑或滯留系統的一部分之情況中，加到流 的LMW陽離子有機聚合物之重量平均分子量係低於加到此 流的陽離子有機聚合物者。 加到LC流的LMW陽離子有機聚合物之量，以要被脫水 的原料之乾物質為基準，係至少〇〇1%。適合地，該量係 在0.05至1.0%的範圍内，較佳在〇1至〇·5%的範圍内。 在本發明的較佳具體態樣中，在將含LMW陽離子有機 聚合物的LC流導入含一或多種滞留成分的Hc流内以形成 生成水流後，沒有其它滯留成分導入該生成水流中。該生 成水流的形成較佳係發生在稀釋網前箱中，但是亦可發生 在網前箱外部。 ^本發明的方法亦可適用於所有的造紙方法及纖維素懸 洋液，且其特別有用於由具有高導電度的原料來製造紙中 在/凊況中，在渡網上被脫水的原料之導電度通常係至 5.〇mS/cm〇In another-preferred embodiment of the present invention, a retention system is used which comprises-or more cationic organic polymers and one or more anionic organic polymers. Suitably, the retention system comprises a cationic organic polymer having one or more aryl groups and / or—anionic di-organic polymers having—or more aryl groups, as defined herein. The anionic inorganic particles used in accordance with the present invention include anionic stone-stone particles and smectite-type clay. It is more suitable to separate particles, that is, particles based on SiO 2 or light, including colloidal stones and polystyrosine and polysilicates. Anionic silica-based particles are usually supplied as an aqueous colloidal dispersion, a so-called sol. The vermiculite-based sol suitable according to the present invention may also contain other elements such as nitrogen, aluminum and boron. This element can exist in modified forms of nitrogen-containing organic compounds, aluminum-containing compounds, and boron-containing compounds. These compounds may be contained in an aqueous sol and / or silica-based particles. Retention and dehydration systems containing appropriate anionite particles are disclosed in U.S. Patent Nos. 4,388,150, 4,927,498, 4,954,220, 4,961,825, 4,980,025, 5,127,994,5 , 176,891, 5,368,833, 5,447,604, 5,470,435, 5,543,014, 5,571,494, 5 '584' 966, 5 '603, 805, and 6, 379, 500, which are incorporated herein by reference. Suitable anionic lithocene-based particles have an average particle size of less than about 50 nm, preferably less than about 20 nm, and more preferably about 100 nm! To about 1 () nm. The particle size system, as is known in petrochemicals, refers to the average size of primary particles, which may be aggregated or non-aggregated. The specific surface area of the silica-based particles is preferably 50 m / g or more, and preferably 100 m2 / g or more. Generally, the specific surface area is at most about n_vg, and the best reading is at most $ 1000m2 / g. In a known manner, Na 疋 H is used to drip the tritium, for example, Se㈣ in Analytical Chemistry (1 956). 12, 1981-1983 and U.S. Patent No. 5,176,891 = in the proper removal or adjustment of the sample The specific surface area is measured after the presence of any interfering elements or compounds such as aluminum and boron. The area paid therefore represents the average specific surface area of the particles. In a preferred aspect of the invention, Anionic inorganic particles are silica gadolinium particles, which have a product range of 50 to 100 m2 / g, preferably 100 to 950 m2 / g, than that of surface perchlor dunnin. Recognize carefully ^ ^ ^ m #, anionic inorganic The particle system exists in silica gel, and its s value is in the range of 45 to 0, preferably 10 to 200426275 35%, and the specific surface area is in the range of 300 to 1,000 mVg. The silica-based particles are suitably in the range of 500 to 950 mVg. The particles may be those not modified by aluminum or modified by aluminum, and suitably those modified by aluminum on the surface. The measurement and calculation of the s value are such as Iler & J. Phys. Chem. 60 (1956), 955-957. The s value indicates the degree of aggregation or microgel formation And a lower s value indicates a higher degree of aggregation. In yet another preferred embodiment of the present invention, the anionic inorganic particles are selected from the group consisting of polysilicic acid, which reacts with aluminum as needed, and has a high specific surface area. Suitably it is above about 1000 mVg. The specific surface area is in the range of 1,000 to 1700 m2 / g ·, preferably 1050 to 1 600 mvg. In the art, polysilicic acid is also known as Polymeric silicic acid, polysilicic acid microgels, polysilicates, and polysilicate microgels are all encompassed within the term polysilicic acid as used herein. Polysilicic acids containing these materials are often referred to as Both aluminum silicate and polyaluminum silicate microgels are encompassed by the term polysilicic acid as used herein. The smectite-type clay-based techniques useful in the method of the present invention are known and include naturally occurring, Synthetic and chemically treated materials. Examples of suitable smectite clays include montmorillonite / bentonite, hectorite, beidellite, cystite, and talc, preferably bentonite, especially after swelling Those having a surface area of 400 to 800 m2 / g are preferred. A suitable clay system is disclosed in U.S. Patent No. 4,75 3, 710, 5, 071, 512, and 5, 607, 552, which are incorporated herein by reference. The latter patent discloses anionic silica particles and smectite clay, preferably natural bentonite. Cationic inorganics that can be used The particles include cationic stone-based particles, cationic alumina, and cationic zirconia. Organics suitable for use as a retentant or part of a retention system according to the present invention 15 200426275 The polymers are anionic, nonionic, amphoteric, or cationic, and they They can be obtained from natural or synthetic sources and they can be linear, branched or crosslinked, for example in the form of microparticles. Preferably, the polymer is water-soluble or water-dispersible. Examples of suitable cationic polymers include cationic polysaccharides, such as starch, guar, cellulose, chitin, chitosan, glycan, polysaccharides, polydextrose, xanthan gum, pectin, polysaccharide Mannose, dextrin, preferably starch and guar gum. Suitable starches include potato, corn, wheat, potato, rice, waxy corn, barley, etc .; cationic synthetic organic polymers such as cationic chain growth polymers, such as cationic Ethylene-based addition polymers, such as acrylate-, acrylamide-, vinylamine-, vinylamine-, and allylamine-based polymers, and cationic step-growth polymers, such as cationic polyamidoamine, polymer Ethyleneimine, polyamines and polyurethanes. Cationic starches and cationic acrylamide polymers are particularly good cationic polymers. Both serve as a single retention component and in the retention system, with or without anionic inorganic particles. Examples of suitable cationic organic polymers having one or more aryl groups include those disclosed in WO 02/12626. The weight average molecular weight of the cationic organic polymer varies over a wide range, especially depending on the type of polymer used 'and it is usually above 20,000, and more often above 30,000' Suitably it is above 5,000, 000. The upper limit is not strictly required; it may be about 600,000,000,000, usually 150,000,000, and suitably 100,000,000,000. HC may be introduced according to the present invention Examples of more suitable cationic polymers in the stream include cationic organic polymers having a low molecular weight. The cationic organic polymer includes what is commonly referred to as a cationic waste catcher (hereinafter referred to as atc). 00atc 200426275 The weight average molecular weight of the cationic organic polymer is usually at least 2,000, suitably at least 10,000, and preferably at least 10,000. 50,000, and it is usually up to 2,000,000, and often up to 1,500,000. Suitable ATC include linear, branched, and crosslinked polymers, which are usually highly charged, and are available from natural and synthetic sources. Examples of suitable ATC include low molecular weight degraded polysaccharides, such as based on starch, guar, cellulose, chitin, chitosan, glycan, polygalactose, polydextrose, xanthan gum, pectin, polysaccharide Mannose, dextrin, preferably gluten flour and guar gum. Suitable starches include potatoes, corn, wheat, cassava, rice, waxy corn, barley, etc .; cationic synthetic organic polymers such as cationic chain growth polymers, such as cationic Ethylene-based addition polymers, such as acrylate-, acrylamide-, vinylamine-, vinylamine- and di-propylamine-based polymers, such as homo- and Copolymers, such as those based on diallyldimethyl ammonium vapor, and (fluorenyl) propanamide and (meth) acrylic acid; and cationic step-growth polymers, such as cationic polyamidoamine , Polyethyleneimine, polyamines, such as dimethylamine-¾oxypropane copolymer and polyurethane. Examples of suitable anionic organic polymers according to the present invention are selected from the group consisting of step-growth polymers, chain-growth polymers, glycans, naturally-occurring aromatic polymers and modifications thereof. Examples of suitable anionic step-growth polymers include naphthalene-based and naphthalene-based condensation polymers, preferably naphthalene-material 2: a salt-based condensation polymer; and addition polymers, i.e. Examples of the resulting polymers, such as anionic polyurethanes growing into ΓΓ ion bond growth polymers, include anionic vinyl adducts, such as propionate and propylamine polymers, and include 17 200426275 anionic or potential Anionic monomers, such as (meth) acrylic acid and p-vinylphenol (terephthalene). Examples of suitable naturally occurring aromatic polymers and modifications thereof according to the present invention, namely modified naturally occurring aromatic anionic polymers, include lignin-based polymers, preferably sulfonated lignin, such as Lignin, salt, kraft paper lignin, sulfonated kraft paper lignin, and tannin extract. Examples of other suitable anionic organic polymers having one or more aryl groups include those disclosed in WO2 / 12626. The weight-average molecular weight of the anionic polymer varies within a wide range, "It depends on the type of polymer used, and it is usually at least about 500, suitably above about 2000, and preferably about 5, 000 or more. The upper limit is not strictly required. It may be about 600,000, 000, usually 150,000,000, 100,000, suitably 100,000,000, and preferably 10,000. 〇〇, 〇〇〇. As used herein, the term "step-growth polymer" refers to a polymer obtained by step-growth polymerization, also referred to as a step-reaction polymer and a step-reaction polymerisation, respectively. The term "bond-growth polymer" as used herein refers to a kind of adduct obtained by chain-growth polymerization, which is also called a bond-reactive polymer and a chain-reaction polymer, respectively. The compounds which can be used according to the present invention include surface coating, salt, gasification, nitric acid, polychlorination, polysulfate, polyaluminum compounds containing gas and sulfuric acid = ions, polyaluminosilicate_sulfuric acid. Salt, and mixtures thereof. Polyaluminum compounds may also contain other anions such as those from phosphoric acid, sulfuric acid, organic acids such as citric acid and oxalic acid. The preferred retention system according to the present invention includes ... (1) Anionic cut-stone particles and cationic powder, cationic guar gum, or 18 A compound that can be combined with ATC and / or Combinations; (ii) anionic stone sulphite-based particles are preferably a combination of anionic acrylamide-based and / or ATC; combined polymers with anionic chain-growth polymers and cationic organic polymers and ATC =) bentonite and cationic acrylic Ammonia-based polymers can be combined with ATC and / or aluminum compounds if necessary; a :) cationic glycans, preferably cationic powder, and anionic stepwise combination, preferably with anionic naphthalene-based condensation polymers Combined with ATC and / or aluminum compounds; (V) Cationic ㈣ 'is preferably a combination of positive ion cutting powder and naturally-occurring aromatic anionic polymer and its modification, preferably it can be combined with ATC and / or Shao compounds (VI) A cationic chain growth polymer, preferably a combination of a cationic acrylamide-based polymer and an anionic step-growth polymer, preferably with an anionic naphthalene condensed polymer " if necessary, can be combined with ATC and / or Minghuahe (Vii) cationic chain growth polymer 'preferably a combination of a cationic acrylamine polymer and a natural, aromatic anionic polymer and a modification thereof, preferably with a continuous lignin, if necessary, Combination with ATC and compounds; (..i) Cationic chain polymerization I & In the method of the present invention, the retentate component is introduced into the tritium. Within the stream, the stream is to be mixed with the LC stream, preferably in a net box, to introduce the components into the dilute private sequence to generate the water stream. When using a retention system containing more than one ingredient, 200426275, the ingredients can be added to the original # in a conventional manner, preferably at different points and in any order. When using a retention system containing anionic inorganic particles and cationic polymers, it is preferred to add the cationic polymer to the HC feed stream 'before adding the particulate material, even though the reverse order of addition can be used. When a retention system containing a cationic and anionic organic polymer is used, it is preferred that the cationic polymer is added to the HC feed stream before the anionic polymer is added, even though the reverse order of addition may be used. More preferably, it can be selected from pumping, mixing, and washing before the shearing phase. 'Add a first component, such as a cationic polymer, and after the shearing phase,' add a second component, such as anionic inorganic particles or organic polymer. When using a low molecular weight cationic organic polymer #ATC, it is preferred to be introduced into the HC feed stream before or at the same time as the other retention components. When an aluminum compound is used, it is introduced into the Hc feedstream before or at the same time as the ingredients. In order to introduce the ingredients of the retention system into the raw materials, it will be dehydrated! It can be in a wide range, especially depending on the type of ingredients, material type, filler type, filler content, addition point, etc. In general, the amount of $ cents added will result in better retention than when no ingredients are added. When the ΓΤ inorganic polymer is used as a particulate material, the total amount added is: ‘D G.GG1% by weight, and at least 5% by weight is often required. The dry matter weight of this system is used as a reference. The upper limit is usually h 0.6 weight%. When using anionic silica-based particles in Shedongtian ^ 7 and suitably Tian, the total amount is within a reasonable range of + 0.005 to 0.5% by weight. This system is based on, preferably two? 2 ... is in the range of 1% by weight of dry raw materials such as cations and humans. Organic polymers and anionic polymers are usually added in a total amount of at least 20 200426275 0.001% by weight, and often at least n is A. The upper limit is based on dry raw materials. The upper limit is usually 3% by weight and suitably U% by weight. _ When using low molecular weight cationic organic polymers as ATC, the amount in the stream is dry. The amount of raw material Λ is taken from ㈣ to. 5%: = is at least °. 1%, suitable for the use of aluminum compounds in the process, the total content of the raw materials to be dehydrated depends on the domain compound used and other desired effects from them. For example, it is well known in the art to use a compound as a killer for a rosin-based sizing agent. The total amount added is at least 0.05%, which is calculated based on Al203 and based on dry raw material. A suitable amount is within the range of 0.08 to 28% of chromium 1 ¥! Such as * within the range of the standard paste, preferably ^ to ^ According to the present invention, a low molecular weight cationic organic polymer is introduced into the HC stream to mix the LC In-stream 'is preferably in a dilute mesh front box. Suitable: Molecules 1 (hereinafter referred to as LMW) cationic organic polymers include linear, branched, and crosslinked polymers, which are usually highly charged #, which can be derived from Tianqiu and human sources. Suitable LMW cationic organic polymers include degradable glycans: for example, based on powder, guar, cellulose, chitin, chitosan, polysaccharides, polygalactose, polydextrose, xanthan gum, fruit Gum, polymannose, dextrin are preferably Dian Fan and Guar Gong. Suitable Dian Fan include Ma Lingzhu, Wang Mi: wheat, cassava, rice, waxy corn, barley, etc .; cationic ethylene, addition polymerization Polymers such as acrylic acid, acrylic acid, ethyleneamine, vinylamine, and dipropylamine polymers, such as homo- and copolymers based on diallyldialkylsynthesis, such as Based on both dimethyl dimethyl gasification, and (meth) acrylamidine and (meth) acrylic acid brewing; and Yang Li 21 200426275 gradual growth polymer, such as cationic polyamidoamine , Polyethyleneimine, polyamines, such as dimethylamine-epoxy propane copolymers and polyurethanes. The weight average molecular weight of the LMW cationic organic polymer is usually at least 100,000, suitably at least 500,000, and preferably at least 10,000, and it is usually up to 5,000, suitably up to 3 0,000,000, and preferably up to 2,000,000. Generally, in the case where a cationic organic polymer is added to a HC stream as a retention agent or part of a retention system, the weight average molecular weight of the LMW cationic organic polymer added to the stream is lower than the cationic organic polymerization added to the stream The person. The amount of LMW cationic organic polymer added to the LC stream is at least 0.001% based on the dry matter of the raw material to be dehydrated. Suitably, the amount is in the range of 0.05 to 1.0%, preferably in the range of 0.001 to 0.5%. In a preferred aspect of the present invention, after the LC stream containing the LMW cationic organic polymer is introduced into the Hc stream containing one or more retention components to form a generated water stream, no other retention components are introduced into the generated water stream. The formation of the generated water stream preferably occurs in the dilution net front box, but may also occur outside the net front box. ^ The method of the present invention can also be applied to all papermaking methods and cellulosic suspensions, and it is particularly useful for making raw materials that are dewatered in paper / on-line and in dewatering conditions from raw materials with high conductivity. The conductivity is usually up to 5.0 mS / cm.
^ 準器材，例如Christian Berner所供應的wtw LF 539儀&纟測量導電度。上述所指的值係以藉由測量要 被噴射到漉網上以被脫水的生成水流之導電度來決定。高 22 200426275 導電度意味高鹽（電解質）含量，i 从仏Η ^ m $术自用於形成原料 的材料、來自導入原料内的 ^的各種添加劑、來自供應於製程 的新鮮水，等等。再者，蹿含 现3里在白水被大量循環的製程 中通常係較高的，其將導致醆 中 π双鹽可觀地累積在製程的循環水 環 用 水 噸 本發”涵蓋造紙方法，其中白水被大量循環或再循 即具有兩度的白水密封，例如所製造的每嘲乾紙係使 至30 °㈣新鮮水，通常每賴使用少於20㈣新鮮 適合地少於15嘲’較佳少於10嘲，且特別地少於5 可在任何階段將新鮮水導入製程中，例如新鮮水可混 合纖維素纖維歧形成_種懸浮液，且新鮮水可與一含纖 維素纖㈣濃懸浮液混合以稀釋它，俾形成—種稀懸浮液 ，其當作尚桐度流被送到網前箱内。 依本發明的方法係用於製造紙。本文中所用的術語「 紙」當然不僅包括紙和其之製造，而且包括其它紙幅似產 品，例如板及紙板，以及其之製造。該方法可用於由不同 類型的纖維素纖維懸浮液來製造紙，且㈣浮液應適當地 含有至少25重量％以乾物f重量為基準的該纖維，較佳至 少50重量％。懸浮液可以來自化學紙漿的纖維為基礎，如 以硫酸鹽及亞硫㈣纟《、㈣械紙漿、化學-熱機械紙 聚、有機溶劑罐、精碎紙聚或來自硬質木材和軟質木材 的碎，紙聚，或得自—年生植物，如象草，、亞麻、 稻草等等’且亦用於以回收纖維為基礎的懸浮液。本發明 較佳係應用於由含木材的懸浮液來製造紙的方法。該懸浮 23 200426275 液亦含有傳統類型的礦物填料，例如高嶺土、黏土、二氧 化鈦、石貧、滑石以及天然和合成碳酸妈，例如白堊、重 貝大里石重貝石反酸姜弓及沈殿碳酸約。原料當然亦含有傳 統類型的造紙用添加劑，如濕強度劑、原料膠劑，如基於 松香、乙烯_二聚物、乙烯酮多聚物、烯基琥珀酐等為基 礎者。^ Standard equipment, such as the wtw LF 539 meter & 539 supplied by Christian Berner, measures conductivity. The above-mentioned values are determined by measuring the conductivity of the generated water stream to be sprayed onto the grate to be dehydrated. High 22 200426275 Electrical conductivity means high salt (electrolyte) content, i from 仏 Η ^ m $ from the materials used to form the raw materials, from various additives introduced into the raw materials, from fresh water supplied to the process, and so on. In addition, the water content of 蹿 3 is usually higher in the process in which white water is circulated in a large amount, which will cause the π double salt in 醆 to be significantly accumulated in the circulating water of the process. It is sealed with two degrees of white water after being recirculated or recirculated. For example, each made of dried paper is made to 30 ° ㈣ fresh water, usually less than 20 is used per fresh. 10, and especially less than 5, fresh water can be introduced into the process at any stage, for example, fresh water can be mixed with cellulose fibers to form a suspension, and fresh water can be mixed with a cellulose fiber-containing concentrated suspension In order to dilute it, maggots form a dilute suspension which is sent to the front net box as a Shangtong flow. The method according to the present invention is used to make paper. The term "paper" as used herein certainly includes not only paper And its manufacture, and includes other web-like products, such as boards and paperboard, and its manufacture. This method can be used to make paper from different types of cellulosic fiber suspensions, and the floater should suitably contain at least 25% by weight of the fiber based on the weight of dry matter f, preferably at least 50% by weight. Suspensions can be based on fibers from chemical pulp, such as sulfate and sulfite, sulphate pulp, chemical-thermomechanical paper polymer, organic solvent tanks, fine paper polymer, or crushed wood Paper, or obtained from-annual plants, such as elephant grass, flax, straw, etc. 'and also used in suspensions based on recycled fiber. The present invention is preferably applied to a method for producing paper from a wood-containing suspension. The suspension 23 200426275 liquid also contains traditional types of mineral fillers, such as kaolin, clay, titanium dioxide, stone lean, talc, and natural and synthetic carbonates such as chalk, heavy beidariite, heavy beitite inverse acid ginger bow, and Shendian carbonate. The raw materials of course also contain traditional types of paper-making additives, such as wet strength agents, raw material gums, such as those based on rosin, ethylene dimer, ketene polymer, alkenyl succinic anhydride, and the like.
適合地，本發明係應用於造紙機，其用於製造含木和 的紙及以回收纖維為基礎的紙，如sc、LWC及不同類型合 書紙或新聞紙，及應用於無木印刷紙及筆記紙之製造用^ 機器’術語無木係意味少於約15%的含木纖維。本發明功 可應用於在早層機器上’以及在多層網前箱中製造紙或細 板的機器上，及在具有數個網前箱的機器上製造紙板，玉 中-或多層本質上係由时纖維所構成。在使用多層網廟 箱或數個網前箱的機器中，田#碰 ^ ^ τ用稀釋型網前箱來製造一或多 層，本發明可應用於這些層之_或多個。適合地，本發明Suitably, the present invention is applied to a paper machine for manufacturing wood-containing paper and paper based on recycled fibers, such as sc, LWC, and different types of bound paper or newsprint, as well as wood-free printing paper and ^ Machines used in the manufacture of note paper The term woodless means less than about 15% wood-containing fibers. The function of the present invention can be applied to early-stage machines' and to machines for making paper or slabs in multi-layer net-front boxes, and to make cardboard on machines with several net-front boxes, Yuzhong- or multi-layer essentially Consists of time fiber. In a machine using a multi-layered net box or several net box, Tian #bang ^ ^ τ uses a diluted net box to make one or more layers. The present invention can be applied to one or more of these layers. Suitably, the invention
係應用於α _至测公尺/分鐘運轉的造紙機，且較程 為1 000至2000公尺/分鐘。 然而本發明不意欲 否則份及％係分別 以下實施例更進一步說明本發明 受該些實施例所限制。除非另有指明 指重量份及重量％。 【實施方式】 實施例 用不同的LMW陽離子有機聚合物當作κ㈣ 24 200426275 來试驗本發明的的方法。 在利用稀釋網前箱w翻 一 j相Μ製造sc級的造紙機上，由纖維素 懸浮液來製造紙。將、、恶切 f滯召劑加到HC原料；首先〇· 8公斤， 其為以每噸具有重詈承 千句为子量約1百萬的二甲基胺-環氧 氣丙烷共聚物的乾成品盘I # AL ^ Λ 风口為基準，然後〇· 36公斤，其為以每 、:、有重畺平均刀子里約4·6百萬的陽離子聚丙烯醯胺為 基準。藉由將原料瀝乾以得到LC原料。It is used in paper machines that run from α to metric meters / minute, and has a range of 1,000 to 2,000 meters / minute. However, the present invention is not intended. Otherwise, the parts and percentages are respectively different. The following examples further illustrate that the present invention is limited by these examples. Unless otherwise indicated, parts by weight and% by weight. [Embodiment] Example The method of the present invention was tested using different LMW cationic organic polymers as κ㈣ 24 200426275. Paper was made from a cellulose suspension on a paper machine using sc-stages to make a sc stage using a dilute mesh front box w. Add, and cut the f stagnation agent to the HC raw material; first 0.8 kg, which is a dimethylamine-epoxy propane copolymer with a weight of about 1 million per ton. The dried product I # AL ^ Λ is based on the air outlet, and then 0.36 kg, which is based on the cationic polypropylene amidamine with an average knife weight of about 4.6 million per weight. The LC material was obtained by draining the material.
將500耄升LC原料加到一動力瀝乾槽内，及在 lOOOppm混合15秒，然後將LMW陽離子有機聚合物原料中 及此合30秒。就空白試驗而言，將LC原料加到一動力瀝 乾槽内，及在l〇〇〇ppm混合45秒，但不添加陽離子有 機聚合物。然後將所獲得的“原料瀝乾，及收集濾液，使 通過1微米過濾器。使用具有快速掃描速率的〇cean Optics S2000 UV分光光度計來測量UV吸收度，以當作經 過濾的部份之木瀝青含量的表示。500 liters of LC raw material was added to a power drain tank and mixed at 1,000 ppm for 15 seconds, and then the LMW cationic organic polymer raw material was neutralized for 30 seconds. For the blank test, the LC feed was added to a power drain tank and mixed for 45 seconds at 1000 ppm without the addition of a cationic organic polymer. The obtained "raw material was then drained, and the filtrate was collected and passed through a 1 micron filter. UV absorbance was measured using a Ocean Optics S2000 UV spectrophotometer with a fast scan rate as part of the filtered portion Expression of wood pitch content.
在相同的乾劑量（以LC原料乾物質為基準約4公斤/嘴 ’對應於以總乾物質捲噸數為基準約2公斤/噸）。 LMW-1為一種具有重量平均分子量約12〇,〇〇〇的二甲 基胺—環氧氣丙烷共聚物； LMW-2為一種具有重量平均分子量約1，000, 〇〇〇的二 甲基胺-環氧氣丙烷共聚物； LMW-3為一種具有重量平均分子量約680,000的聚二 烯丙基二甲基氯化銨；及 LMW-4為一種具有重量平均分子量約1，800, 000的聚 25 200426275 二稀丙基二甲基氯化銨。 與空白試驗比較下，所有依本發明的方法 的UV吸收。依本發明最有效的方法係為採用|有减少 分子量約uoo，_的聚二稀丙基二甲基氣化銨者。里千均 這些試驗摘述於表i中，其顯示依本發明的方法及 應於先前技藝的空白組在不同波長的uv吸收度。At the same dry dose (approximately 4 kg / ton based on LC raw material dry matter 'corresponds to approximately 2 kg / ton based on total dry matter volume tonnage). LMW-1 is a dimethylamine-epoxy propane copolymer having a weight average molecular weight of about 120,000; LMW-2 is a dimethylamine having a weight average molecular weight of about 1,000,000 -Epoxy propane copolymer; LMW-3 is a polydiallyldimethylammonium chloride having a weight average molecular weight of about 680,000; and LMW-4 is a poly25 having a weight average molecular weight of about 1,800,000 200426275 Dipropyl dimethyl ammonium chloride. The UV absorption of all methods according to the invention compared with the blank test. The most effective method according to the present invention is to use a polydipropylammonium vaporized gas with a reduced molecular weight of about uoo. Li Qianjun These tests are summarized in Table i, which shows the UV absorbance at different wavelengths of the blank group according to the method of the present invention and the prior art.
26 200426275 表1 :在不同波長的UV吸收度 UV吸收度 波長nm 空白組 LHW-1 LMW-2 LMW-3 LMW-4 241.21 2. 68 2. 656 2.683 2.636 2.647 244. 96 2. 707 2. 744 2. 707 2. 671 2. 657 248.7 2. 705 2.61 2.603 2.499 2.454 252. 44 2.586 2.427 2. 403 2. 296 2.243 256.18 2. 555 2. 345 2.352 2.228 2.156 259. 91 2. 575 2. 376 2. 37 2. 255 2.181 263. 64 2.607 2.454 2.441 2.328 2. 293 267. 37 2. 692 2. 545 2. 567 2.488 2.438 271.1 2.728 2. 666 2. 649 2. 588 2.575 274. 82 2.71 2.682 2. 66 2. 642 2.623 278. 54 2.687 2. 706 2. 666 2. 64 2.633 282. 26 2· 654 2. 653 2. 639 2.621 2.596 285. 97 2. 634 2· 59 2.582 2. 534 2.496 289. 68 2.476 2.331 2.318 2.212 2.164 293. 39 2. 05 1.838 1.823 1.715 1.661 297. 09 1.672 1.463 1.453 1.359 1.31 300.8 1.433 1.239 1.23 1.144 1.101 304. 49 1.284 1.104 1.096 1.017 0.98 308.19 1.172 1.005 0.998 0.927 0.892 311.88 1.073 0.916 0.91 0.844 0.813 315.57 0.97 0.826 0.817 0.757 0. 73 319.26 0.868 0.733 0. 727 0.673 0.648 322. 94 0.768 0. 643 0.638 0.589 0.567 326. 62 0.672 0.558 0.553 0.509 0.49 330.3 0.576 0.4731 0.468 0.43 0.41526 200426275 Table 1: UV absorption at different wavelengths UV absorption wavelength nm Blank group LHW-1 LMW-2 LMW-3 LMW-4 241.21 2. 68 2. 656 2.683 2.636 2.647 244. 96 2. 707 2. 744 2. 707 2. 671 2. 657 248.7 2. 705 2.61 2.603 2.499 2.454 252. 44 2.586 2.427 2. 403 2. 296 2.243 256.18 2. 555 2. 345 2.352 2.228 2.156 259. 91 2. 575 2. 376 2. 37 2. 255 2.181 263. 64 2.607 2.454 2.441 2.328 2. 293 267. 37 2. 692 2. 545 2. 567 2.488 2.438 271.1 2.728 2. 666 2. 649 2. 588 2.575 274. 82 2.71 2.682 2. 66 2 .642 2.623 278. 54 2.687 2. 706 2. 666 2. 64 2.633 282. 26 2 · 654 2. 653 2. 639 2.621 2.596 285. 97 2. 634 2 · 59 2.582 2. 534 2.496 289. 68 2.476 2.331 2.318 2.212 2.164 293. 39 2. 05 1.838 1.823 1.715 1.661 297. 09 1.672 1.463 1.453 1.359 1.31 300.8 1.433 1.239 1.23 1.144 1.101 304. 49 1.284 1.104 1.096 1.017 0.98 308.19 1.172 1.005 0.998 0.927 0.892 311.88 1.073 0.916 0.91 0.844 0.813 315.57 0.97 0.826 0.817 0.757 0. 73 319.26 0.868 0.733 0. 727 0.673 0.648 322. 94 0.768 0.643 0.638 0.589 0.567 326. 62 0.672 0.558 0.553 0.509 0.49 330.3 0.576 0.4731 0.468 0.43 0.415
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