1278555 玖、發明說明： 【發明所屬之技術領域】 本發明關於-種製造紙的方法，其中在纖維素原料由 網前箱（—χ)喷射到i網上以形成紙幅之前，將造紙天 加劑導入該纖維素原料内。 4 【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 料及从、加J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—成形漉網上。纟由原料排出，俾在 I網上形成濕紙幅’及更將紙幅脫水及在造紙機的乾躁段 中被乾燥。木又 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滯留劑，其之例子包括 不同刀子畺的陰離子性、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 留在漉網上的細粒子，而該白水通常在不同的流動迴路中 被输環。 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 铜度流體。網前箱具有一系列的混合段或稀釋線分佈在網 1278555 前箱的寬戶上。 /、 ^ ^ 。水係被注入混合段内以便局部控制原料 的稀釋，粗IV JT^ L> 9 >成可變的稠度輪廓，其以固定的體積流速 肖隹開堰板縫隙。兮乂 4 °亥稀釋網别箱設計係提供對紙張特性的較 ,猎調整稀釋f，即在橫過機；II的稀釋網前箱之 固點的向稠度流體對低稠度流體的比例，則能以改良的 的:、：拴制紙幅的基重，且在橫機器向中使成本質上均勻 :、、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（Piteh)沈積控制。 在衣乂各種紙張中，造紙機上的木瀝青積聚及最後紙 、主歷月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、樹脂狀材津斗，其在碎襞程序期間由木材釋放出 。木瀝青Φ包括起源於經塗覆的廢紙及經回㈣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 廉製，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 膠態木遞青粒子在纖維素懸浮液中黏聚或沈積在漉=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 量製程水閉合，如大量的白水循環之造紙廠中，這歧問題 係被放大。 1278555 【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； (i i)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； (111)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 入A 3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 (v 1 )將孩生成水流喷射到漉網上及將該生成水流脫水 ，以形成紙幅。 本毛明更針對一種在含有#釋網前箱的造紙機上製造 紙的方法，其包括：1278555 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明The agent is introduced into the cellulosic feedstock. 4 [Prior Art] In the papermaking technology, a cellulose fiber, a filler selected as needed, and an aqueous suspension (referred to as a raw material) from J and J are fed into a head box, which will be The raw material is sprayed onto the forming web. The crucible is discharged from the raw material, and the wet web is formed on the I mesh, and the web is further dehydrated and dried in the dry section of the paper machine. The wood typically introduces a retentate into the feedstock which increases the adsorption of particles such as fine particles and filler particles onto the cellulosic fibers so that they are retained by the fibers on the web. 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 knives. Due to incomplete retention, the water obtained by dewatering the raw material and the wet paper web, referred to as white water, contains fine particles that are not retained on the crucible network, and the white water is usually transported in different flow circuits. In a paper machine with a dilute headbox, white water is used to dilute the material in the pre-net phase. Thereby, the high-copper fluid is diluted with a low-consistency fluid derived from white water. The headbox has a series of mixing sections or dilution lines distributed over the wide compartment of the 1278555 front box. /, ^ ^. The water system is injected into the mixing section to locally control the dilution of the raw material, and the coarse IV JT^L> 9 > becomes a variable consistency profile which is opened at a fixed volumetric flow rate.兮乂 4 ° Hai Diluted Grid Box Design provides a comparison of paper characteristics, hunting adjustment dilution f, that is, the ratio of the consistency fluid to the low consistency fluid at the fixed point of the dip net front box of II; It can be improved:: the basis weight of the paper web, and the cost uniformity in the transverse machine direction: , and obviously 'when using high-performance retention agent, the papermaking method has been experienced and the method has been produced. The paper characteristics are still not fully satisfactory and have been attributed to improper Piteh deposition control. Among the various papers in the placket, the problems caused by the accumulation of wood asphalt on the paper machine and the formation of the final paper and the main moon have been recognized. Wood asphalt generally refers to an emulsified hydrophobic organic compound. Wood asphalt can be defined as a viscous, resinous material that is released from the wood during the mashing process. Wood asphalt Φ includes viscous materials originating from coated waste paper and recycled (four) fibers, such as additives, and is often referred to as glue or glue. In papermaking, water, wood asphalt is unstable, A colloidal suspension of hydrophobic particles is present. Thus, typical papermaking process conditions, such as hydrodynamic and mechanical shear forces, as well as drastic changes in temperature and chemical environment and balance, may cause colloidal wood adchlorite particles to cohere or deposit in cellulosic suspensions. On the surface of the device. This can result in quality defects in the finished product, such as the formation of dots or holes and poor quality paper surfaces, as well as reduced equipment life, operational time, paper machine downtime, and ultimately lost paper mill profits. In paper mills with high-content process water closure, such as large white water cycles, this problem is magnified. 1278555 SUMMARY OF THE INVENTION The present invention is generally directed to a method of making paper comprising: (i) providing a primary water stream comprising cellulose fibers; (ii) introducing one or more retention components into the main water stream to form a main stream comprising one or more retentate components; (111) providing a dilution water stream; (iv) introducing a low molecular weight cationic organic polymer into the dilution water stream to form a dilution comprising a low molecular weight cationic organic polymer The water stream 'the low molecular weight cationic organic polymer has a weight average molecular weight of up to 5, 〇〇〇, 〇〇〇; (v) the dilution water containing the low molecular weight cationic organic polymer flows into the main component of A 3 with one or more retention components The water stream is formed to form a generated water stream; and then (v 1 ) the child-generated water stream is sprayed onto the crucible network and the resultant water stream is dewatered to form a web. Ben Maoming is more directed to a method of making paper on a paper machine containing a #release net front box, comprising:
合所獲得的稀釋 ”入一含有纖維素纖維的主水 A胃稀釋網前箱内； 里敢南為5，〇〇〇，〇〇〇的低 —稀釋用水流内，及將所獲 ⑷8555 (iv)將該生成水流噴射 ，以形成紙幅。 、/ 、’祠上及將該生成水流脫冰 本發明亦針對一種由人 填料之水性懸浮液來製造:的=素纖維和視需要選用的 留成分導入懸浮液内，接 古’，包括將-或多種滞 5, 000,000的低分子旦、八重量平均分子量最高為 讥刀子里％離子有機聚人 及然後在漉網上形成及瀝乾懸浮液。：…夜内， 依本發明’已經於 ,„ ^ 、 精由在將原料於漉網上脫水以# 成紙幅之前，以特定的方々腺、★ 』上脱水以形 士 I主 式將添加劑導入該原料則可減W、 木瀝月問題。此發現亦特別有用皮 ^ 稀釋網前箱的造紙機上寧造 、 八有 灶仏， 紙。亦已經發現依本發明可較 么也控制造紙系統中木瀝青的沈積。更已經 方法係能製造具有改良特性的紙。、 … s明的 稀釋網前箱（dllutlGnheadbQx)A體上可被敘述成一 種衣置，其包括至少-個第_部分體積流用入口、至少一 個第二部分體積流用入口、至少—個供混合該些部分體積 流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 、5^6>383、 5, 545, 293 及 5, 549, 793 中所揭示者。 本文中所用的術語「主水流」係指含纖維素纖维及視 需要選用的填料之主流，其在進入網前箱，具有高稠度（ 1278555 以下稱為/c)，即高固體含量，HC原料，因此代表高稍度 流（以下稱為HC流）^ HC流的稠度範圍可為〇.丨至3 5重 量％，適合地為0.3至2·2重量％，且較佳為〇 4至^ 9重 量％。本文中所用的術語「稀釋用水流」係指—種用於稀 釋HC流的水流，且其與HC流有關，係具有低稠度⑽， 即低固體含量，IX原料，因此代表低㈣流（以下稱為K 流hLC流的稠度範圍可為G_15重量％，適宜地為q . 0.9重量％’且較佳為0.005_0.8重量％，限制條件為Μ流 的稠度係低於HC流。較宜地，在網前箱内，Hc流係被a 流所混合及稀釋，例如在緊鄰擾流產生器之前，以形$成一 種生成洲_，其排放到漉網上以便脫水。He流 法 L 的體 積比在99:1至50:50的範圍内，適宜地在Μ』至6 的範圍内，較佳為在95:5至75:25的範圍内，且並型上 85:15。如稀釋網前箱中所習知者，肊流和lc、& ' 較佳係在橫過網前箱的寬度之數個點 2 —積比 釋量，俾能較佳的所形成的紙幅之基重截面整稀 分體積流’即HC流和LC流，係在網前箱中混八，、’部 -種生成HC/LC混合物體積流，其由網前箱被匕;:形成 其在橫機器方向係本質上恒定的。 、，且 稀釋用的LC水流可選自於新鮮水、白水及 中循環的水流。該稀釋用的“流可能含有纖維二及2 ，且在將其送入網前箱之前可用任何純化 ：填料 可用於純化或澄清這些類型水流的適合步驟之例二里：。 濾、夺選、沈降、厭氣及好氣處理。較宜地 匕括過 ，LC流係白水 1278555 ’其含有例如鐵维去 ^ 士# 、准素、、、田物、卒取物及其它在碎漿過程中由 木材所釋放出的材斜 的填料，以及¥人Hc流内但不保留在漉網上 的具科和添加劑。辦 斤用的白水較佳為藉由在漉網上將原料 mic而得到者，且其在送人稀釋網前箱之前可 ::上述地被澄清°LC流通常具有不同於hc流的組成4 二中使^時」LC流的填料含量通常不同☆ HC流： 通吊具有較鬲的填料含量，以該流而非以Η 物質百分率來表示。 ^ 除了如上述進人網前箱内的κ流及Μ流，依本發明 二：至〃個進入網前箱的額外流。該額外流較佳為一種 3早獨水的流。該額外流亦為—種原料或紙漿流，其之钢 度及/或組成係不同於Hc流。 依本發明所要導入HC流内的滞留成分為單一滞留 -種滯留系統’例如任何以下所定義者。單一成分可為任 何具有滞留劑功能的成分，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。 在本發明一較佳具體態樣中，使用-種滯留系統。本 文中所用的術語「滞留系統」係指二或多種成分或劑，盆 當加到原料時，會得到優於不添該二或多種成分或劑者:、 滯留系統的成分較佳係選自於二或多種有機聚合物及—或 夕種承合物與鋁化合物及/或無機微粒子的組合。 在本發明的一較佳具體態樣令’使用一種微粒子滞留 系統。本文中所用的術語「微粒子滯留系統」係指一種滞 12 ^278555 =:其包括微粒狀材料，或微粒子， 羲的陰離子無機粒子、陽離子+文中所心 极狀材料係與至少一種复二入彳機微粒子。微 有機聚合物，本文中亦猶A 士方人 、韦至夕一種 卜“ 冉為主聚合物，較佳為陽離子、Λ 性或陰離子聚合物。陰離子微粒子較兩 及/或陽離子聚合物組合使用 ；、广種兩性 與至少-種兩性及…：二：離子微粒子較佳為 ㈣；…Α 次陰離子聚合物組合使用。較宜地， 一：*子無機粒子。更佳為該微粒子係在粒度的脒 恶範圍内。；帶囟会M , 的. 系、，充，例如含微粒子的系統，可包括多# =的成分，如，其可為三一分滯留二： :m“:r包括紹化合物及低分子量陽離子有機聚 ,㊉，印邊糸統，包含微粒子滯留系統，亦得到比 不冰加D亥成少刀日守較佳的脫水’而且該系統一般被稱為滞留 及脫水系統。 ，在本發明的另一較佳具體態樣中，使用一種滞留系統 其包括一或多種陽離子有機聚合物及一或多種陰離子有 機聚合物。適宜妯，士方、、狀&么p ^ t 、且地忒冗留糸統包括一具有一或多個芳基 的陽離子有機聚人％芬/々 久口物及/或一具有一或多個芳基的陰離子 有機聚合物，如本文中所定義。 本赉月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。較宜使用陰離子矽石系粒子，即基於 Sl〇2或矽酸的教子，包括膠態矽石及不同類型的聚矽酸和 聚矽酸鹽。陰離子矽石系粒子通常係以水性膠態分散液來 仏應即所渭的溶膠。依本發明適合的矽石系溶膠亦可含 1278555 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 、5，1 27,994 、5，1 76,891 、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。 適合的陰離子矽石系粒子具有平均粒度低於約5〇nm， 較佳為低於約2〇nm，且更佳為在約i至約1〇nm的範圍内 如矽石化學中所習知者，粒度係指初級粒子的平均大小 八可為♦集的或非聚集的。矽石系粒子的比表面積適宜 ，係50m2/g以上，較佳1〇〇m2/g以上。通常，比表面積最 高為約170〇mVg，且較佳最高為1〇〇〇m2/g。以已知的方式 用_滴定的方式，例如Sears在Wytic 28(1 956):1 2，198卜1 983及美國專利第5，1 76,891號中所 述者’在適當地移除或調整樣品中所存在的之可能干擾滴 定的任何元素或化合物如！呂和硼物後，測量比表面積。所 得到的面積因此代表粒子的平均比表面積。 在本發明的-較佳具體態樣中，陰離子無機粒子係石夕 石糸粒子，其具有比表面積在5〇至则m2/g的範圍内， 較佳1 00至950m2/g。較宜地，险離工也 奶陰離子無機粒子係存在於矽 石系溶膠中，其之s值係在8至45%的範圍内，較佳1〇至 14 1278555 35%，含有比表面積在3〇〇至i〇〇〇m2/g範圍内的矽石系粒 子，適宜地在500至950m2/g的範圍，該粒子可為非經鋁 改質或經铭改質者，適合地為表面經鋁改質者。s值的測 !及計算係如 Her & J· Phys· Chem· 60(1 956)，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lOOOmVg以上。比表面積在1〇〇〇至17〇〇m2/g 的範圍内，較佳為1050至160〇mVg。在技藝中，聚矽酸亦 稱為聚合矽酸、聚碎酸微凝膠、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。含鋁的 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石夕酸之内。 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 及⑺石畚，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, 71 0、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 子矽石系粒子、陽離子氧化鋁及陽離子氧化錯。 依本發明適用當作滯留劑或滞留系統的一部分之有機 I278555 =物為陰離子性、非離子性、 “天然或合成源，且它們可為線型它們可 微粒子形式。較宜地，繫人#^ 刀枝或父聯，例如 較且地聚合物係水溶性或水可分 適合的陽離子聚合物之例子 月 粉、瓜耳膠、纖維素、幾丁質==子多畴，例如- 糖、聚葡萄糖、音原酸膠、果 x 聚醣、聚半乳 為搬粉及瓜耳；：八： 聚甘露糖、糊精，較佳 十：耳务，適合的搬粉包括馬鈴著、玉米、小麥、 陽離子鏈生長聚合物，例如陽= ::::…丙稀醯胺-、乙稀胺…乙稀醯胺二2 二;:？，及陽離子逐步生長聚合物，例如陽離子聚酿胺 二:广浠醯亞胺、聚胺及聚胺甲酸酿。陽離子殿粉及 %料丙烯醢胺系聚合物係特佳的陽離子聚合物，兩者當 2單-滞留成分以及在滯留系統中’有或無陰離子無機： 適口的具有一或多個芳基的陽離子有機聚合物之例子 匕括W0 02/12626中揭示者。陽離子有機聚合物的重量平 均分子ϊ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2,000,000以上，更常為在3，_，剛以 上，適合地為在5,000,000以上。上限係未嚴袼要求的； 其可為約600,0〇〇,〇〇〇，通常15〇,〇〇〇,〇〇〇，且適合地為 1 00, 000, 000 〇The dilution obtained by the combination is entered into a front tank containing a cellulosic fiber in the main water A stomach dilution net; Li Gannan is 5, 〇〇〇, 〇〇〇 low-dilution water flow, and the obtained (4) 8555 ( Iv) spraying the resultant water stream to form a paper web., /, 'on the top and deicing the produced water stream. The invention is also directed to an aqueous suspension of human filler: a plain fiber and optionally retained The ingredients are introduced into the suspension, and the mixture is composed of - or a plurality of low molecular weight deniers of 5,000,000, and the average molecular weight of the eight weights is the maximum concentration of the ions in the knives and then formed and drained on the crucible. .:... In the night, according to the invention 'has already, „ ^, Jing Yu dehydrates the raw material on the 漉 network to form a paper web, dehydrates with a specific square parotid gland, and then adds the additive to the shape of the formula I The introduction of this raw material can reduce the problem of W and wood leaching. This finding is also particularly useful for the use of leather on a paper machine that dilutes the front box of the net, eight stoves, and paper. It has also been found that the deposition of wood pitch in a papermaking system can be controlled in accordance with the present invention. Moreover, the method has been able to produce paper with improved properties. , s Ming's dilution net front box (dllutlGnheadbQx) A can be described as a garment comprising at least one _ part volume flow inlet, at least one second partial volume flow inlet, at least one for mixing The partial volume streams are formed to form a section of the mixed volume stream, and at least one outlet for injecting the mixed volume stream. Preferably, the dilute headbox includes a plurality of the inlets, segments and outlets across a working width thereof. Examples of suitable dilute headboxes are disclosed in U.S. Patent Nos. 4,909,904, 5,196, 5, 6, 383, 5, 545, 293, and 5,549,793. As used herein, the term "main stream" refers to the mainstream of cellulose-containing fibers and, if desired, fillers, which have a high consistency (referred to as /c below 1278555), ie high solids, HC. The raw material, thus representing a high degree of flow (hereinafter referred to as HC flow), may have a consistency in the range of from 0.5 to 5% by weight, suitably from 0.3 to 2.2% by weight, and preferably from 〇4 to ^ 9% by weight. As used herein, the term "diluted water stream" means a stream of water used to dilute a stream of HC, and which is associated with a stream of HC, having a low consistency (10), ie a low solids content, IX starting material, thus representing a low (four) stream (below) The consistency of the K-flow hLC stream may be in the range of G-15% by weight, suitably q. 0.9% by weight 'and preferably 0.005-0.8% by weight, with the constraint that the consistency of the turbulent flow is lower than the HC flow. Ground, in the headbox, the Hc flow system is mixed and diluted by the a stream, for example, in the vicinity of the spoiler generator, in the form of a type of formation, which is discharged onto the crucible network for dehydration. The volume ratio is in the range of 99:1 to 50:50, suitably in the range of Μ 』 to 6, preferably in the range of 95:5 to 75:25, and 85:15 on the merging. In the case of the dilute head box, the turbulent flow and lc, & ' are preferably at a number of points 2 across the width of the head box, and the ratio of the product is better. The basis weight section and the thin fractional volume flow 'that is, the HC flow and the LC flow are mixed in the headbox, and the 'part-species generate HC/LC mixture volume flow, which is collapsed by the headbox; It is essentially constant in the cross machine direction. The LC water stream for dilution can be selected from fresh water, white water and a circulating water stream. The "flow" for this dilution may contain fibers 2 and 2, and Any purification can be used before it is fed into the headbox: the filler can be used to purify or clarify the appropriate steps for these types of water streams: filtration, selection, sedimentation, anaerobic and aerobic treatment. Preferably, LC Flowing white water 1278555 'It contains, for example, iron-dimensional to ^shi #, quasi-sugar,,, field, stroke, and other materials that are released from the wood during the pulping process, and ¥Hc flow However, it does not retain the specialties and additives on the Internet. The white water used for the charge is preferably obtained by the raw material mic on the sputum, and it can be delivered before the dilution of the front box: Clarification °LC flow usually has a different composition than the hc flow. The content of the filler is usually different. ☆ HC flow: The sling has a relatively high filler content, expressed by the flow rather than the percentage of sputum. ^ In addition to the above-mentioned CK flow in the front box of the net Flow, according to the invention 2: to an additional stream entering the headbox of the net. The additional stream is preferably a stream of 3 early water alone. The additional stream is also a raw material or pulp stream, the steel and/or Or the composition is different from the Hc stream. The retention component to be introduced into the HC stream according to the present invention is a single retention-type retention system, such as any of the following definitions. The single component can be any component having a retention agent function, preferably a cation. A polymer, such as defined herein. In this particular aspect, the amount of the component introduced into the main stream should be sufficient to provide a retention which is superior to the absence of the component. In a preferred embodiment of the invention, Use of a retention system. As used herein, the term "retention system" means two or more ingredients or agents that, when added to a feedstock, are superior to those that do not contain the two or more ingredients or agents: Preferably, the component is selected from the group consisting of two or more organic polymers and/or a combination of an aluminum compound and/or inorganic fine particles. In a preferred embodiment of the invention, a microparticle retention system is employed. As used herein, the term "microparticle retention system" means a lag 12 ^ 278555 =: it includes particulate material, or microparticles, an anionic inorganic particle of cerium, a cation + a polar material in the text, and at least one complex binary enthalpy Machine particles. Micro-organic polymers, also referred to herein as A. Fang, Wei Zhi Xi, a 冉-based polymer, preferably a cationic, an anionic or an anionic polymer. Anionic microparticles are used in combination with two and/or cationic polymers. ; a wide variety of sexes and at least - amphoteric and ...: two: ionic microparticles are preferably (four); ... Α sub-anionic polymer is used in combination. Preferably, one: * sub-inorganic particles. More preferably the micro-particles in the particle size Within the scope of abhorrence; a system with a sputum M, a system, a charge, such as a microparticle-containing system, may include multiple #= components, such as, which may be three-in-one stagnation: :m ":r includes The compound and the low molecular weight cationic organic poly, ten, the Indian system, including the microparticle retention system, also get better dehydration than the non-ice plus D Haicheng, and the system is generally called the retention and dehydration system. . In another preferred embodiment of the invention, a retention system is used which comprises one or more cationic organic polymers and one or more anionic organic polymers. Suitable for 妯, 士, 状, 么 ^, and 忒 忒 包括 包括 且 且 包括 包括 包括 包括 包括 包括 包括 包括 包括 包括 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子 阳离子A plurality of aryl anionic organic polymers, as defined herein. The anionic inorganic particles used in this month include anionic Shishiite particles and smectite clays. It is preferred to use anionic vermiculite particles, i.e., based on Sl2 or tannic acid, including colloidal vermiculite and different types of polyphthalic acid and polyphthalate. The anionic vermiculite particles are usually in the form of an aqueous colloidal dispersion. Suitable vermiculite sols in accordance with the present invention may also contain 1,278,555 other elements such as nitrogen, aluminum and boron. This element may be present in a modified form containing a nitrogen-containing organic compound, an aluminum-containing compound, and a boron-containing compound, respectively. These compounds may be present in the aqueous sol and/or vermiculite particles. Retention and dehydration systems containing suitable anionic smectite particles are disclosed in U.S. Patent Nos. 4,388,150, 4,927,498, 4,954,220, 4,961,825, 4,980,025, 5,1 27,994, 5,1 76,891, 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 vermiculite particles have an average particle size of less than about 5 Å, preferably less than about 2 Å, and more preferably in the range of from about i to about 1 〇 nm, as is known in meteorite chemistry. The particle size means that the average size of the primary particles can be ♦ set or non-aggregated. The vermiculite particles have a specific surface area of 50 m 2 /g or more, preferably 1 〇〇 m 2 /g or more. Generally, the specific surface area is up to about 170 〇 mVg, and preferably up to 1 〇〇〇 m 2 /g. The sample is suitably removed or adjusted in a known manner by means of _ titration, for example as described by Sears in Wytic 28 (1 956): 1 2, 198, 1 983 and U.S. Patent No. 5,176,891. Any element or compound present in the cell that may interfere with titration! After Lv and boron, the specific surface area was measured. The resulting area thus represents the average specific surface area of the particles. In a preferred embodiment of the present invention, the anionic inorganic particles are sarcophagus particles having a specific surface area in the range of 5 Å to then m 2 /g, preferably 1 00 to 950 m 2 /g. Preferably, the dangerous anion inorganic milk particles are present in the vermiculite sol, and the s value thereof is in the range of 8 to 45%, preferably 1 to 14 1278555 35%, and the specific surface area is 3 The vermiculite particles in the range of i〇〇〇m2/g are suitably in the range of 500 to 950 m 2 /g, and the particles may be modified by aluminum or modified by the name, suitably a surface Aluminium upgrader. The measurement of the s value and the calculation are as described in Her & J. Phys Chem. 60 (1 956), 955-957. The s value indicates the degree of aggregation or microgel formation, and the lower s value indicates a higher degree of aggregation. In still another preferred embodiment of the present invention, the anionic inorganic particles are selected from the group consisting of polydecanoic acid, optionally reacted with aluminum, and have a high specific surface area, suitably above about 1000 mVg. The specific surface area is in the range of 1 Torr to 17 〇〇 m 2 /g, preferably 1050 to 160 〇 mVg. In the art, polyphthalic acid is also known as polymeric phthalic acid, polyacid microgels, polysilicates, and polycaprate microgels, all of which are encompassed by the term polyphthalic acid as used herein. The aluminum-containing polyphthalic acid is commonly referred to as polyaluminum silicate and polyaluminum silicate microgels, all of which are encompassed by the term polylithic acid as used herein. The smectite-type clays useful in the methods of the present invention are known and include naturally occurring, synthetic, and chemically treated materials. Examples of suitable smectite clays include montmorillonite/expanded soil, hectorite, beidellite, smectite and (7) sarcophagus, preferably bentonite, especially after swelling, preferably having a surface area of 400 to 800m2/g. Suitable clays are disclosed in U.S. Patent Nos. 4,753,712, 5, 071, 512, and 5, 607, 552, the disclosures of each of Preferably, it is natural bentonite. Useful cationic inorganic particles include cationic vermiculite particles, cationic alumina, and cationic oxidation. Organic I278555 as a retentate or retention system in accordance with the invention is an anionic, nonionic, "natural or synthetic source, and they may be in the form of a linear form of microparticles. Preferably, the system #^ An example of a cationic polymer, such as a sugar, a poly-type Glucose, yoke acid gum, fruit x-glycan, polygalactite for moving powder and guar; 8: Polymannose, dextrin, preferably 10: ear work, suitable for moving powder including horse bell, corn, Wheat, cationic chain growth polymer, such as cation =::::... acrylamide-, ethyleneamine... acesulfame 225;;?, and cationic step-growth polymers, such as cationic polyamine II : Hirose imine, polyamine and polyuric acid. The cationic powder and the acrylamide polymer are excellent cationic polymers, both of which are 2 single-retention components and in the retention system. Or no anionic inorganic: a palatable cationic organopoly having one or more aryl groups Examples of compounds include those disclosed in WO 02/12626. The weight average molecular weight of the cationic organic polymer varies over a wide range, depending in particular on the type of polymer used, and is typically above 2,000,000, more often at 3 , _, just above, suitably above 5,000,000. The upper limit is not strictly required; it may be about 600,0 〇〇, 〇〇〇, usually 15 〇, 〇〇〇, 〇〇〇, and suitably For 1 000, 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)。ATC ]6 1278555 陽離子有機聚合物的重量平均分子量通常為至少、2，_， :合地為至少1〇’_ ’且較佳至少50, 000，且其通常為最 1 2’咖，剛’及常常最高1，5GG，GG()。適合的ATC包括線 尘刀枝及又聯聚合物，通常係高度帶電的，其可得自天 然及合成源。適合@ ATC例子包括低分子量降解之多醣， 例如基於歲粉、瓜耳膠、纖維素、幾丁質、幾丁聚糖、聚 醣*半礼糖、聚葡萄糖、黃原酸膠、果膠、聚甘露糖、 精車又仏為' 馬·粉及瓜耳膠，適合的殺粉包括馬鈴薯、玉 米J、麥、木薯、稻求、糯玉米、大麥等；陽離子合成有 機承口物如陽離子鏈生長聚合物，例如陽離子乙稀系加成 聚：物，如丙浠酸雖_、丙烯醯胺_、乙稀胺_、乙烯醯胺_ 及烯丙基胺系聚合物’例如基於二烯丙基二烷基鹵化銨的 均-和共聚物，例如基於二烯丙基二甲基氯化銨者，以及( 甲基）丙稀醯胺及（甲幻丙烯酸及陽離子逐步生長聚合 物’心二陽離子聚醯胺基胺、聚乙烯亞胺、聚胺，：如： 甲基胺-環氧氯丙烷共聚物及聚胺甲酸酯。 依本發日月適合的陰料有冑聚合物之例子選自於逐步 生長聚合物、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险 離子基於苯及基於萘的縮合聚合物’較佳為基於萘—碏： 及基於萘磺酸鹽的縮合聚合物；及加成聚合物，即藉由逐 步生長加成聚合所得到的聚合物，例如 二 。適合的陰離子鍵生長聚合物之例子包括陰離子乙I;: 成聚合物，例如丙稀酸醋—及丙烯醯胺系聚合物，其包括 17 1278555 陰離子或潛在陰離子單 、，一 —乂 平餸如（甲基）丙烯酸及對乙烯基酚（ 土苯烯）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， :包：基於木質素的聚合物，較佳為磺化木質t，例如木 貝素K ^ i、+皮紙木質素、績化牛皮紙木質素及單寧萃 取物。其它適合的具有一或多個芳基的陰離子有機聚合物 之例=係包括W0 02/12626中所揭示者。陰離子聚合物的 重量平均分子量在寬廣範圍内變①，尤其取決於所用的聚 否物類5L且其通常至少約5〇〇，適合地在約〇⑽以上 ，且較佳為在約5, 000以上。上限係未嚴格要求的；其可 為約600, 〇〇〇, 〇〇〇，通常150,000,000，適合地為 1 00,000,000，且較佳為 1〇,〇〇〇,〇〇〇。 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「鏈生長聚合物」係 才曰一種由鏈生長聚合所得到的聚合物，亦分別稱為鏈反應 聚合物及鏈反應聚合。 依本發明所可用的鋁化合物係包括明礬、鋁酸鹽、氣 化铭、端酸紹及聚氯化鋁、聚硫酸鋁、含氯和硫酸根離子 的聚銘化合物、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。 依本發明較佳的滯留系統包括： (i)陰離子矽石系粒子與陽離子澱粉、陽離子瓜耳膠或 18 1278555 陽離子丙烯醯胺系聚合物的組合，視需要可與atc及/或鋁 化合物組合； (i i)陰離子矽石系粒子與陰離子鏈生長聚合物的組合 ’較佳為陰離子丙烯醯胺系聚合物與陽離子有機聚合物及 /或ATC的組合； (⑴)膨土與陽離子丙烯醯胺系聚合物，視需要可與 ATC及/或铭化合物組合； (iv)陽離子聚SI ’較佳陽離子殿粉，與陰離子逐步生 長务人合物的組合，較佳為盘除连任工贫么 平1H陰離子奈糸縮合聚合物；視需 要可與ATC及/或銘化合物組合； + (v)陽離子㈣’較佳陽離子殿粉，與天然發生芳族陰 離子承合物及其改質物的組合，較佳與磺化木質素，視需 要可與ATC及/或|g化合物組合； (v:l)陽離子鏈生長聚合物，較佳陽離子丙烯醯胺系聚 三物與陰離子逐步生長聚合物的組合，較佳為與陰離子 桌系縮合聚合物；;見需要可與ATC及/或鋁化合物組合； (vii)陽離子鏈生長聚合物，較佳陽離子丙稀醯胺系聚 口物與天然發生芳族陰離子聚合物及其改質物的組合， 較佳與確化木質素，視需要可與ATC及/或魅合物組合； (111)陽離子鏈生長聚合物，較佳陽離子丙烯醯胺系 聚合物，與ATC的組合。 在本發明的方法中，滯留成分係被導入HC流内，該流 :要/、LC /爪此合，較佳為在網前箱内，藉以將成分導入稀 釋長序t的生成水流。當使用含有多於—種成分的滯留系 19 1278555 二，可以傳統方式將該.成分加到原較佳為在不同點 =!?順序。當使用一含陰離子無機粒子和陽離子聚合 統時，較佳為在添加微粒狀材料之前，將陽離 子“物加到Hc原料流，縱使可使用相反的添加順序。卷 使用含有陽離子及陰離子有機聚合物的滞留系統時，較佳 =在=陰離子聚合物之前’將陽離子聚合物加到HC原料 -、’、使可使用相反的添加順序。更佳為在剪切階段之前 陽二可選自於系打、混纟、清洗等’添加第一成分，例如 Μ隹子聚合物，及在剪切階段之後，添加第二成分，例如 ::子無機微粒子或有機聚合物。當使用低分子量陽離子 1機聚合物當# ΑΚ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，較佳為在其 它滯留成分之前或同時地，導入HC原料流内。 ’、 旦滞留系統的成分係被導入原料内，其將被脫水，脫水 量可在寬廣的範圍β，尤其取決於成分的類型和數目，原 料類型，填料類型，填料含量，添加點， 八 日 寸。通吊，成 刀9添加量係能得到比不添加成分時較佳的滯留。告使用 陰離子無機聚合物當作微粒狀材料時，所添加的總^通常 為至少0.001重量％，常常至少0.005重量％，此係以原料 的乾物質重為基準。上限通常為丨.0重量％，且適合地為 〇·6重量％。當使用陰離子矽石系粒子時，總量適合4係在 0.005至0.5重量％内，此係以Si〇2計算且係以乾原料物質 為基準’較佳為在0.01至〇·2重量％的範圍内。有機聚合 物，例如陽離子及陰離子聚合物，通常的添加總量係二: 20 1278555 其；里％巾吊至少、〇.005重量％ ’此係以乾原料物質 、土準上限通系為3重量％，且適合地為1. 5重量％。當 使用低分子量陽離子有機聚合物當作atc時，直導入此原 料流内的量，以乾原料物質為基準，係至少U1%，適I 的量係在〇.〇5%至〇.5%。當使用紹化合物於製程時，導入 將要脫水的原料内之總量係取決於所用的紹化合物之類型 及其它來自彼的所欲效果。例如，技藝中眾所周知利用紹 化合物當作松香系施膝劑的沈殿劑。所添加的總量通常為 至v 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0.08至2.8%的範圍内，較佳在 的範圍内。· · 依本發明’低分子量陽離子有機聚合物係導入將要與 HC机此σ的LC流内，較佳為在稀釋網前箱中。適合的低 分子量（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，通常為高度帶電的，其可衍生自天然及合 成源。適合的LMW陽離子有機聚合物包括㈣降解聚酿， 例如基於殿粉、瓜耳膠、纖維素、幾丁質、幾丁聚糖、聚 醣、聚半乳糖、聚㈣糖、黃原酸膠、果膠、聚甘露糖、 糊精’較佳為殿粉及瓜耳勝，適合的殿粉包括馬鈐薯、玉 米】麥、木薯、稻米、糯玉米、大麥等；⑽陽離子乙 烯系加成聚合物，如丙烯酸醋_、丙烯醯胺_、乙烯胺_、乙 稀醯胺-及烯丙基胺系聚合物，例如基於二烯丙基二炫基 齒化敍的均-和共聚物’例如基於二稀丙基二甲基氯化錄 者’以及（甲基）丙稀酸胺及（甲基）丙稀酸醋；及陽離 21 1278555Examples of more suitable cationic polymers which can be introduced into the HC stream in accordance with the present invention include cationic organic polymers having a low molecular weight. The cationic organic polymer includes what is commonly referred to as a cationic waste entrapment (hereinafter referred to as Atc). ATC ] 6 1278555 The cationic organic polymer generally has a weight average molecular weight of at least 2, _, : a combination of at least 1 〇 ' _ ' and preferably at least 50,000, and which is usually the most 1 2 ' coffee, just ' And often up to 1,5GG, GG(). Suitable ATCs include wire dust knives and re-polymers, which are typically highly charged and are available from natural and synthetic sources. Suitable for @ ATC examples include low molecular weight degradation of polysaccharides, such as based on age powder, guar gum, cellulose, chitin, chitosan, glycan * sugar, polydextrose, xanthan gum, pectin, Polymannose and refined car are also known as 'ma· powder and guar gum. Suitable powders include potato, corn J, wheat, cassava, rice, waxy corn, barley, etc.; cationic synthetic organic mouthpieces such as cationic chains A growing polymer, such as a cationic ethylene addition polymer: such as propionic acid, acrylamide, ethyleneamine, vinylamine, and allylamine polymers, for example based on diallyl a homo- and copolymer of a dialkylammonium halide, for example based on diallyldimethylammonium chloride, and (meth) acrylamide and (methacrylic acid and cationic step-growth polymer 'heart two Cationic polyamidoamines, polyethyleneimine, polyamines, such as: methylamine-epichlorohydrin copolymers and polyurethanes. Examples of suitable tantalum polymers based on the date of the present invention. Selected from progressively growing polymers, chain-growth polymers, glycans, naturally occurring aromatic polymerizations And modified materials thereof. Examples of suitable anionic step-growth polymers include ionic and benzene-based and naphthalene-based condensation polymers' preferably based on naphthalene-oxime: and naphthalenesulfonate-based condensation polymers; a polymer, that is, a polymer obtained by stepwise growth addition polymerization, for example, 2. Examples of suitable anion bond growth polymers include an anion B; a polymer, such as acrylic acid vinegar - and acrylamide a polymer comprising 17 1278555 anionic or potentially anionic mono-, mono-plutonium such as (meth)acrylic acid and p-vinylphenol (m-phenylene) according to the invention, suitable naturally occurring aromatic polymers and modifications thereof A qualitative example, a modified naturally occurring aromatic anionic polymer, : a lignin-based polymer, preferably a sulfonated wood t, such as mubein K ^ i, + lignin lignin, Kraft lignin and tannin extract. Examples of other suitable anionic organic polymers having one or more aryl groups include those disclosed in WO 02/12626. The weight average molecular weight of the anionic polymer is wide. Widely varying from 1, especially depending on the type of poly5L used and which is usually at least about 5, suitably above about 10 (10), and preferably above about 5,000. The upper limit is not critical. It may be about 600, 〇〇〇, 〇〇〇, usually 150,000,000, suitably 1,000,000, and preferably 1 〇, 〇〇〇, 〇〇〇. The term "step-growth polymer" is used herein. Refers to a polymer obtained by step-growth polymerization, also known as a stepwise reaction polymer and a stepwise reaction polymerization. The term "chain-growth polymer" as used herein is a polymer obtained by chain-growth polymerization. Also known as chain reaction polymer and chain reaction polymerization, respectively, the aluminum compounds available in the present invention include alum, aluminate, gasification, terminal acid and polyaluminum chloride, polyaluminum sulfate, chlorine and Polyester compound of sulfate ion, polyaluminum citrate-sulfate, and mixtures thereof. The polyaluminum compound may also contain other anions such as anions derived from phosphoric acid, sulfuric acid, organic acids such as citric acid and oxalic acid. Preferred retention systems according to the present invention comprise: (i) a combination of anionic vermiculite particles with cationic starch, cationic guar or 18 1278555 cationic acrylamide polymer, optionally in combination with atc and/or aluminum compounds (ii) a combination of an anionic vermiculite-based particle and an anionic chain-growth polymer 'preferably a combination of an anionic acrylamide-based polymer and a cationic organic polymer and/or ATC; ((1)) bentonite and cationic acrylamide a polymer, if desired, in combination with ATC and/or a compound; (iv) a combination of cationic poly-SI's preferred cationic powder, and an anionic step-growth compound, preferably re-elected 1H an an anthraquinone condensation polymer; if desired, in combination with ATC and/or a compound; + (v) a cation (four) 'preferably a cationic powder, in combination with a naturally occurring aromatic anion acceptor and a modified substance thereof, preferably And sulfonated lignin, if necessary combined with ATC and / or | g compound; (v: l) cationic chain growth polymer, preferably cationic propylene amide amine polytrim and anion step-growth polymer combination, Optimum and anionic table-based condensation polymers;; can be combined with ATC and / or aluminum compounds as needed; (vii) cationic chain growth polymer, preferably cationic acrylamide-based poly- agglomerates and naturally occurring aromatic anionic polymerization a combination of a substance and a modified substance, preferably and a lignin, optionally combined with ATC and/or an enchant; (111) a cationic chain growth polymer, preferably a cationic acrylamide polymer, and ATC combination. In the process of the present invention, the retained component is introduced into the HC stream, which is preferably /, LC/claw, preferably in the headbox, whereby the component is introduced into the produced stream of the dilute long-order t. When a retention system containing more than one component is used, the composition can be added to the original, preferably at a different point, in the conventional manner. When an anion-containing inorganic particle and a cationic polymerization system are used, it is preferred to add a cationic "material to the Hc feed stream prior to the addition of the particulate material, even if the opposite order of addition can be used. The roll uses a cationic and anionic organic polymer. In the case of a retention system, it is preferred to 'add a cationic polymer to the HC starting material before the anionic polymer,' so that the opposite order of addition can be used. More preferably, before the shearing stage, the second can be selected from the system. , mixing, washing, etc. 'adding a first component, such as a hazelnut polymer, and after the shearing stage, adding a second component, such as: a sub-inorganic microparticle or an organic polymer. When using a low molecular weight cationic polymerization machine Preferably, when it is #ΑΚ, it is introduced into the HC raw material stream before or at the same time as the other retained components. When the aluminum compound is used, it is preferably introduced into the HC raw material stream before or at the same time as the other retained components. The components of the retention system are introduced into the raw material, which will be dehydrated, and the amount of dehydration can be in a wide range β, especially depending on the type and number of ingredients, raw materials. , filler type, filler content, addition point, eight-day inch. Through hanging, the addition amount of the knife 9 can obtain better retention than when no component is added. When an anionic inorganic polymer is used as the particulate material, it is added. The total amount is usually at least 0.001% by weight, often at least 0.005% by weight, based on the dry matter weight of the raw material. The upper limit is usually 丨.0% by weight, and suitably 〇·6% by weight. When an anion 矽 is used. In the case of the stone-based particles, the total amount is suitably in the range of 0.005 to 0.5% by weight, which is calculated as Si〇2 and is preferably in the range of 0.01 to 〇·2% by weight based on the dry raw material. Polymers, such as cationic and anionic polymers, usually added in a total amount of two: 20 1278555; in the middle of the towel hanging at least, 〇.005% by weight 'this is based on dry raw materials, soil-based upper limit is 3% by weight And suitably 1.5% by weight. When a low molecular weight cationic organic polymer is used as the atc, the amount directly introduced into the raw material stream is at least U1% based on the dry raw material, and the amount is In 〇.〇5% to 〇.5%. When the compound is used in the process, the total amount of the raw material to be dehydrated is determined depending on the type of the compound used and other desired effects from the other. For example, it is well known in the art to use the compound as a rosin-based knee-applying agent. The total amount added is usually up to v 0.05% 'this is calculated as Al2〇3 and is based on dry raw materials. Suitable amount is in the range of 0.08 to 2.8%, preferably within the range According to the invention, the low molecular weight cationic organic polymer is introduced into the LC stream which is to be σ with the HC machine, preferably in the dilution headbox. Suitable low molecular weight (hereinafter referred to as LMW) cationic organic polymer These include linear, branched and crosslinked polymers, usually highly charged, which can be derived from natural and synthetic sources. Suitable LMW cationic organic polymers include (4) degraded poly-branches, such as based on temple powder, guar gum, cellulose, chitin, chitosan, polysaccharides, polygalactose, poly(tetra)ose, xanthan gum, Pectin, polymannose, dextrin' is better for temple powder and melon, suitable for temple powder including horse potato, corn, wheat, cassava, rice, waxy corn, barley, etc.; (10) cationic ethylene addition polymerization , such as acrylic acid vinegar, acrylamide, vinylamine, ethylene amide, and allylamine polymers, such as homo- and copolymers based on diallyl didentate Based on dipropyl dimethyl chloride chlorinator' and (meth) acrylamide and (meth) acrylate vinegar; and cation 21 21278555
子逐步生長聚合物，例如陽離子聚醯胺基胺、聚乙烯亞胺 、聚胺，例如二甲基胺-環氧氯丙烷共聚物及聚胺曱酸酯 。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, 000，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, 000, 000，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 流中當作滯留劑或滯留系統的一部分之情況中，加到LC流 的LMW陽離子有機聚合物之重量平均分子量係低於加到HC 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· 01%。適合地，該量係 在〇· 05至1· 〇%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 水合物的LC流導入含一或多種滯留成分的Hc流内以形成 生成水流後，沒有其它滞留成分導入該生成水流中。該生The polymer is gradually grown, such as a cationic polyamidoamine, a polyethyleneimine, a polyamine such as a dimethylamine-epichlorohydrin copolymer and a polyamine phthalate. The LMW cationic organic polymer typically has a weight average molecular weight of at least 100,000, suitably at least 500,000, and preferably at least 1, 〇〇〇, 〇〇〇, and usually up to 5,000,000, suitably Up to 3,000,000, and preferably up to 2, 〇〇〇, 000. Typically, in the case where a cationic organic polymer is added to the HC stream as part of a retentate or retention system, the weight average molecular weight of the LMW cationic organic polymer added to the LC stream is lower than the cationic organic added to the HC stream. Polymer. The amount of the LMW cationic organic polymer added to the LC stream is at least 〇·01% based on the dry matter of the raw material to be dehydrated. Suitably, the amount is in the range of 〇·05 to 1·〇%, preferably in the range of 〇·1 to 〇·5%. In a preferred embodiment of the invention, after the LC stream containing the LMW cationic organic hydrate is introduced into the Hc stream containing one or more retentate components to form a water stream, no other retentate components are introduced into the resulting water stream. The student
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费 吁液，且其特別有用於由具有高導電度的原料來製造紙4 在忒情況中，在漉網上被脫水的原料之導電度通常係^ 、· 5mS/cm，適合地至少 3· 5mS/cm，且較佳 5· 〇ms/cm。The formation of the water stream preferably takes place in the front tank of the dilution grid, but may also occur outside the headbox. - the process of the invention can also be applied to all papermaking processes and cellulosic liquids, and it is particularly useful for the manufacture of paper from a material having a high electrical conductivity in the case of a crucible. The conductivity is usually ^, 5 mS/cm, suitably at least 3.5 mS/cm, and preferably 5 〇ms/cm.
可使用標準器材’例如.istian Berner所供應的WTW L 、+義-來'則里導電度。上述所指的值係以藉由測量凑 皮噴射到漉網上以被脫水的生成水流之導電度來決定。高 22 !278555 導電度意味高鹽（電解質）含量，其通常來自用於形成房料 ， 的材料、來自導入原料内的各種添加劑、來自供應於掣呈 . 的新鮮水，等等。再者，鹽含量在白水被大量循環的製^ 中通常係較高的，其將導致鹽可觀地累積在製程的循環水 中。 本發明更涵蓋造紙方法，其中白水被大量循環或再循 ， 衣，即具有高度的白水密封，例如所製造的每噸乾紙係使 、 用〇至30噸的新鮮水，通常每噸紙使用少於2〇噸的新鮮 水，適合地少於15噸，較佳少於1〇噸，且特別地少於$ φ 頓。、可在任何階段將新鮮水導入製程中，例如新鮮水可混 合纖維素纖維以便形成一種懸浮液，且新鮮水可與一含= 維素纖維的i農料液混合以稀釋它，俾形& 一種稀懸浮液 其¥作南稠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「 氏」田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 ，型的纖維素纖維懸浮液來製造紙，且該懸浮液應適當地 _ ,有至少25重量%以乾物質重量為基準的該纖維，較佳至 夕50重！ ％。懸浮液可以來自化學紙浆的纖維為基礎，如 以&酸鹽及亞硫酸鹽、紙漿、熱機械紙漿、化學-熱機械紙 裝、有機溶劑紙褒、精碎紙漿或來自硬質木材和軟質木材 的〜木紙漿，或得自_年生植物，如象草、蔗潰、亞麻、’ #曰草等等’且亦用於以回收纖維為基礎的懸浮液。本發日月 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 1278555 液亦含有傳統類型的礦物填料，例如高嶺土、黏土、二氧 化鈦、石膏、滑石以及天然和合成碳酸鈣，例如白要、重 貝大理石重貝石灰酸鈣及沈澱碳酸鈣。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、乙烯酮二聚物、乙烯綱多聚物、烯基琥珀酐等為基 礎者。 適口地本發明係應用於造紙機，其用於製造含木材 的紙及以回收纖維為基礎的紙，如sc、lwc及不同類型的 書=或新聞紙’及應用於無木印刷紙及筆記紙之製造用的 機器’術語無木係意味少於、約15%的含木纖維。本發明亦 可應用於在早層機器上，以及在多層網前箱中製造紙或紙 板的機Si ’及在具有數個網前箱的機器上製造紙板，其 中-或多層本質上係由时纖維所構[在使用多層網前 箱或數個網前箱的機器巾，用稀釋型網前箱來製造—或多 層’本發明可應用於這些層之-或多冑。適合地，本發明 係應用於以300 ? ?Rnn八π /、 至心00公尺/分鐘運轉的造紙機，且較佳 為1 000至2000公尺/分鐘。 以下只轭例更進一步說明本發明，然而本發明不意欲 受該些實施例所限制。除非另有指明，否則份及%係：二 指重量份及重量％。 【實施方式】 實施1 用不同的LMW陽離子有機聚合物當作LC原料的添加劑 24 1278555 來減驗本發明的的方法。 在利用稀釋網前箱以製造sc級的造紙機上，由纖雉素 懸吁液來製造紙。將滯留劑加到HC原料；首先8公斤， 其為以每噸具有重量平均分子量約丨百萬的二甲基胺_環氧 氯丙烷共聚物的乾成品為基準，然後〇· 36公斤，其為以每 頓具有重里平均分子量約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。 將500毫升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 及混合30秒。就空白試驗而言，將原料加到一動力瀝 乾槽内，及在l〇〇〇ppm混合45秒，但不添加LMW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;慮的部份之木瀝青含量的表示。 在相同的乾劑量（以LC原料乾物質為基準約4公斤/噸 ，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-環氧氯丙烷共聚物； LMW-2為一種具有重量平均分子量約1〇〇〇,〇〇〇的二 曱基胺-環氧氯丙烷共聚物； LMW-3為一種具有重量平均分子量約680, 〇〇〇的聚二 烯丙基二甲基氣化銨；及 LMW-4為一種具有重量平均分子量約18〇〇,〇〇〇的聚 25 1278555 二烯丙基二甲基氣化銨。 與空白試驗比較下，所有依本發明的 々凌係顯示減少 的uv吸收。依本發明最有效的方法係為採用且 /、有重量平均 分子量約1，800, 000的聚二稀丙基二甲基氣化錢者。- 這些試驗摘述於表1中，其顯示依本發明的方法 應於先前技藝的空白組在不同波長的uv吸收度。Standard equipment such as WTW L, + meaning-to-send conductivity supplied by .istian Berner can be used. The values referred to above are determined by measuring the conductivity of the generated water stream which is sprayed onto the web to be dehydrated. High 22 !278555 Conductivity means high salt (electrolyte) content, which is usually derived from the materials used to form the materials, from the various additives introduced into the feedstock, from fresh water supplied to the crucible, and the like. Furthermore, the salt content is generally higher in the process in which white water is largely circulated, which will result in a considerable accumulation of salt in the circulating water of the process. The present invention further encompasses a papermaking process in which white water is recycled or recycled in large quantities, i.e., has a high degree of white water seal, such as per ton of dry paper produced, used up to 30 tons of fresh water, typically per ton of paper. Less than 2 tons of fresh water, suitably less than 15 tons, preferably less than 1 inch, and especially less than $ φ. 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 an i-containing liquid containing weisu fiber to dilute it. A dilute suspension is sent to the headbox in the south consistency stream. The method according to the invention is used for the manufacture of paper. As used herein, the term "氏氏" includes not only paper and its manufacture, but also other web-like products such as board and paperboard, and the manufacture thereof. The process can be used to make paper from different types of cellulosic fiber suspensions, and the suspension should suitably have at least 25% by weight, based on the weight of the dry matter, of the fiber, preferably up to 50 weights! %. Suspensions can be based on fibers from chemical pulp, such as & acid salts and sulfites, pulp, thermomechanical pulp, chemical-thermo-mechanical paper, organic solvent paper, finely ground pulp or from hardwood and soft Wood ~ wood pulp, or from _ annual plants, such as grass, sugar cane, flax, '#曰草, etc.' and also used for recycled fiber based suspension. The present day is preferably applied to a method of making paper from a wood-containing suspension. The suspension 23 1278555 also contains conventional types of mineral fillers such as kaolin, clay, titanium dioxide, gypsum, talc, and natural and synthetic calcium carbonates such as white, heavy marble, limestone and calcium carbonate. The raw materials of course also contain conventional types of papermaking additives such as wet strength agents, raw material gels, such as those based on rosin, ketene dimer, vinyl polymer, alkenyl succinic anhydride and the like. Preferentially, the present invention is applied to a paper machine for producing wood-containing paper and recycled fiber-based paper such as sc, lwc and different types of book=or newsprint' and for wood-free printing paper and note paper. The machine for manufacturing 'the term wood-free means less than about 15% wood-containing fibers. The invention can also be applied to machines for making paper or paperboard in an early-layer machine, as well as in a multi-layer headbox, and on a machine having several headboxes, wherein - or more than one layer is essentially The structure of the fiber [in the case of a machine bed using a multi-layer net front box or a plurality of head boxes, made with a dilute head box - or a plurality of layers] the invention can be applied to these layers - or multiple layers. Suitably, the invention is applied to a paper machine operating at 300 ? Rnn 八 /, to a center of 00 meters / minute, and preferably from 1 000 to 2000 meters / minute. The invention is further illustrated by the following yoke, but the invention is not intended to be limited by the examples. Unless otherwise indicated, parts and % are: two parts by weight and % by weight. [Embodiment] The method of the present invention was carried out by using 1 different LMW cationic organic polymer as an additive for the LC raw material 24 1278555. On a paper machine using a dilution head box to produce an sc-stage, the paper is made from a cellulosic suspension. Retention agent is added to the HC raw material; first 8 kg, which is based on a dry product of dimethylamine-epichlorohydrin copolymer having a weight average molecular weight of about 10,000 per ton, and then 36 kg, It is based on a cationic polyacrylamide having a weight average molecular weight of about 4.6 million per ton. The Lc raw material is obtained by draining the raw material. 500 ml of LC material was added to a power drain tank and mixed at 1000 ppm for 15 seconds, and then the LMW cationic organic polymer material was mixed and mixed for 30 seconds. For the blank test, the feedstock was added to a power drain and mixed at 1 Torr for 45 seconds without the addition of LMW cationic organic polymer. The obtained raw material was then drained, and the filtrate was collected to pass through a 1 micron filter. The uv absorbance was measured using a 〇cean Optics S2000 UV spectrophotometer with a fast scan rate as a representation of the wood pitch content of the treated portion. At the same dry dose (about 4 kg/ton based on dry matter of LC raw material, corresponding to about 2 kg/ton based on the total dry matter volume tonnage). LMW-1 is a dimethylamine-epichlorohydrin copolymer having a weight average molecular weight of about 12 〇, 〇〇〇; LMW-2 is a ruthenium having a weight average molecular weight of about 1 〇〇〇, 〇〇〇 a base amine-epichlorohydrin copolymer; LMW-3 is a polydiallyldimethylammonium vaporate having a weight average molecular weight of about 680, 〇〇〇; and LMW-4 is a weight average molecular weight of about 18 〇〇, 聚 Poly 25 1278555 Diallyldimethylammonium hydride. All of the sputum lines according to the present invention showed reduced uv absorption compared to the blank test. The most effective method according to the present invention is a polydipropyldimethyl methoxide which employs and/or has a weight average molecular weight of about 1,800,000. - These tests are summarized in Table 1, which shows the uv absorbance at different wavelengths of the blank set according to the prior art according to the method of the present invention.
26 1278555 表1 :在不同波長的UV吸收度 UV吸收度 波長nm 空白組 LMW -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 1278555 Table 1: UV absorbance at different wavelengths UV absorbance wavelength nm blank group LMW -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. 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 0.58 9 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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