200819491 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種高吸水性樹脂的製造方法，尤其是一種可 溶物含量低的吸水性樹脂的製造方法。 鬲吸水性樹脂具有強大的保水力，可吸收百倍甚至於千倍於本 身重量的水’且吸水後可膨潤具有保持不流動的狀態，即使施加 壓力也不會滲漏，且被吸收的水可緩緩地在大氣帽&。由於具 有上述之特性，所以最早朗於農森浦的土雜水劑，近年因 ，吸水性樹脂的生產技術有相當大的進步，所以也廣泛地運用於 衛生用品如尿布、成人失禁用品及婦女衛錢品的吸水劑及保存 食物用的保鮮應用等。 【先前技術】 面吸水性樹脂的成分材料有遇水分解型的澱粉丙烯腈 (=ydr〇iyzed starch_acryl〇niwie)接枝聚合物（日本專利公報 =49⑽4)~43,395 )，中和之殿粉丙烯酸接枝聚合物（日本專利 I報日Q 51 (1976)-125, 468)，皂化乙烯醋酸丙烯醋共聚物（日 開公報昭52(1977)_14, _，水解丙烯腈共聚物或_ =胺共聚物（日本專利公報昭53 (197δ)_ΐ5，叫及部份中和 來丙稀酸（日本專利公開公報昭55(1980)-84,3()4) #。其中以 200819491 使用丙^及_酸鹽進行交聯聚合所得之高吸水性樹脂佔最大 P伤也最為、、工其原因為丙烯酸可迅速由市售取得，且紫得的 ^及水性聽財高的财能力，及具有製造成本低廉且最具經 …效血’故成為最普遍化的高吸水性樹脂。 XK 口丙烯酸及丙稀酸鹽形成高吸水性樹脂的方法已被多方面 2開發成功’且有多種已應用於卫業界生產，其聚合方法有鑄膜 =合反應（日本專利公報昭48(1973) _42,466)，於輸送帶上進行 聚合反應（日本專利公開公報昭58(1983) -49,714)，粉碎之授 拌刀片的轉機巾進行聚合反應（日本專利公開公報昭 57(1982)-34,101) ’進行勒驗液聚合反應（日本專利公開公 報日σ 59(1984)-37, _)’或將單體喷灑或塗覆於纖絲質上進行 聚合反應（日本專利公開公報昭62(1987)-53,309)。 【擬解決之課題】 上述聚合方法大多是將聚合單體、聚合引發顺交聯劑等反 應原料-同進行自由絲合反應喊娜狀_，如此整個聚合 反應不易控制，可溶物含量也較高。 【解決問題之技術手段】 t於此，本發明提供一種高吸水性樹脂的製造方法，其聚合 反應過程姆來說較為狱，反賴也不致於過高，除了改善操 200819491 作環境之外，更提高了產品質量。本發g_提供的製造方法至小 包括： / 1) 使中和率5G mole%以上之含酸基單體水溶液與聚合反應 引發劑於管線中滞留，進行自由基聚合反應而得到預^物: 2) 添加親水性多元環氧基化合物於預聚物中，並於管線出口 處以光照的方式引發預聚物轉變成高分子量的黏祠液體； 3) 黏雛體由直立式反觸上方人料，#勘底部液體轉變 成膠體時，槽絲封機構即開啟，而條會帶轉體向下 移動’並進行絞碎與造粒的步驟； 4) 以/皿度100 C至250 C熱風進行乾燥、粉碎、篩選； 5) 表面交聯劑塗覆處理； 6) 溫度80°C至230°C加熱表面處理； 7) 添加惰性無機鹽粉末。 預聚合反應可以在一個預聚合反應器中進行，該反應器需具 備能夠使聚合反應原料混合均勻且進行預聚合的作用。預聚合反 應器除了可以採用一般安裝有攪拌葉的反應槽外，也可採用一種 臥式的筒狀容裔，中心安裝有使物料單向流動的攪拌葉、單螺桿 或並列之雙螺桿。這樣可以保證反應物料單向向前運動而不出現 回流的現象，從而避免了聚合反應物料在反應器中停留時間過長 而形成旋膠狀固體。表後，黏稠的反應物料排出至皮帶反應器上 進而硬化成膠體。 200819491 上述類型之反應器通常採用批次 化生產，且末段之皮帶反應器佔地大不利於工業 一大阻礙。麟此，本發明脖—種可、^成4未來增加產能的 量之高吸水賴脂财法，財法具觀可溶物含 瞢綠中、，此取人 特徵在於將單體溶液滯留於 p反丨制加人至管線中使麵基單體進行自由基 物混合，並騎«σ;分顿魏基化合 5糾口處以方式(例如：水銀燈、Α素燈、 =外線或I射線等)使預聚物轉變成分子量更高的細液體 後，使黏_反應簡由-直立歧應槽上方人料，當槽内底部 液體硬化祕體時’密職構即，㈣體齡藉著二個 以上滾輪的帶_向下移動，並進人下—步之賴絞碎與造粒步 •上述本發明之特徵，第—步是_含酸基之單體溶液於管線 中滯留’並將聚合引發劑加人至管線中，使其進行自由基聚合反 應而成黏_高分子。第二步，將魏基化合物加人至管線中， 並於管線出口處以光照方式使上述預聚物的分子量與黏度提高。 最後，再將高黏度之預聚物由一直立式反應槽上方入料，當槽内 底部液體轉變成膠體時，槽底密封機構即開啟，而輥輪會帶動膠 體向下移動，並進入絞碎與造粒的步驟。 於官線中進行預聚合除了較一般反應槽或筒狀容器節省空間 外，更能夠確保反應單體水溶液先進先出的原則，使得預聚合過 9 200819491 程裡無反應早體朗於管射，進而降絲合反應過度的情形發 生。反應物料於管線中的滞留時間，係為本發明控制預聚合反應的 重要因素，如滞科·，咖聚合反應越完全，縣物黏度與 分子置也私’成品的可溶份也較低，但較容紐生於管線中過 度聚合的現象。如滯留時間短，則預聚物黏度與分子量較低，成 品可溶份較高，但發生過度聚合的機會較少。此外，反應單體水 溶液與聚合服劑，乃至照光反麟之縣物與架橋劑的混合均 勻性也疋響預聚合反應與照光反應的重要因素。為了提高上述 各流體彼此之間的混合效果，通常可使用下列方法··（丨）於管線中 通入惰性氣體，如··氮氣、或二氧化碳、或氦氣、或氖氣、或其 混合氣體，（2)於管線中加裝螺旋葉片或具混合效果的填充物 如：拉西環、或波耳環，（3)使用汽液型靜態混合器。 本發明的預聚合反應共分兩段，前段於管線中進行，後段則 經由光照引發後於直立式反應槽中進行。鑑於此，管線出口處的 光照時間也是影響預聚合反應的重要因素之一，通常控制在丨〜卯 秒之間，以5〜15秒之間為佳，照度以3. 〇3J/cm2〜9. 35J/em2。 最重要的是’後段之預聚物係於直立式反應槽内硬化成膠 體，此直立式反應槽係由一長方體反應槽〇)，槽體由不鏽鋼焊接 而成，一槽頂（2)設有一反應物料入料管（2a)與一氮氣管（2b)，一 槽底具有一密封機構而該機構為一活動式閘門（3)，及在密封機構 200819491 上具有至少-健輪⑷所構成，除了較一般輸送帶式反應器節省 空間之外，也能夠與後段膠體絞碎與造粒的機構相銜接。這項直 立式反應槽除了能夠簡化工廠設備的配置之外，更可以成為未來 擴充產能上佔一大優勢。 本發明所製造之高吸水性樹脂所需的含酸基單體除了丙稀酸 外，尚可使用其它具有不飽合雙鍵的水溶性單體，如：甲基丙婦 酸、或馬林酸、或富馬酸、或2一丙烯胺甲基丙烧石黃酸等:單體 選用不特定關只可使用-種，亦可合併多鮮體—齊使用，^ 可視情況需要添加具有不飽和雙鍵其純水性的單體，如：丙稀酿 胺、甲基丙烯醯胺、丙烯酸2_烴基乙_、曱基丙烯酸2_烴基乙酿: :烯酸甲醋、丙烯酸乙酯、二甲胺丙烯丙烯醯胺、氯化丙烯丙； 驢胺基三甲齡添加量料破壞高吸水性樹脂之物性為原則。 在進行自由基聚合反應前，單體水溶液濃度宜控制在重量百分 比2〇Wt%至55wt%間，適當濃度為30wt%至45wt%之間，濃度在^ 量百分比2Gwtte下時，聚合後水合體太軟且有黏性不利機械加 工，添加濃度在重量百分比55wt%以上，接近飽和濃度，不易調配 且反應太快反應熱不易控制。 含酸基單體之羧酸基應部份中和以控制成品之即值，使呈中 性或微酸性，中和劑為氫氧碰、氫氧化納、氫氧化鉀、碳酸鐘、 碳酸釣、碳酸卸、礙酸氫鐘、碳酸氫納、碳酸氫卸及氨。含酸基 11 200819491 單體之羧酸基將部份中和成鋰鹽或鈉鹽或鉀鹽或銨鹽或兩種以上 混合鹽類，中和濃度莫耳百分比為45m〇i%至85mol%，適當濃度為 50mol%至75moU’中和濃度莫耳百分比為奶购丨％以下時成品之pH 值冒偏低’中和浪度莫耳百分比為以上時成品之pH值會偏 咼，成品PH值若非呈中性或微酸性時，不慎與人體接觸時均不太 適合也較不安全。 預聚合反應由聚合引發劑的分解產生自由基開始。聚合引發劑 •可選用熱分解型起始劑，適合的熱分解型起始劑有過氧化物，如： 過氧化氳、二-第三丁基過氧化物、過氧化醯胺或過硫酸鹽（銨鹽、 驗金屬鹽）等，及偶氮化合物如·· 2.2，—偶氮基雙(2—脉基丙烧)二 鹽酸鹽、2· 2’ -偶氮基雙(n，N一二伸甲基異丁滕）二鹽酸鹽；亦可 使用還原劑，使成為氧化還原型起始劑，如：酸性亞硫酸鹽、硫 代硫酸鹽、抗壞錯歧賴；或將氧化還原型起始劑和熱分解 型起始劑合併使用，首先氧化還原起始劑先進行反應產生自由 基，當自由基轉移至單體上即引發聚合反應的進行，由於聚合反 應進打時會釋放出大量的熱量而使溫度升高，當溫度到達熱分解 型起始劑的分解溫度時，又會引發第二段熱分解型起始劑的分 解’而使整個聚合反應更臻於完全。—般自由絲合反應起始劑 適當用量為重量百分比為〇· 〇_%至1〇韻以中和丙稀酸鹽重量 為基準），更適當用量則在〇·祕❶至5wt%之間，使用重量百分比 〇·〇_%以下時，反應太慢不利經濟效益；使用重量百分比腕％ 12 200819491 以上4 ’反應太快反應熱不緒制且料聚合過度而形成凝a 固體。 ’竣膠狀 進仃光起始聚合反麟應添加㈣劑稀麵聚 、阳 1 父聯齊| 可^用具有兩個或兩個以上不飽和雙鍵的化合物，如:N冬雙(2 丙烯基)胺、N，N -次甲基雙丙烯醯胺、N，N ‘―次甲基雙曱爲丙广 醢胺、丙烯酸丙烯酉旨、乙二醇二丙烯酸酉旨、聚乙二醇二内稀^酉广 乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、甘油三丙； W曰、甘油三曱基丙烯_旨、甘油附加環氧乙烧之三丙稀酸酿或 三甲基丙烯酸酯、三曱醇丙烧附加環氧乙烧之三丙烯酸喊三甲 基丙稀酸酯、三甲醇秘三甲基丙烯_旨、三甲醇丙垸三丙稀酸 酉曰、N，N，N-二(2-丙烯基)胺、二丙稀酸乙二醇酯、二丙稀三甘醇 @曰等’亦可翻具有兩碱兩個以上環氧基的化合物，如山梨醇 聚縮水甘_、聚丙三醇聚縮水甘_、乙二醇二縮水甘油鱗、 二乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、雙丙三醇聚縮 水甘油轉。錢行自由基反應魏可使高吸樣難具有適當 交聯度，而使高吸水性樹轉體有適當的加讀。自由基聚合反 應交聯劑可單獨使贼兩種以上混合使用。自由基聚合反應交聯 劑適當的添加劑量在重量百分比Q.QQlwt%s 5wt%之間（以反應物 總固形份為鮮），更適當咖量重量百分比在丨至㈣之 間’添加劑量在重量百分比〇 〇〇lwt%以下聚合後水合體太軟且有 黏性不利機械加工，添加劑量在重量百分比5wt%以上吸水性太 13 200819491 低，降低樹脂性能。 黏麵聚物可於觀帶式反脑上或財勝#之橫式反應 為中進行光起始聚合反應’製備出之高吸水性凝膠體先利用絞碎 機切成粒徑20刪以下小凝膠體，粒徑1〇咖以下更佳，再進行烘 乾0 本發明之烘乾奴可於刚。c至25(rc下進行乾燥，乾燥溫度 則以12GC至副。(：進行烘乾為宜’當烘乾溫度溫度12(rc以下則 供乾時間太久不具轉效益’烘乾溫度⑽。c以上烘乾使交聯劑提 早進行㈣反應’使得後續的乾燥過程中，因交聯度過高而無法 有效的去除殘存單體，達到降低低殘存單體之效果。 乾燥後進行粉碎、篩選固定粒徑，再進行表面交聯劑塗覆處 理。師選固定粒徑以〇 〇6刪至1〇〇刪間為宜，以〇.翻至 〇.850mm間較佳，粒徑〇6mm以下細粉使成品粉塵提高，粒徑 1· 00mm以上粒子使成品吸水速率變慢。 吸水性樹脂為不簡化之親水性聚合體，樹軸料有均句性 n:構般為了改善品質如：提高吸收速率、提高膠體強 H塊fi、液體渗透料’會在樹簡表面再作進一步 =此絲_她咖跑娜咖乡官能細 二、古此=已有許多專利提出；如：分散高吸水性樹脂與交聯 ^於機洛劑中進行表面交聯處理（JP-A-56-131608、 14 200819491 JP+57-44627、JP+58-426G2、IP-A58-117222)使用無機粉 末直接將交聯劑與交聯劑溶液混入高吸水性樹脂處理 (JP-A60-_56、】P-A鲁255814)，添加交制後以蒸氣處理 UP+1-11_) ’使时機溶劑、水及多元醇進行表面處理 (JP-A-63-270741 > JP-A-64-50707 > JP-A-1-292004) 溶液、水、醚（ether)化合物（Jp_A_2_1539〇3)等；這些表面 處理的方/έ雖⑧吸收速率提高壓力下吸水倍率，但將造成保 持力下降過多的不良後果，降低實際應用之性能。 上根據本發明，筛選固定粒徑後於表面處理時能同時進行反應的 父聯劑可為多元醇如：丙三醇、乙二醇、二乙二醇、三乙二醇、 艰乙一知丙―知、！，4 丁二醇、三烴基曱基丙烧、山梨醇等；或 可使用多元胺如··乙二胺、二乙二胺、三乙二胺、聚乙二胺；或 可使用具有兩個或兩似上環氧基的化合物如：山梨醇聚縮水甘 趣、聚丙三醇聚縮水甘_、乙二醇二縮水甘油_、二乙二醇 二縮水甘_、聚乙二醇二聚縮水甘_、雙^㈣縮水甘油 科，亦可使用碳酸亞煙酉旨如：乙二醇碳酸醋、4〜甲基义3_二氧 雜環戊烷―2’、4’ 5m 3-二氧轉戊烷-2-酮、4’4-二甲 基3-二氧雜環戊燒相、4_乙基乂 3_二氧雜環姐+酮、 ，二，轉己龄，、4,6m 3—二氧雜環己燒㈣威 種以7T嫩-2娜。表面處交聯細法可單獨使用或雨 心使用。表面處交聯劑的適當添加剩量在重量百分比 15 200819491 0.00M至l〇wt%之間（以反應物總固形份為基準），更適當的用旦 在〇.〇幌%至5wt%之間，表面處交聯劑添加劑量在重:百分^ O.OOlwU以下時無法_效果，表面處交聯舰加舰在重量百 分比10wt%以上時，吸水性太低，降低樹脂性能。 表面交聯劑塗覆處理時，表面交聯劑之添加可為表面交聯劑直 接添加，或調成表面交聯劑水溶液添加，或調成表面交聯劑親水 性有機溶劑水溶液添加。親水性有機賴如甲醇、乙醇、丙醇、 異丁醇、_、㈣、乙轉沒有特殊限制，可形成溶液即可， 其中以甲醇、乙醇較佳。表面交聯劑添加時高吸水樹脂中可添加 惰性無機聽末’叫助溶較散’舰無機贿材為硫酸銘、 或二氧切，或氧她，或氧傾等或其混合物，其中以硫酸銘、 二氧化雜佳。·無機末添加翻在重量百分比Q.嶋找 至10. OwU之間，其中以〇. 〇1^%至4. 〇的％較佳。 進行表面交賴塗覆處理後，再以啊至2机減處理，使 表面交聯舰進行交聯反應，並使内部交聯舰行交聯反應而達 至体發明之效果。處理溫度8{rc以下交聯反應時間太久，不具經 濟效ϋ ’處理溫度g23(rc時’樹脂易劣化影響品質。至於處理時 間則以2〜150分鐘為宜，依處理溫度調整，溫度高則時間短，溫 度低則時間長。 由於砂水性翻旨具有賴後結塊的财，為避免在高濕度地 16 200819491 區使用高吸水性樹齡有吸濕後結塊導致加卫不順，合一 吸水性樹脂表面塗附惰性無機鹽粉末或界面活性劑會在高 親油性而使高吸水_絲顿祕Μ結塊二略具 機鹽粉末可選用硫酸紹、或二氧化石夕、或氧化^或氧== ^簡、或高駐、或碳_、或碳酸鮮或其混合物。通常此 惰性無機藤柄添加量與無機麵末雕純大,〗、 粒粒徑較小其無機胁末絲錄A，職有靖^末 用量可較小，其惰性無機鹽粉末添加範圍為重量比百现分比 〇. 005撕1〇Wt%之間，其中則.觀4. _較佳。惰性無 機鹽粉末其粒徑為〇.謝—至，若選用顆粒小於◦ 〇_ Μ的無機贿末職本過私觀4化生產，若翻顆粒大於 1〇〇鎖的無機鹽粉末則有添加量過高影響高吸水性樹脂吸收力的 問題。惰性錢錄末可單縣域可雜界面活賴或具枯度 有機化合物加入。其界面活性劑或具枯度有機化合物可選用則 值12以上非離子性界面活性劑、或水溶性陰離子型界面活性劑、 或陽離子1界面性劑、或陰陽兩性型界面活性劑、或其混合物。 通常界面活_或擁度有機化合物可使用甘油、乙二醇、己六 醇承氧乙稀醇、或聚乙一醇、或硬腊酸聚乙二醇醋、或硬脂酸 醇己/、Sa、或聚氧化乙稀壬苯趟、或聚氧化乙稀辛苯趟、 或聚氧化乙料H絲減乙舰細、絲氧化乙稀月 4t鍵等此界面活性劑或具粘度有機化合物可調配成水溶液型態加 17 200819491 入或單獨加入，適當的界面活性劑或具粘度有機化合物添加劑量 在重量百分比0· OOlwt%至5wt%之間（以反應物總固形份為基準）， 更適當的用量重量百分比在〇.〇lwt%至3wt%之間。 本發明提供一種可連續生產具低可溶物含量之高吸水性樹脂 的方式，其步驟為：第一步，利用含酸基之單體溶液於管線中滯 留’並將聚合f丨發劑加人至管線巾，使其進行自由絲合反應而 成黏稠的高分子。第二步，將環氧基化合物加入至管線中，並於 官線出口處以光照方式使上述預聚物的分子量與黏度提高。最 後，高黏度之預聚物由-直立式反應槽上方人料，#槽内底部液 版轉變成賴時，槽底密封機構即開啟，喃輪會帶動膠體向下 移動，並進行絞碎與造粒的步驟。透過此生產方式，除了節省空 間外，更能夠確保反應流體先進先出的原則，而達到連續式生產 的目的。本發明所提供之高吸水性樹脂製造方絲了提高生產操 作性、工廠設備簡倾節省操触間外，產品質量也大大提高， 尤其對於降低可溶物含量具有很明顯的效果。 _為€不本發明高吸水性樹脂的低可溶物含量之特性，可溶物 ^的測定步驟如下：先秤取〇· 5 g高吸水性樹脂，再加入〇· 9 心鹽水185 g，纟__轉速下授拌一個小時後，以濾紙過濾 出SAP萃取液。取後，秤取該萃取液2〇容，先以〇·劃_滴定， 再使用G.1N HC1進行反滴定以求出SAp可溶物的含量。 18 200819491 【實施方式】 以下以實施例說明本發日月，但本發明範圍不受這些實施例所限 制。 實施例一： (1) 先於中和槽中加入1760重量份的丙烯酸及2263·7重量份的 水’之後於冰洛下將1476· 3重量份的氫氧化納水溶液(濃度為 45%)緩緩加入上述丙烯酸水溶液中。此時得到單體濃度為 38· 6wt%的水溶液，其中有68 mol%的丙烯酸中和為丙烯酸納。 (2) 中和程序完成後，利用調溫水控制部分中和之丙烯酸納鹽水溶 液為20°C左右。 (3) 調整上述單體溶液的流量為1〇()公升/小時，使其通過一支直 仅為5公分、總長度為25· 48米的不鏽鋼管。此外，不鏽鋼管 入端5公分與1〇公分處侧邊分別連接一支直徑〇· 5與〇· 9公 分的不鏽鋼管。前者導入氮氣，流量控制為2〇〇公升/小時， 後者則通入過硫酸卸/亞硫酸氫納= 1/1(重量比），流量控制為 2晕:升/小時。預聚和反應溫度控制在2〇°c，所得之預聚物魏 度為 78· 5cps。 (4) 距離管線出口端85公分處側邊連接二支直徑〇· 9公分的不錄 鋼管，一支導入偶氮二異庚月青，流量控制為2〇毫升/小時， 19 200819491 另糾導入丙二醇聚乙二醇三縮水甘油驗(㈣），流量控制 為15毫升/小時。 ⑸錄出咳裝置有高強度料線照賴，细棘置照射上述 混合液體5秒（照度=3. 03J/cm2)。 ⑹混合液體由直立式反應槽(請參考附圖）上方之入料，待槽内液 2硬化_後，_峨_啟，鱗_由滾輪的 帶動而向下。 ⑺利用切錢碎機紅轉體域2mm錄町峡膠體。 (8)以130 C溫度乾燥2小時；利用篩網篩選G. i咖ϋ固定 粒徑，得粉狀高吸水性樹脂。 ⑼秤取此高錄_ 1(%，加人硫_縣&，待混合均句 後再加入乙二醇碳_/水/¥醇=1/1/1(重量比)溶液包，以 215 C溫度加熱處理10分鐘。 〇〇)冷卻後’加入lg碳酸辦台塑公司生產品名糊 X合液2g均勻混合後即得高性能高吸水性樹脂。測定 保持力-33.5g/g ’ 49 g/cm2壓力下吸水倍率=2 可 溶物含量= 10. 7%。 · 實施例二： ⑴重複實施例一，料照時間改為15秒(照度為9. 35J/cm2)，所 得之高吸水性樹脂的保持力則為3G. lg/g，49 g處力下吸 水倍率= 22.6g/g’可溶物含量二⑽。 20 200819491 實施例三： ⑴重複實施例-，但獨鋼管總長纽為5i. 25米長，所得 物黏度為205cps;所得之高吸水性樹脂的保持力為36的， 49 g/cm2壓力下吸水倍率i.lg/g，可溶物含量=90%。 實施例四： ⑴重複實施例三’但光照時間改為15秒(照度為9•如㈤，所 得之高吸雜__持力為32 9g/g，49⑽壓力下吸水 倍率= 23· 3g/g，可溶物含量=1〇· 8%。 實施例五·· ⑴先於中和槽中加入重量份的丙烯酸及2263 7重量份的 水’之後於冰浴下將1476. 3重量份的氫氧化納水溶液(濃度為 45%)緩緩加入上述丙烯酸水溶液中。此時得到單體濃度為 38· 6wt%的水溶液，其中有68 mol%的丙烯酸中和為丙烯酸鈉。 (2) 中和程序完成後，利用調溫水控制部分中和之丙烯酸鈉鹽水溶 液為20°C左右。 (3) 调正上述單體溶液的流量為1〇〇公升/小時，使其通過一支直 控為5公分、總長度為26· 35米且内部充滿直徑5_拉西環的 不鏽鋼管。此外，不鏽鋼管入口端5公分與1〇公分處侧邊分 別連接一支直徑〇· 5與〇· 9公分的不鏽鋼管。前者導入氮氣， 流置控制為200公升/小時，後者則通入過硫酸鉀/亞硫酸氫鈉 21 200819491 一 1/1(重量比）’流量控制為2毫升/小時。預聚和反應溫度控 制在20°c，最後所得之預聚物黏度為113. 5cps。 ⑷距離管線出口端85公分處側邊連接二支直徑Q· 9公分的不錄 鋼5 ’ -支導入偶氮二異庚月#，流量控制為2〇毫升/小時， 另支則導入丙二醇聚乙二醇三縮水甘油峻(n=7)，流量控制 為15毫升/小時。 ⑸管線丨Π歧置有高強度料_賴，细職置照射上述 混合液體5秒（照度=.3. 03J/Cm2)。 ⑹此口液版由直立式反應槽（請參考附圖）上方之入料，待槽内液 肢硬化祕體後，槽絲峨構即顺，而雜會藉由滾輪的 帶動而向下。 ()利用刀式、、、交碎；^將上述膠體切成2麵直徑以下的凝膠體。 ⑻以13(TC溫度乾燥2小時；利用篩網_ G. imm〜〇. 85腿固定 粒徑，得粉狀高吸水性樹脂。 ⑼秤取此高吸水性樹脂_，加人硫酸鱗末lg ’待混合均勻 後再加入乙二醇碳酸醋/水/甲醇=1/1/1(重量比)溶液始，以 215 C溫度加熱處理丨〇分鐘。 (10)冷πΡ後加入lg碳酸詞（台塑公司生產品名·U_)及⑽ 甘油水岭液2g ’均勻混合後即得高性能高吸水性樹脂。測定 保持力一34.6g/g ’ 49 g/cm2壓力下吸收倍率= 23.7g/g，可 溶物含量= 8.1%。 22 200819491 實施例六： ⑴重複實施例五，照射時間為i5秒(照度為9.35關，所得 之冋吸水性樹月曰的保持力為32.軌，奶⑽壓力下吸收倍 率= 23.〇g/g，可溶物含量料胱。 實施例七·· ⑴重複貝施例五’ 不鏽鋼管總長度52· 75米，所得之預聚物黏 度為挪·㈣；所得之高吸水性樹脂的保持力為38· lg/g，49 g/cm壓力下吸收倍率為23·阶，可溶物含量為 實施例八： ⑴重複實施例七，但光照時間為15秒(照度為9. 35J/cm2)，所得 之高吸水性樹脂的保持力為35. 9· lg/g，49 g/cm2壓力下吸收 倍率為22.9g/g，可溶物含量為9 3% 實施例九： ⑴先於中和槽中加入176〇重量份的丙稀酸及纖.7重量份的 水。，之後於冰浴則476. 3重量份喊氧蝴水溶液(濃度為 45.緩加入上述丙烯酸水溶液中。此時得到單體漢度為 38· 6爾水溶液，其中有68 _的丙烯酸中和為丙稀酸納。 ⑵中和程序完碰，_調溫水控制部分巾和之__鹽水溶 液為20°C左右。 ⑶調整上述單體溶液的流量為⑽公升/辦，使其通過一支直 23 200819491 位為5公为、總長度為27. 20米的氣液型靜態混合器（礙牌· N0RITAKE)，其螺旋葉片混合部分長度為30公分。此外，不鐵 鋼管入口端5公分與1〇公分處側邊分別連接一支直徑〇· 5與 0· 9公分的不鏽鋼管。前者導入氮氣，流量控制為2〇〇公升/ 小時，後者則通入過硫酸鉀/亞硫酸氫鈉= 1/1(重量比），流量 控制為2毫升/小時。預聚和反應溫度控制在2〇它，最後所得 之預聚物黏度為lOlcps。 (4) 距離管線出口端85公分處侧邊連接二支直徑〇· 9公分的不鏽 鋼管，一支導入偶氮二異庚月青，流量控制為2〇毫升/小時， 另一支則導入丙三醇聚乙二醇三縮水甘油醚(n=7)，流量控制 為15毫升/小時。 (5) 將（4)所述之反應流體加入到傳送帶上，傳送帶上方|置有高 強度紫外線照射機，利用該裝置照射上述混合液體5秒（照度 =3· 03 J/cm2) 〇 (6) 管線出口處裝置有高強度紫外線照射機，利用該裝置照射上述 混合液體5秒（照度=3. 03J/cm2)。 (7) 利用切式絞碎機將上述膠體切成2mm直徑以下的凝膠體。 (8) 以130 C溫度乾燥2小時；利用篩網篩選〇· imm〜〇· 85mm固定 粒徑，得粉狀高吸水性樹脂。 (9) 秤取此尚吸水性樹脂i〇〇g，加入硫酸鋁粉末ig，待混合均勻 24 200819491 後再加入乙二醇碳酸酯/水/曱醇=1/1/1(重量比）溶液4g，以 215°C溫度加熱處理1〇分鐘。 (10)冷卻後’加入酸甸（台塑公司生產品名：NS—2〇〇〇)及2〇% 甘油水溶液2g ’均句混合後即得高性能高吸水性樹脂。測定 保持力=33.2g/g，佔g/cm2壓力下吸水倍率=：24.1g/g，可 溶物含量=5. 5%。 實施例十： (1)重複實施例九’但光照時間為15秒（照度為9.35J/cm2),所得 之高吸水性樹脂的保持力為3Ug/g，仙g/cm2壓力下吸水倍 率= 24· 5g/g，可溶物含量=7.1%。 實施例十一： (1)重複貫施例九’但不鏽鋼管總長度改為54.5G米長，所得預聚 物的黏度為285CPS ;高吸水性樹脂的保持力則為37阶，初 _2壓力下吸水倍率= 23. 6g/g，可溶物含量—掷。 實施例十二： ⑴重複實施例十-，但光照時間改為15秒(照度為9脱心2)， 所得之高吸水性樹脂的保持力為34. 9g/g，49 _壓力下吸 水倍率= 24· Og/g，可溶物含量=6, 7%。 25 200819491 比較例一： ()貝施例’但步驟(3)所述之反應單體溶液於通氮氣（流量 r控制在200公升/小時）下注入一具有高速攪拌能力的攪拌槽 才二制日守間為3〇min左右，所得預聚物黏度為I45cps。 出料後發現攪拌葉片上有少許聚合物。 ⑵黏稠的職物排出至皮帶反應社，進而硬化成膠體。 (3)其餘步驟同貫施例一中的⑺〜（1〇)，所得之高吸水性樹脂的 保持力則為33.2g/g，49g/cm2壓力下吸水倍率= 23.2g/g，可 溶物含量=13. 8%。 比較例二： (1)重複實施例一，但步驟(3)所述之反應單體溶液於通氮氣（流量 牷制在200公升/小時)下注入一具有高速攪拌能力的攪拌槽 中’控制滞留時間為6〇min左右，所得預聚物黏度為262cps。 出料後發現擾拌葉片和反應槽内有部分聚合物殘留的現象。 ⑵黏稠的縣物翻至皮帶反應紅，触硬化膚體。 (3)其餘步驟同實施例一中的（7)〜（10)，所得之高吸水性樹脂的 保持力則為36· 2g/g，49 g/cm2壓力下吸水倍率= 23· lg/g，可 溶物含量= 13. 3%。 26 200819491 【圖式簡單說明】 第1圖為本發明之直立式反應槽示意圖 【主要元件符號說明】 1. 不鏽鋼槽體 2. 槽頂 2a.反應物料入料管 2b.氮氣管 3. 輥輪 4. 活動式密封機構 27200819491 IX. Description of the Invention: [Technical Field] The present invention relates to a method for producing a super absorbent resin, and more particularly to a method for producing a water-absorbent resin having a low soluble content.鬲Water-absorbent resin has strong water retention capacity, can absorb hundreds of times or even thousands of times its own weight of water' and can swell after water absorption to maintain a non-flowing state, even if pressure is applied, it will not leak, and the absorbed water can be Slowly in the atmosphere cap & Due to the above characteristics, the soil water-repellent agent which was first used in Nongsenpu has been widely used in hygienic products such as diapers, adult incontinence products and women's health in recent years due to considerable progress in the production technology of water-absorbent resins. Water-absorbing agent for money and fresh-keeping applications for preserving food. [Prior Art] The component material of the surface water-absorbent resin is a water-decomposable starch acrylonitrile (= ydr〇iyzed starch_acryl〇niwie) graft polymer (Japanese Patent Publication No. 49(10)4)~43,395), and the neutralized temple powder acrylic acid Grafted polymer (Japanese Patent I, Japanese Journal No. Q 51 (1976)-125, 468), saponified ethylene acetate propylene vinegar copolymer (Japanese Open Bulletin Sho 52 (1977) _14, _, hydrolyzed acrylonitrile copolymer or _ = amine Copolymer (Japanese Patent Publication No. 53 (197δ)_ΐ5, and partially neutralized acrylic acid (Japanese Patent Laid-Open Publication No. Sho 55 (1980)-84, 3 () 4) #. Among them, 200819491 The superabsorbent resin obtained by cross-linking polymerization of the acid salt accounts for the largest P-injury, and the reason is that acrylic acid can be quickly obtained from the market, and the purple-capacity and water-based financial ability are high, and the manufacturing is high. It is the most popular superabsorbent resin because of its low cost and the most effective effect of blood. The method of forming superabsorbent resin from XK acrylic acid and acrylate has been successfully developed in many aspects. Manufactured by the industry, the polymerization method is cast film = combined reaction (Japan) In Japanese Patent Publication No. Sho 48 (1973) _42, 466), a polymerization reaction is carried out on a conveyor belt (Japanese Patent Laid-Open Publication No. Sho 58 (1983) - 49, 714), and a transfer towel of a pulverized mixing blade is subjected to polymerization (Japanese Patent Publication No. 57) (1982)-34,101) 'Perform a liquid polymerization reaction (Japanese Patent Laid-Open Publication No. 59(1984)-37, _)') or spraying or coating a monomer on a filament to carry out a polymerization reaction (Japanese Patent) [Public Gazette No. 62 (1987)-53, 309). [Problems to be Solved] Most of the above-mentioned polymerization methods are a reaction raw material such as a polymerization monomer or a polymerization-initiating cis-crosslinking agent, which is subjected to a free-knit reaction. The polymerization reaction is not easy to control, and the content of soluble matter is also high. [Technical means for solving the problem] Here, the present invention provides a method for producing a highly water-absorptive resin, in which the polymerization process is relatively prison, and the reliance does not Excessively high, in addition to improving the environment of 200819491, the product quality has been improved. The manufacturing method provided by the present invention includes: / 1) An aqueous solution of an acid-containing monomer having a neutralization rate of 5 G mol% or more Polymerization initiator Retention in the pipeline, free radical polymerization to obtain the preform: 2) Adding a hydrophilic polybasic epoxy compound to the prepolymer, and inducing the conversion of the prepolymer into a high molecular weight binder by light at the outlet of the pipeline. 3) The viscous body is inverted from the top of the human body. When the bottom liquid is converted into a colloid, the groove sealing mechanism is opened, and the strip will move downward with the rotating body' and is mashed and granulated. Step; 4) Drying, pulverizing and screening with hot air of 100 C to 250 C; 5) Surface cross-linking agent coating treatment; 6) Heating surface treatment at 80 ° C to 230 ° C; 7) Adding inert inorganic Salt powder. The prepolymerization can be carried out in a prepolymerization reactor which is required to have a uniform mixing of the polymerization raw materials and to carry out prepolymerization. In addition to the reaction tank in which the stirring blade is generally installed, the prepolymerized reactor may also be a horizontal cylindrical body in which a stirring blade, a single screw or a parallel twin screw for one-way flow of the material is installed. This ensures that the reaction material moves forward in one direction without reflow, thereby preventing the polymerization material from staying in the reactor for too long to form a colloidal solid. After the table, the viscous reaction material is discharged to the belt reactor and hardened into a colloid. 200819491 Reactors of the above type are usually produced by batch production, and the belt reactor at the end of the belt is largely unfavorable for industrial hindrance. In this case, the present invention is capable of increasing the capacity of the neck in the future, and the high-yield lyophilized fat method of the invention has the characteristics that the monomer solution is retained in the green matter. The p-reverse system is added to the pipeline to make the surface-based monomer to be free-radical mixed, and to ride the «σ; split Wei-Ki compound 5 to correct the mouth (for example: mercury lamp, halogen lamp, = outside line or I-ray, etc.) After the prepolymer is converted into a fine liquid with a higher molecular weight, the viscous reaction is simplified by the erecting of the shovel. When the liquid at the bottom of the tank hardens the secret body, the structure is dense, that is, (4) The belt of two or more rollers moves downward and enters the lower part - the step of granulation and granulation. The above features of the present invention, the first step is that the monomer solution containing acid groups is retained in the pipeline and will The polymerization initiator is added to a pipeline to carry out radical polymerization to form a viscous polymer. In the second step, the Wei-based compound is added to the pipeline, and the molecular weight and viscosity of the prepolymer are increased by illumination at the outlet of the pipeline. Finally, the high-viscosity prepolymer is fed from above the vertical reaction tank. When the bottom liquid in the tank is converted into a colloid, the bottom sealing mechanism is opened, and the roller will drive the colloid to move downward and enter the strand. The steps of crushing and granulating. The pre-polymerization in the official line not only saves space compared with the general reaction tank or the cylindrical container, but also ensures the principle of the first-in-first-out reaction of the aqueous solution of the reaction monomer, so that the pre-polymerization has no reaction in the process of 9 200819491. Further, the situation in which the silk-reduction reaction is excessive occurs. The residence time of the reaction material in the pipeline is an important factor for controlling the prepolymerization reaction of the present invention, such as the stagnation, the more complete the coffee polymerization reaction, the lower the solubleness of the product and the molecular weight of the product. However, the more recent nucleus is caused by excessive polymerization in the pipeline. If the residence time is short, the viscosity and molecular weight of the prepolymer are lower, and the soluble fraction of the product is higher, but the chance of excessive polymerization is less. In addition, the mixing homogeneity of the reaction monomer aqueous solution and the polymerization agent, and even the illuminating anti-Linzhi County and the bridging agent also swells the important factors of the prepolymerization reaction and the illuminating reaction. In order to improve the mixing effect of the above fluids, generally, the following method can be used to introduce an inert gas such as nitrogen gas, or carbon dioxide gas, or helium gas, or helium gas, or a mixed gas thereof into the pipeline. (2) Adding spiral blades or mixed fillers such as Raschig rings or wave earrings to the pipeline, and (3) using a vapor-liquid static mixer. The prepolymerization of the present invention is divided into two stages, the first stage is carried out in a pipeline, and the latter stage is initiated by light irradiation in an upright reaction tank. In view of this, the illumination time at the outlet of the pipeline is also one of the important factors affecting the prepolymerization reaction, and is usually controlled between 丨~卯 seconds, preferably between 5 and 15 seconds, and the illuminance is 3. 〇3J/cm2~9 . 35J/em2. The most important thing is that the 'pre-polymerized prepolymer is hardened into a colloid in a vertical reaction tank. The vertical reaction tank is made up of a rectangular reaction tank. The tank is made of stainless steel and the top of the tank is set. There is a reaction material inlet pipe (2a) and a nitrogen pipe (2b), a groove bottom has a sealing mechanism and the mechanism is a movable gate (3), and at least a - wheel (4) is formed on the sealing mechanism 200819491. In addition to saving space compared to the general conveyor belt reactor, it can also be connected with the mechanism of the rear colloidal grinding and granulation. In addition to simplifying the configuration of plant equipment, this vertical reaction tank can be a major advantage in future expansion capacity. The acid-containing monomer required for the superabsorbent resin produced by the present invention may use other water-soluble monomers having unsaturated double bonds, such as methyl acetoacetate or marlin, in addition to acrylic acid. Acid, or fumaric acid, or 2-propenylamine methyl propyl sulphate, etc.: Monomers can be used in a non-specific manner, and can also be used in combination with multiple fresheners, and can be added as needed. Saturated double bond, its pure water-based monomer, such as: acrylamide, methacrylamide, 2, hydrocarbyl 2-, thioglycol 2, hydrocarbyl, ethyl: enoate, ethyl acrylate, Dimethylamine propylene acrylamide and propylene chloride; The hydrazine-based tri-aged addition material destroys the physical properties of the superabsorbent resin. Before the radical polymerization reaction, the concentration of the aqueous monomer solution is preferably controlled between 2% by weight and 55% by weight, the appropriate concentration is between 30% and 45% by weight, and the concentration is 2% by weight of the polymer hydrate after polymerization. It is too soft and sticky. It is unfavorable for mechanical processing. The added concentration is above 55wt% by weight, close to the saturation concentration. It is difficult to formulate and the reaction is too fast. The reaction heat is not easy to control. The carboxylic acid group of the acid group-containing monomer should be partially neutralized to control the value of the finished product to make it neutral or slightly acidic. The neutralizing agent is hydrogen oxychloride, sodium hydroxide, potassium hydroxide, carbonic acid, and carbonic acid. , carbonic acid unloading, acid hydrogen clock, sodium bicarbonate, hydrogen carbonate and ammonia. Acid group 11 200819491 The carboxylic acid group of the monomer will be partially neutralized into a lithium salt or a sodium salt or a potassium salt or an ammonium salt or a mixture of two or more kinds, and the concentration of the neutralizing concentration is 45 m〇i% to 85 mol%. When the appropriate concentration is 50mol% to 75moU', the concentration of the molar concentration is less than or equal to the milk purchase percentage, and the pH value of the finished product is low. The neutralization wave percentage is above, and the pH value of the finished product is biased. If the value is not neutral or slightly acidic, it is not suitable or safe to contact with the human body. The prepolymerization starts by the decomposition of the polymerization initiator to generate a radical. Polymerization initiator • Optional thermal decomposition initiator, suitable thermal decomposition initiators include peroxides such as: ruthenium peroxide, di-tert-butyl peroxide, guanidinium peroxide or persulphate (ammonium salt, metal salt), and azo compounds such as 2.2, azobis(2-cyanopropenyl) dihydrochloride, 2·2'-azobis (n, N a two-fold methyl isobutyrene dihydrochloride; a reducing agent may also be used to make a redox initiator, such as an acid sulfite, thiosulfate, or an anti-misculation; or it will oxidize The reducing initiator and the thermal decomposition initiator are used in combination. First, the redox initiator starts to react to generate a radical, and when the radical is transferred to the monomer, the polymerization reaction is initiated, and the polymerization reaction proceeds. A large amount of heat is released to raise the temperature, and when the temperature reaches the decomposition temperature of the thermal decomposition type initiator, the decomposition of the second stage thermal decomposition type initiator is induced to make the entire polymerization more complete. The appropriate amount of the free silk reaction initiator is 重量· 〇 _% to 1 〇 以 以 以 以 以 以 以 以 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , When using the weight percentage 〇·〇_% or less, the reaction is too slow, which is unfavorable economic benefit; the weight percentage of the wrist is used. 12 200819491 The above 4 'reaction is too fast, the reaction heat is not formed, and the material is excessively polymerized to form a solid a solid. '竣 状 仃 仃 起始 起始 起始 起始 应 应 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四Acryl)amine, N,N-methinebis propylene amide, N,N '-methine bismuth is propylene amide, acrylic propylene, ethylene glycol diacrylate, polyethylene glycol二内稀^酉Guangdong ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triglyceride; W曰, glyceryl tridecyl propylene _ glycerine, glycerin plus ethylene ethoxide tripropylene Sour or trimethacrylate, tridecyl alcohol, propylene oxide, triacetate, trimethyl acrylate, trimethyl methacrylate, trimethyl ketone, trimethyl acrylate曰, N, N, N-bis(2-propenyl)amine, ethylene glycol diacrylate, dipropylene triethylene glycol@曰, etc. can also be turned into a compound having two or more epoxy groups. , such as sorbitol polycondensed water _, polyglycerol polycondensed water _, ethylene glycol diglycidyl scale, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, double glycerol polycondensation Glycerol turns. The free radical reaction of the money can make it difficult to have a high degree of cross-linking of the high-absorption sample, and the super-absorbent tree-transformed body has an appropriate reading. The radical polymerization reaction crosslinking agent can be used alone or in combination of two or more thieves. The amount of the appropriate additive of the radical polymerization crosslinking agent is between Q.QQ1wt%s and 5wt% by weight (total total solids of the reactants is fresh), and more suitable weight percentage is between 丨 and (4) Weight percentage 〇〇〇lwt% or less The hydrated body is too soft and viscous after polymerization, which is unfavorable for mechanical processing. The amount of the additive is more than 5% by weight and the water absorption is too low. The cohesive polymer can be used for photoinitiating polymerization in the cross-reaction of the anti-brain or the cross-reaction of the yinsheng. The prepared superabsorbent gel is first cut into a particle size of 20 by a mincer. Small gel, particle size below 1 〇 coffee is better, and then drying 0. The drying slave of the present invention is just after. C to 25 (drying under rc, drying temperature is 12GC to vice. (: drying is appropriate) when the drying temperature is 12 (the rc is below the dry time for too long without the benefit of the drying temperature (10). c The above drying causes the crosslinking agent to proceed early (4) to make the reaction in the subsequent drying process, because the crosslinking degree is too high, the residual monomer can not be effectively removed, and the effect of reducing the residual monomer is reduced. After pulverization, screening and fixing The particle size is further coated with a surface cross-linking agent. The fixed particle size is selected from 〇〇6 to 1〇〇, and it is better to turn it to 〇.850mm, and the particle size is less than 6mm. The powder improves the dust of the finished product, and the particles with a particle size of 1.00 mm or more make the water absorption rate of the finished product slower. The water-absorbent resin is a hydrophilic polymer which is not simplified, and the tree-axis material has a uniformity of n: the structure is like to improve the quality, such as: improving absorption The rate, the increase of the colloidal strong H block fi, the liquid penetrant material will be further on the surface of the tree. = This silk _ her coffee run Naka township function fine two, ancient this = many patents have been proposed; such as: dispersion of high water absorption Resin and cross-linking ^ surface crosslinking treatment in the agent JP-A-56-131608, 14 200819491 JP+57-44627, JP+58-426G2, IP-A58-117222) directly mixing a crosslinking agent and a crosslinking agent solution into a super absorbent resin using an inorganic powder (JP- A60-_56, 】PA Lu 255814), after treatment, steam treatment UP+1-11_) 'surface treatment of solvent, water and polyol (JP-A-63-270741 > JP-A- 64-50707 > JP-A-1-292004) solution, water, ether compound (Jp_A_2_1539〇3), etc.; these surface treated square/έ8 absorption rate increases the water absorption ratio under pressure, but will cause retention The adverse effect of excessive force drop reduces the performance of practical application. According to the present invention, the parent-linked agent which can simultaneously react at the time of surface treatment after screening the fixed particle diameter may be a polyhydric alcohol such as glycerol or ethylene glycol. Diethylene glycol, triethylene glycol, difficult ethylene, knowing, knowing, 4, butanediol, trihydrocarbyl mercaptopropene, sorbitol, etc.; or using polyamines such as ethylenediamine, diethylene Amine, triethylenediamine, polyethylenediamine; or a compound having two or two epoxy-like groups such as sorbitol polycondensation, polypropylene Triol polycondensate _, ethylene glycol diglycidyl _, diethylene glycol diglycidyl _, polyethylene glycol dimerized glycine _, bis ^ (four) glycidyl family, can also use the fumigation of fumigation : ethylene glycol carbonate, 4~methyl-3_dioxolane-2', 4' 5m 3-dioxo-pentan-2-one, 4'4-dimethyl 3-diox Heterocyclic pentylene phase, 4_ethyl 乂 3 _ dioxane ketone + ketone, , 2, transfer age, 4,6 m 3 - dioxane burned (four) Wei seed to 7T tender -2 Na. The cross-linking fine method at the surface can be used alone or in the rain. Appropriate addition of crosslinker at the surface is between 15,2008,1949, 0.00M to 1% by weight (based on the total solids of the reactants), more suitably in the range of 〇.〇幌% to 5% by weight. In the meantime, the amount of cross-linking agent additive is not effective when the weight is less than or equal to O.OOlwU. When the surface cross-linking ship is more than 10% by weight, the water absorption is too low, and the resin performance is lowered. In the surface crosslinking agent coating treatment, the surface crosslinking agent may be added directly to the surface crosslinking agent, or added to the surface crosslinking agent aqueous solution, or adjusted to form a surface crosslinking agent hydrophilic organic solvent aqueous solution. The hydrophilic organic solvent such as methanol, ethanol, propanol, isobutanol, _, (4), and ethylene is not particularly limited, and a solution may be formed, and methanol or ethanol is preferred. When the surface cross-linking agent is added, an inert inorganic sputum can be added to the super-absorbent resin, which is called sulphuric acid, or the sulphuric acid, or oxygen, or oxygen, or the like, Sulfuric acid Ming, good oxidation. The addition of the inorganic end in the weight percentage Q. 嶋 finds to between 10. OwU, wherein 〇. 〇1^% to 4. 〇% is preferred. After the surface treatment is applied, the surface cross-linked ship is subjected to cross-linking reaction by ah to 2 machine treatment, and the internal cross-linking ship is cross-linked to achieve the effect of the invention. Processing temperature 8{rc below the crosslinking reaction time is too long, no economic effect ϋ 'Processing temperature g23 (rc when 'resin is easy to deteriorate affect quality. As for the processing time is 2~150 minutes is appropriate, according to the processing temperature adjustment, high temperature The time is short, the temperature is low, and the time is long. Because the sand water-based reversal has the advantage of agglomerating, in order to avoid the use of high-absorbency in the high-humidity area, the high-absorbency tree age has moisture absorption and agglomeration, resulting in unsatisfactory The surface of the water-absorbent resin is coated with an inert inorganic salt powder or a surfactant which will be highly lipophilic and highly absorbent. The agglomeration of the salt can be selected from the salt of the machine salt, or the sulphur dioxide, or the oxidized ^ Or oxygen == ^ simple, or high resident, or carbon _, or fresh carbonate or a mixture thereof. Usually the amount of this inert inorganic cane is purely larger than the inorganic face, 〗 〖, the particle size is smaller, its inorganic threat A, the amount of the application can be small, the inert inorganic salt powder is added in the range of weight ratio to 10,000. 005 tear 1 〇 Wt%, which is 4. _ better. Inert inorganic salt The particle size is 〇. Xie-to, if the particle size is less than ◦ 〇 _ The inorganic bribes of the cockroaches have been privately produced. If the granules are larger than the shackles of the inorganic salt powder, there is a problem that the excessive amount of the superabsorbent resin affects the absorption capacity of the superabsorbent resin. The inertia can be counted at the end of the county. The hetero interface is active or has a dry organic compound added. The surfactant or the organic compound having a dryness may be selected from a value of 12 or more of a nonionic surfactant, or a water-soluble anionic surfactant, or a cationic 1 interface agent. Or an yin-yang-type surfactant, or a mixture thereof. Generally, the organic compound or the organic compound may be glycerin, ethylene glycol, hexaol-oxyethylene glycol, or polyethylene glycol, or barium glycolic acid. Glycol vinegar, or stearic acid alcohol /, Sa, or polyethylene oxide benzoquinone, or polyethylene oxide octyl benzoquinone, or polyethylene oxide H wire minus the ship fine, silk oxidation of ethylene 4t The bond or the like or the viscosity organic compound can be formulated into an aqueous solution type and added or separately, and the appropriate surfactant or viscosity organic compound additive is between 0.001 wt% and 5 wt% ( Total reactants The basis weight is based on a more appropriate amount by weight of 〇. 〇1wt% to 3% by weight. The present invention provides a method for continuously producing a superabsorbent resin having a low soluble content, the steps of which are: In one step, the monomer solution containing the acid group is retained in the pipeline and the polymerization initiator is added to the pipeline towel to be free-knitted to form a viscous polymer. The second step is to epoxy. The base compound is added to the pipeline, and the molecular weight and viscosity of the prepolymer are increased by illumination at the outlet of the official line. Finally, the high-viscosity prepolymer consists of a man-up material in the vertical reactor, and a bottom plate in the tank. When turning into Lai, the groove bottom sealing mechanism is opened, and the methane wheel will move the colloid downward and carry out the steps of grinding and granulating. Through this production method, in addition to saving space, the reaction fluid can be ensured to be first-in-first-out. Principle, and achieve the purpose of continuous production. The superabsorbent resin provided by the invention has the advantages of improving the production operation, saving the operation of the factory equipment, and improving the product quality, especially for reducing the soluble content. _ is the characteristic of the low soluble content of the superabsorbent resin of the present invention, and the measuring procedure of the soluble substance is as follows: firstly, 〇·5 g of super absorbent resin is added, and then 185 g of 〇·9 heart water is added. After mixing for one hour at 纟__, the SAP extract was filtered through a filter paper. After taking it, weigh the extract 2, first titrate with 〇· _, and then use G.1N HC1 for back titration to determine the content of SAp solubles. 18 200819491 [Embodiment] Hereinafter, the present invention will be described by way of examples, but the scope of the present invention is not limited by the embodiments. Example 1: (1) 1760 parts by weight of acrylic acid and 2263·7 parts by weight of water were added to the neutralization tank, and then 1476·3 parts by weight of an aqueous solution of sodium hydroxide (concentration: 45%) was placed under ice. It is slowly added to the above aqueous acrylic acid solution. At this time, an aqueous solution having a monomer concentration of 38.6 wt% was obtained, in which 68 mol% of acrylic acid was neutralized as sodium acrylate. (2) After the completion of the neutralization process, the partially neutralized sodium acrylate solution is controlled by the tempering water to about 20 °C. (3) Adjust the flow rate of the above monomer solution to 1 〇() liter/hour through a stainless steel tube of only 5 cm straight and a total length of 25.48 m. In addition, a stainless steel pipe with a diameter of 〇·5 and 〇·9 cm is connected to the side of the stainless steel pipe 5 cm and the side of 1 cm. The former introduces nitrogen gas, the flow rate is controlled to 2 liters liter per hour, and the latter is introduced with persulfate desorption/hydrogen sulfite = 1/1 (weight ratio), and the flow rate is controlled to 2 halo: liter / hour. The prepolymerization and reaction temperature were controlled at 2 ° C, and the resulting prepolymer has a WE of 78·5 cps. (4) Two pipes of diameter 〇·9 cm are connected to the side of the outlet of the pipeline at a distance of 85 cm, one is introduced with azobis-iso-gumamine, and the flow rate is controlled to 2 〇ml/hr, 19 200819491 Propylene glycol polyethylene glycol triglycidil test ((4)), flow control is 15 ml / hour. (5) The cough device is recorded with a high-strength material line, and the mixed liquid is irradiated for 5 seconds (illuminance = 3. 03 J/cm 2 ). (6) The mixed liquid is fed from above the vertical reaction tank (please refer to the drawing), and the liquid 2 in the tank is hardened _ afterwards, _峨_start, scale _ is driven downward by the roller. (7) The use of the cutting machine red turn body 2mm recorded in the Miyao colloid. (8) Drying at a temperature of 130 C for 2 hours; screening the G. i curry to fix the particle size by a sieve to obtain a powdery superabsorbent resin. (9) The scale takes this high record _ 1 (%, add people sulfur _ county &, after mixing the sentence, then add glycol water _ / water / ¥ alcohol = 1 / 1 / 1 (weight ratio) solution package, Heat treatment at 215 C for 10 minutes. 〇〇) After cooling, add lg carbonate to Taiwan Plastics Co., Ltd. product name paste X mixture 2g evenly mixed to obtain high performance superabsorbent resin. Determination of holding power -33.5 g / g ' 49 g / cm 2 pressure absorption ratio = 2 soluble content = 10. 7%. · Example 2: (1) Repeat the first embodiment, the irradiation time is changed to 15 seconds (illuminance is 9.35J/cm2), and the retention of the obtained super absorbent resin is 3G. lg/g, 49 g force Water absorption ratio = 22.6 g / g 'soluble matter content two (10). 20 200819491 Example 3: (1) Repeat the example - but the total length of the single steel tube is 5i. 25 meters long, the viscosity of the obtained product is 205 cps; the retention of the obtained super absorbent resin is 36, and the water absorption ratio under the pressure of 49 g/cm2 I. lg / g, soluble content = 90%. Example 4: (1) Repeat Example 3 'but the illumination time is changed to 15 seconds (illuminance is 9 • such as (5), the obtained high gettering__ holding capacity is 32 9g/g, and the water absorption ratio under 49 (10) pressure = 23·3g/ g重量的含量为1476. 3重量份。 After the weight of the acrylic acid and 2263 7 parts by weight of water in the neutralization tank, after the ice bath will be 1476. 3 parts by weight An aqueous solution of sodium hydroxide (concentration: 45%) was gradually added to the above aqueous solution of acrylic acid. At this time, an aqueous solution having a monomer concentration of 38.6 wt% was obtained, in which 68 mol% of acrylic acid was neutralized to sodium acrylate. (2) Neutralization After the completion of the procedure, the sodium acrylate aqueous solution neutralized by the temperature control water is controlled to be about 20 ° C. (3) The flow rate of the above monomer solution is adjusted to 1 〇〇 liter / hour, so that it is passed through a direct control 5 cm, total length of 26·35 m and internal filled with stainless steel tube with diameter 5_Rasi ring. In addition, the inlet end of the stainless steel tube is 5 cm and the side of 1 cm is connected with a diameter 〇·5 and 〇·9 Stainless steel tube of centimeters. The former is introduced with nitrogen, the flow control is controlled to 200 liters/hour, and the latter is passed through sulfur. 5之间。 Potassium / sodium bisulfite 21 200819491 a 1 / 1 (weight ratio) 'flow control is 2 ml / hr. Prepolymerization and reaction temperature is controlled at 20 ° C, the resulting prepolymer viscosity is 113. 5cps. (4) distance At the outlet end of the pipeline, 85 cm is connected to two sides of the diameter of Q·9 cm. The non-recorded steel 5 '- branch is introduced into azo diiso-gumamine #, the flow rate is controlled to 2 〇 ml/hr, and the other is introduced into propylene glycol. Alcohol triglycidyl sulphate (n=7), flow control is 15 ml / hr. (5) Pipeline 丨Π 置 置 高 high-strength material _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ (6) The liquid plate is fed from the top of the vertical reaction tank (please refer to the drawing). After the liquid body in the tank is hardened, the groove structure is smooth, and the miscellaneous is driven by the roller. () Using a knife, a, and a cross; ^ The above colloid is cut into a gel having a diameter of 2 or less. (8) Drying at 13 (TC temperature for 2 hours; using a sieve _ G. imm ~ 〇. 85 legs) Fix the particle size to obtain a powdery superabsorbent resin. (9) Weigh this superabsorbent resin _, add human sulfuric acid scale lg 'to be mixed evenly, then add two Carbonic acid vinegar / water / methanol = 1 / 1 / 1 (by weight) solution, heat treatment at 215 C for 丨〇 minutes. (10) After adding lg 冷, add lg carbonate word (Forminal Company's product name · U_) and (10) 2 g of glycerol lyophile liquid was uniformly mixed to obtain a high-performance superabsorbent resin. The retention of the force was 34.6 g/g, and the absorption ratio under the pressure of 49 g/cm 2 was 23.7 g/g, and the soluble matter content was 8.1%. 200819491 Example 6: (1) Repeat Example 5, the irradiation time is i5 seconds (illuminance is 9.35), the obtained retention capacity of the water-absorbing tree is 3232. Orbital, milk (10) under the pressure absorption ratio = 23.〇g/ g, soluble matter content of cyst. Example VII (1) Repeating the example of the five-stainless stainless steel tube, the total length of the stainless steel tube is 52·75 m, and the obtained prepolymer viscosity is No. (4); the retention of the obtained superabsorbent resin is 38·lg/g, 49 g. The absorption ratio is 23·step under the pressure of /cm, and the soluble matter content is the eighth embodiment: (1) Example 7 is repeated, but the illumination time is 15 seconds (illuminance is 9.35 J/cm 2 ), and the obtained super absorbent resin is maintained. The force is 35.9·lg/g, the absorption ratio under the pressure of 49 g/cm2 is 22.9 g/g, and the soluble content is 93%. Example 9: (1) 176 parts by weight of C is added before the neutralization tank Dilute acid and fiber. 7 parts by weight of water. Then, in an ice bath, 476. 3 parts by weight of an aqueous solution of oxo butterfly (concentration of 45. was slowly added to the above aqueous solution of acrylic acid. At this time, an aqueous solution having a monomerity of 38·6 liters was obtained, wherein 68 _ of acrylic acid was neutralized. (2) The neutralization procedure is finished, _ tempering water control part of the towel and the __ saline solution is about 20 ° C. (3) Adjust the flow rate of the above monomer solution to (10) liter / do, let it pass a Straight 23 200819491 The gas-liquid static mixer (obtrusion · N0RITAKE) with a total length of 27.20 meters, the length of the spiral blade mixing part is 30 cm. In addition, the inlet end of the non-ferrous steel pipe is 5 cm. One side of the 1 cm section is connected to a stainless steel tube with a diameter of 〇·5 and 0·9 cm. The former is introduced with nitrogen, the flow rate is controlled to 2 liters liter per hour, and the latter is introduced with potassium persulfate/sodium hydrogen sulfite = 1/1 (weight ratio), the flow rate is controlled to 2 ml / hour. The prepolymerization and reaction temperature are controlled at 2 Torr, and the resulting prepolymer viscosity is 10 mls. (4) The side connection is 85 cm from the outlet end of the line. Two stainless steel tubes with a diameter of 〇·9 cm, one imported with azo Gengyueqing, flow control is 2 〇 ml / hour, the other is introduced glycerol polyethylene glycol triglycidyl ether (n = 7), flow control is 15 ml / hour. (5) will (4) The reaction fluid is added to the conveyor belt, above the conveyor belt | is placed with a high-intensity ultraviolet irradiation machine, and the mixed liquid is irradiated by the device for 5 seconds (illuminance = 3·03 J/cm2) 〇 (6) The outlet of the pipeline is high. The intensity ultraviolet ray irradiator was used to irradiate the mixed liquid for 5 seconds (illuminance = 3.03 J/cm 2 ). (7) The gel was cut into a gel having a diameter of 2 mm or less by a cutter. (8) The temperature was dried at 130 C for 2 hours; the sieve was used to screen the fixed particle size of 〇·imm~〇·85mm to obtain a powdery superabsorbent resin. (9) Weighing this water-absorbent resin i〇〇g, adding aluminum sulfate powder ig After mixing, uniformity 24 200819491, then add 4g of glycol carbonate / water / sterol = 1 / 1 / 1 (weight ratio) solution, heat treatment at 215 ° C temperature for 1 。 minutes. (10) After cooling 'join Acidian (Former Plastics Company's product name: NS-2〇〇〇) and 2%% glycerin aqueous solution 2g 'High performance after mixing Water-absorbent resin: measured retention = 33.2 g / g, water absorption ratio under g / cm 2 pressure =: 24.1 g / g, soluble content = 5. 5%. Example 10: (1) Repeat Example 9 However, the illumination time was 15 seconds (illuminance was 9.35 J/cm 2 ), and the retention of the obtained super absorbent resin was 3 Ug/g, and the water absorption ratio under the pressure of g/cm 2 = 24·5 g/g, and the soluble matter content = 7.1. Example 11: (1) Repeat the application of Example IX 'but the total length of the stainless steel tube is changed to 54.5 G meters long, the viscosity of the obtained prepolymer is 285 CPS; the retention of the super absorbent resin is 37 steps, the initial _ 2 water absorption rate under pressure = 23. 6g / g, soluble content - throw. Example 12: (1) Repeat Example 10 -, but the illumination time is changed to 15 seconds (illuminance is 9 decentering 2), the retention of the resulting superabsorbent resin is 34. 9g / g, 49 _ pressure absorption ratio under pressure = 24· Og/g, soluble content = 6, 7%. 25 200819491 Comparative Example 1: () Shell Example 'but the reaction monomer solution described in step (3) is injected into a stirred tank with high-speed stirring ability under nitrogen (flow rate controlled at 200 liters / hour). The daily stagnation is about 3 〇 min, and the obtained prepolymer viscosity is I45 cps. After discharge, a small amount of polymer was found on the stirring blade. (2) The viscous body is discharged to the belt reaction society, and then hardened into a colloid. (3) The remaining steps are the same as (7) to (1〇) in the first embodiment, and the retention of the obtained super absorbent resin is 33.2 g/g, and the water absorption ratio under the pressure of 49 g/cm 2 = 23.2 g/g, soluble. Content = 13.8%. Comparative Example 2: (1) The first embodiment was repeated, but the reaction monomer solution described in the step (3) was injected into a stirred tank having a high-speed stirring ability under a nitrogen gas flow rate (flow rate of 200 liters/hour). The residence time is about 6 〇 min, and the obtained prepolymer viscosity is 262 cps. After discharge, it was found that there were some polymer residues in the disturbing blades and the reaction tank. (2) The sticky county material turned to the belt to react red, and touched the skin. (3) The remaining steps are the same as those of (7) to (10) in the first embodiment, and the retention of the superabsorbent resin obtained is 36·2 g/g, and the water absorption ratio under the pressure of 49 g/cm 2 = 23·lg/g , soluble content = 13.3%. 26 200819491 [Simple description of the diagram] Figure 1 is a schematic diagram of the vertical reaction tank of the present invention [Description of main components] 1. Stainless steel tank 2. Tank top 2a. Reaction material inlet pipe 2b. Nitrogen pipe 3. Roller 4. Movable sealing mechanism 27