200813146 九、發明說明： 【發明所屬之技術領域】 發明係有關於一種高吸水性樹脂的製造方法，尤其是一種可容 物含章低的吸水性樹脂的製造方法。 【先前技術】 尚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，且吸水後可膨潤财保持不流_狀態，即使^加 壓力也不會滲漏，且被吸收的水可緩緩地在大氣中釋出。由於具 有上述之躲’所以最早使驗農雜㈣土聰糊，近年因 向吸水性樹脂社產技術有相當大的進步，所以也廣泛地運用於 俯生用品如尿布、成人失制品及婦女衛錢品的吸水劑及保存 食物用的保鮮應用等。 高吸水性樹脂的成分材料有遇水分解型的殿粉丙婦猜 (hydrolyzed StarCh-acryl〇nitrile)接枝聚合物（日本專利公開 公教昭49(1974)”），中和之殿粉丙稀酸接枝聚合物（日本 專利公開公報昭51 (1976H25,468)，皂化乙烯醋酸丙稀酿共聚 物（日本專利公開公報昭52⑽7)—14, 689)，水解丙稀腈共聚物 或丙稀雜共聚物（日本專利公報昭53 (1978)_15,959)，及部 份中和聚丙烯駿（日本專利公開公告昭55(1__84,3Q4)等。 其中以使用丙稀酸及丙稀酸鹽進行交聯聚合所得之高吸水性樹脂 200813146 佔最大部份也最為經濟，其棚躺烯酸可迅勃市售取得，且 衣付的问吸水倾脂具有高的吸水能力，及具有製造成本低廉且 最具經濟效益，故成綠普遍化的高吸水性樹脂。 聚合丙_及丙烯酸卿成高吸水性樹闕方法已被多方面 的開發成功，且有多種已勒於与界生產，其聚合方法有轉膜 聚合反應（日本專利公開公報昭48(1973) _42，傷），於輪送帶上 進行聚合反應（日本專利公開公報昭58⑽3) _49,7⑷，粉碎之 攪拌刀片的捏拌機中進行聚合反應（日本專利公開公報昭 57(1982)-34,101 ) ’進行逆相懸浮液聚合反應（日本專利公開公 報昭59⑽4)-37’_)，或將單體倾或塗覆於纖絲質上、進行 聚合反應（日本專利公開公報昭62(1987)_53,3Q9)。 【擬解決之課題】 ，上δ方法大夕疋將聚合單體、聚合引發劑與交聯劑等反應 原料-同進行自由絲合反應而歧職_，如此整個聚合反 應不易控制，可溶物含量也較高。鑑於此，本發明提供—種高吸 水性樹脂義造綠，絲合反應過軸驗域定，反應 熱也不致於過高，除了改善操作環境之外，更提高了產品質量。 本發明所提供的製造方法至少包括： 1)使中和率50 mole%以上之含酸基單體水溶液與聚合反應 〃引發撕管線巾滯留，作自由絲合反應得_的預聚 200813146 物’其含酸基單體係選自丙烯酸或曱基丙晞酸或2_内稀胺 - ―2—甲基丙烧磺酸或其混合物； ‘ 2)添加錢、高親水性的多元環氧基化合物於軸預聚物 巾，_光起始聚合的方式進—步生成轉狀固體； 3) 以溫度loot：至250°C熱風進行乾燥、粉碎、篩選； 4) 表面交聯劑塗覆處理； 5) 再以溫度8〇c至230°C加熱表面處理； # 6)添加惰性無機鹽粉末。 上叙縣合反應可以在—個縣合反脑巾進行，該反應 器需具備纟_找合反顧觀合均自且進行爾合的作用。^ 聚合反應器除了可以採用一般安裝有攪拌槳之直立式反應槽外， 也可以採用種臥式的筒狀容器，中心安裝有使物料單向流動的 攪拌水單螺才干或並列之雙螺桿，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 ⑩中停留時間過長而形成凝膠狀固體。然而，上述類型之反應器通 常採用批次入料的方式，較不利於工業化生產。 心 【解決課題之技術手段】 ί;此本發明提供一種可連續生產具備低可溶物含量之高 吸水f生树月曰的方法，其特徵在於··第一步，使單體溶液於管線中 滞留，並將聚合引發劑加入至管線中，使含酸基單體進行自由基 水口反應而成黏稠的高分子。第二步，黏稠的預聚物與多元環氧 200813146 基化合物混合之後，可連續“域帶反應II上，其上方利用各 式光源(例如：餅線、紅外線、x_射線或r _射糊刪聊 聚物轉變成硬化成凝膠狀固體。 於g、种進仃鮮合除了較—般直立式反應槽韻狀容器節 痛空間外，更㈣確保反應單體水溶液先触出的，使得預 聚合過程減反鮮體殘管針，進轉健合反應過度的 情形發生。反鮮體水驗於管線中的滞留咖是控_聚合反 應的重要因素之-，如滞留時間長，則預聚合反應越完全，預聚 _度與分子量也越高，成品的可溶份也較低，但較容易發生於 管線中過棘合的現象；如滯留_短，咖聚物黏度與分子量 較低’成品可溶份較高，但發生過度聚合的機會較少。此外，反 應單體溶液絲合引制，乃至照歧應前之棘物與架橋劑的 混合均勻性也是影響職合反應與照光反應的重制素。為了提 高上述各流體彼此之關混合效杲，通常可_下列方法：⑴: 管線中通人惰性氣體，如：氮氣、或二氧化碳、或氦氣、或氮氣、、 或其混合氣體，紅業界為節省成本及考慮便於取得，通常使用 氮氣或二氧化碳或其混合氣體。此外，惰性氣體的屢力要高於管 線内壓力，才可㈣性氣體順敝人含單體水溶液管線内而使^ 反應流體_混合的效果，⑵於請中加魏旋料或呈混人二 果的填充物如：㈣環、或波耳環，⑶使贱㈣務混合7。 光起始聚合技術發展純熟，應用也相當廣泛，例如：塗裳、 200813146 印刷業、PCB/LCD製程、鞋業等等。利用照光引發聚合的方式具有 許多優勢，如：縮短製程、提昇產能與節省能源等等。光源種類 繁多，包括紫外線、紅外線、χ_射線或7_射線等等，一般以紫= 線最為大眾所使用，它具有波長較短⑽.nm)，穿透力強的特 性。值得注意的是，-般製程用的紫外線燈源強度為職心2 丽/αη，這往往對承載工作物的輸送帶造成嚴重的耗損。如此： 來，輪送帶就必須經常性的更換，生產成本也跟著增加。鐘於此， 本發明舰之光起絲合係將光齡為_，⑽輸送帶前段 紫外線’後段則為紅外線。由於一般輸送帶的表面材質為娜月^， 可財熱至15G-2GG C，且具有抗沾雜耐化學_的特性，然而浴 不具耐光性。本發明前段絲用穿透力強的紫外絲引發單」 液由底層向上地進行聚合反應，而後段則使： 穿透力較弱，但加熱效果佳的紅外線光幸^ 個聚合反應，餘於輸送帶均腦賤祕體。如此一^ 工作物照射料蝴㈣碰嫌⑽的騎強度相 _也減低了輸送帶的耗損。重要的是，紅外線不需熱介質的: 遠，可直賊工作物加熱，效率極高，所以並 士 間縮短而降低了反應· 故照射设備亚分使得製程空間過大，且溫 、 ’ 燈源酬餅停止加熱，安全性較高。W·1容易、迅逮， 本發明所製造之高吸水性樹脂所需的含酸基單體除了丙场酸 200813146 外，尚可使用其它具有不飽合雙鍵的水溶性單體，如：T基丙稀 .酸、或馬林酸、或富馬酸、或2-丙稀胺I甲基丙烧石夤酸等。單體 .選用不特定限·可制-種，亦可合併多種單體—齊使用，: 可歸況轉添加射不麵魏其純雜醉體，如：丙稀酿 胺、甲基丙稀_、丙烯酸2_烴基乙醋、甲基丙稀酸2_煙基乙酉旨、 =稀酸㈣、丙烯酸⑽、二甲胺丙稀丙稀_、氣化丙稀丙稀 祕基二f雜添加量以不破壞高吸水性·旨之物性絲則。 ^ 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20wt%至55wt%間’適當濃度為黯%至45wt%之間，濃度在重 量百分比20wt%以下時，聚合後水合體太軟且有黏性不利^成加 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pH值，使呈中 ❿性或微酸性，中和劑為氫氧化鐘、氫氧化鈉、氫氧化钟、後酸鐘、 碳酸納、碳酸鉀、碳酸氫鐘、碳酸氫納、碳酸氫鉀及氨。含酸基 單體之紐基將部份中和成鐘鹽或納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45mol%至85mol% /適當濃度為 50mol%至75mol%’中和濃度莫耳百分比為45m〇1%以下時成品之四 值會偏低’中和濃度莫耳百分比為85m〇1%以上時成品之押值會偏 南，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。 200813146 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： .聽域、二-第三丁基過氧化物、魏化_或過雜膽鹽、 齡屬鹽）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,-偶氮基雙齡二伸甲基異丁勝）二鹽酸鹽；亦可 使㈣· ’使絲氧化還顧起始劑，如：酸性亞硫酸鹽、硫 代硫酸鹽、抗壞域或亞鐵鹽；或將氧化還原型起·和熱分解 I㉟起始齡併使肖’錢氧化還原起始航進行反應產生自由 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 應進行N·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 適冨用里為重里百分比為〇· OOlwt%至以中和丙烯酸鹽重量 ’ 為基準），更適當用量則在〇. lwt%至5wt%之間，使用重量百分比 験 0. OOlwt%以下時，反應太慢不利經濟效益；使用重量百分比 以上時’反應太快反應熱不易控制且容易聚合過度而形成凝膠狀 固體。 進行光起始聚合反應前應添加交聯劑於黏稠預聚物中，交聯劑 可選用具有兩個或兩個以上不飽和雙鍵的化合物，如：N，N_雙（2一 丙烯基)胺、N，N ‘-次甲基雙丙烯醯胺、n，n ‘一次曱基雙甲基丙烯 酸胺、丙稀酸丙烯酯、乙二醇二丙烯酸醋、聚乙二醇二丙烯酸醋、 12 200813146 乙二醇二f基丙烯酸酯、聚乙二醇二甲基丙烯酸酉旨、甘油三丙婦 酸酯、甘油三甲基丙雜酯、甘油附加環氧乙烧之三丙烯酸醋或 -甲基丙烯酸酯、二甲醇丙細加環氧乙烧之三丙烯酸酷或三曱 基丙蝉酸酯、二甲g洲完三曱基丙稀酸酯、三甲醇丙烧三丙稀酸 酉曰、N，N，N-二（2-丙烯基）胺、二丙烯酸乙二醇酯、二丙烯三甘醇 酉旨等，亦可具有兩個或兩個以上職基的化合物，如山梨醇 聚縮水甘細、聚丙三醇雜水甘簡、乙二醇二縮水甘油鍵、 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 欠甘油荨。在進行自由基反應後就可使高吸水性樹脂具有適當 交聯度，而使高吸水性樹脂膠體有適當的加工性。自由基聚合反 應交聯劑可單獨使用或兩種以上混合使用。自由基聚合反應交聯 制適當的添加劑量在重量百分比〇』〇1的％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· _%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 低，降低樹脂性能。 黏稠預聚物可於輸送帶式反應器上或裝有攪拌葉之橫式反應 扣中進行一段式光起始聚合反應，製備出之高吸水性凝膠體先利 用絞碎機切成粒徑2〇mm以下小凝膠體，粒徑i〇mm以下更佳，再 進行烘乾。 烘乾溫度可於loot：至25(TC下進行乾燥，乾燥溫度則以12〇 13 200813146 C至18GC進行烘乾為s，#烘乾溫度溫度⑽。c以下醜乾時間 • 太久不〜纟〜齊效显’烘乾溫度180°C以上烘乾使交聯劑提早進行交 %反應使诚乾燥過程巾，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_定解，再進行表面交聯劑塗覆處 理。耗固定粒徑以〇· 06mm至^ 〇〇腿間為宜，以〇· 1〇咖至 眷 Q.85Gmm削述’_0.06顧叮崎使成品粉塵提高，粒徑 1· 00mm以上粒子使成品吸水速率變慢。 吸水性樹脂為不溶解化之親水性聚合體，樹脂内部具有均勾性 的架橋結構，-般為了改#品質如：提高吸收速率、提高谬體強 度、提南抗結塊性、液體滲透性等，會在樹脂的表㈤再作進一步 架橋，此表面交聯處理即利用具有能與酸基反應之多官能基交聯 劑’在此之前已有許多專概出；如：分散高吸水性樹脂與交聯 • 劑於有機溶劑中進行表面交聯處理（JP-A-56-131608、 JP+57-44627、IP-A-58-侧2、JTP-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-A6G-163·、】P-A-6G-255814)，添加交制後以蒸氣處理 (1P-A-1-113權），使用有機溶劑、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+2_1539〇3)等；這些表面 處理的方法雖能提高吸收速率提高壓力下吸水倍率，但將造成保 14 200813146 持力下降過多的不良後果，降低實際應用之性能。 篩選固定粒徑後，根據本發明於可表面處理時能同時及 的交聯齊J可為多元醇如··丙三醇、乙二醇、二乙二醇、：—應 聚乙二醇、丙二醇、1，4 丁：醇、三 可使用多元胺如:乙二胺、二乙二胺、三乙二胺、聚乙:。 可使用具有兩個或兩個以上職基合物如：㈣ 廿 油酸、聚丙三醇聚縮水甘油_、乙二醇二縮水甘_、二^^醇 水:油醚、聚乙二醇二聚縮水甘油醚、雙丙三醇聚縮水甘： 醚寺；亦可使用碳酸亞烴酉旨如：乙二醇碳酸酿、4〜甲基U ^ 雜環戊烧—2一輞、4,5~二甲基二氧雜環戊垸〜2督4’ 基-!，3-4轉狀相、4_乙基3_二氧雜環姐相、 ’--乳崎m4,6m，3_二氧雜環己烧_2-酮或 錄--嫌嫩-2-_。表面處交聯劑的用法可單獨使用或雨 以上齡㈣。表面處交·的適t添力,量在重量百分此 〇.謝魏歸之間（以反應物總固形份為基準），更適當的用量' 在0.005Λ至5wt%之間，表面處交聯劑添加劑量在重量百分比 〇.〇斷伽下時無法_效果，絲處交聯输加継在重量有 7刀比10wt%以上時，吸水性太低，降低樹月旨性能。 接天表面交聯劑塗覆處理時’表面交聯劑之添加可為表面交聯劍直 或峨表面交聯劑水溶液添加，或調成表面交聯劑親水 性有機溶獻溶液添加，親水性有機溶劑如曱醇、乙醇、丙醇、 15 200813146 異丁醇、丙酮、_、乙醚等沒有特殊限制，可形成溶液 八中以m、乙醇較佳。表面交聯劑添力。時高吸 惰性無機鹽粉末，以幫助溶液分散，惰性無機鹽粉末可加 或二氧切，錢触’編_或其混合物。其巾似=、 二乳化频佳。雜無機鐘末添加細在重量百分比u、 至1〇相之^其中以0.01龜4.0爾佳。.0一 進仃表面交聯劑塗覆處理後，再卩8{rciL 230。匚加熱處理， 表面父聯舰進行交聯反應，並使内部交聯劑進行交聯反應而 1 树明之效果。處理溫度8Gt以下交聯反應時間太久^具經 ’處理溫度纖。C時’樹脂易劣化影響品質。至於處理時 =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。皿 「由於高吸水性樹赎有簡後結塊的現象，為避免在高渴度地 二使用=吸雜樹齡有賴後結塊_叫順，—般會在高 ^、尺叫絲φ麵紐域胁末或界面活性劑，使表面略具 2性而使高财性_保有吸祕料結塊的躲，此惰性無 、或二氧切、或氧脑、或_、或 棒a或阿駐、或石炭酸甸、或碳酸鎮等或其混合物；通常此 機麵末的添加麵無機末驗粒徑大小有關，若顆 東;用旦乂]/、热機鹽粉束比表面積較大，所以有效惰性無機鹽粉 σ車又]其丨胃性無機鹽粉末添加範圍為重量比百分比 16 200813146 ( 〇 〇〇5wt龜1Q輕之間，其中以Q· _。至嶋交佳，惰性無 粉末其_為請⑽至⑽•若選賴粒小於請i, 1機4棚成本過高不利於工業化生產，若選賴粒大於 //M的熟機鹽粉末則有添加量過高影響高吸水性樹脂吸收力的 機驗末可單獨添加或可伴隨界面活性劑或具枯度 有機化口物加人’其界面活倾或具钻度有機化合物可選用腦 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、 鲁姐軒型界騎性劑、或陰陽兩性型界面活侧、或其混合物， 通常界面活性劑或具粘度有機化合物可使用甘油、乙二醇、己六 知、聚氧乙烯醇、或聚乙二醇、或硬脂酸聚乙二醇酯、或硬脂酸 XK乙二醇己六酯、或聚氧化乙烯壬苯醚、或聚氧化乙烯辛苯瞇、 或聚氧化乙烯十二苯醚、或聚氧化乙烯烷基醚、或聚氧化乙烯月 桂峻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 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 ® 在重量百分比〇· 〇〇lwt%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O.Olwt%至3wt°/〇之間。 17 200813146 【發明内容】 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’其特徵在於：第一步，使含酸基單體水溶液與聚合引發 劑通過於一長管線中，而此長管線之約1/5及1/2處各設有導入 氮及熱分解型起始劑;距出口處約85公分處設有2支導入偶氮化 合物或環氧化合物進行自由基聚合反應而成黏稠的預聚物。第二 步’預聚物與多元環氧基化合物混合之後連續加入至皮帶反應器 上’其上方以前段為紫外光；後段則為紅外線二種不同的光源引 备黏稠縣物轉變硬化成狀固體。本發騎提供之上述生產 方式具有下列特點：（1)預聚物相對於液體反應物料的黏度明顯提 门机動〖生卩牛低，更容易與之後的皮帶反應器相匹配，而且使整 τΆ顧議度提〶，反應熱不至於過高，⑵使膽線反應 讀了節省郎外，且更能夠確保反應越先進先出的原則，而 達到連續式生產的目❸，⑶使用二段式照光的作法，減少紫外 線對於輸送皮帶的照射日_強度，降低耗她 紅外線加熱效率極佳，可筋省处、、原廿且古p a 成本乂） 了即^此源亚具有刼作簡便與安全性高的 ‘二占，（5)縮短製程、摇并嘉A匕古口 如升產彻亚提问產貝量，尤其是降低可[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 content and a low content. [Prior Art] The water-absorbent resin has a strong water-retaining power, can absorb 100 times or even thousands of times its own weight of water, and can swell and keep the flow _ state after water absorption, even if it is pressurized, it will not leak, and The absorbed water can be slowly released in the atmosphere. Because it has the above-mentioned hiding, it has been used for the first time in the past. Because it has made considerable progress in the production technology of water-absorbing resin, it is also widely used in the products such as diapers, adult products and women's health. Water-absorbing agent for money and fresh-keeping applications for preserving food. The component material of the superabsorbent resin is a hydrolyzed StarCh-acryl〇nitrile graft polymer (Japanese Patent Publication No. Sho 49 (1974)), Neutral Hall Powder Acid-grafted polymer (Japanese Patent Laid-Open Publication No. SHO 51 (1976 H25, 468), saponified ethylene-acetic acid-acrylic-acrylic copolymer (Japanese Patent Publication No. Sho 52(10)7) - 14, 689), hydrolyzed acrylonitrile copolymer or acrylic Copolymer (Japanese Patent Publication No. Sho 53 (1978) _15, 959), and partially neutralized polypropylene (Japanese Patent Laid-Open Publication No. Sho 55 (1__84, 3Q4), etc., in which acrylic acid and acrylate are used. The superabsorbent resin 200813146 obtained by cross-linking polymerization is the most economical and the most economical, and its squalene is commercially available, and the water-absorbing fat-removing oil has high water absorption capacity and low manufacturing cost. It is the most economical, so it is a highly water-absorbent resin that has become universal in green. The method of polymerizing C- and acrylic acid into high-absorbency tree shrub has been successfully developed in many aspects, and there are many kinds of polymerization methods that have been produced in the boundary. Transfer polymerization (Japan Japanese Patent Publication No. Sho 48 (1973) _42, Injury), polymerization reaction is carried out on a belt (Japanese Patent Laid-Open Publication No. SHO 58(10)3) _49, 7(4), a kneading machine for pulverizing a stirring blade, and a polymerization reaction is carried out (Japanese Patent Laid-Open Publication) Sho 57(1982)-34,101) 'Performed reverse phase suspension polymerization (Japanese Patent Laid-Open Publication No. SHO 59(10)4)-37'_), or tilted or coated a monomer onto a fibril, and carried out a polymerization reaction (Japanese Patent Public Gazette Sho 62 (1987) _53, 3Q9). [Problem to be solved], the upper δ method is a reaction material such as a polymerization monomer, a polymerization initiator and a crosslinking agent, and a free silk reaction is carried out. _, the entire polymerization reaction is not easy to control, and the soluble content is also high. In view of the above, the present invention provides a high water-absorbent resin, which is green, and the silk reaction reaction is determined by the axis, and the heat of reaction is not too high. In addition to improving the operating environment, the product quality is further improved. The manufacturing method provided by the present invention at least comprises: 1) retaining an aqueous solution of an acid group-containing monomer having a neutralization ratio of 50 mole% or more and a polymerization reaction crucible to induce a tearing line towel, Free silk reaction Pre-polymerized 200813146's whose acid-containing monosystem is selected from acrylic acid or mercaptopropionic acid or 2_endoamine-2-methylpropanesulfonic acid or a mixture thereof; '2) adding money, The highly hydrophilic polybasic epoxy compound is subjected to a stepwise polymerization to form a rotating solid in a shaft prepolymer towel; 3) drying, pulverizing and screening with a hot air at a temperature of 25 ° C; 4 Surface crosslinking agent coating treatment; 5) heating surface treatment at a temperature of 8 ° C to 230 ° C; # 6) adding an inert inorganic salt powder. The reaction of the upper Syrian county can be carried out in a county-integrated anti-brain towel. The reactor needs to have the function of 纟 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ^ In addition to the vertical reaction tank in which the stirring paddle is generally installed, the polymerization reactor can also adopt a horizontal cylindrical container, and the center is equipped with a stirring water single screw or a parallel twin screw for one-way flow of materials. This ensures that the reaction material moves forward in one direction without reflow, thereby preventing the polymerization material from staying in the reactor 10 for too long to form a gelatinous solid. However, reactors of the above type are generally employed in batch feeds and are less advantageous for industrial production. Heart [Technical means for solving the problem] ί; The present invention provides a method for continuously producing a highly water-absorbing raw tree with a low soluble content, characterized in that: · the first step, the monomer solution is in the pipeline The medium is retained, and a polymerization initiator is added to the pipeline to cause the acid group-containing monomer to undergo a free radical reaction to form a viscous polymer. In the second step, after the viscous prepolymer is mixed with the polyepoxide 200813146-based compound, it can be continuously "domain-band reaction II", and various light sources are used above it (for example: pie line, infrared, x-ray or r-ray The poly-polymer is converted into a gelatinous solid. In addition to g, the seed-in-the-sea is in addition to the pain-free space of the rhythm-shaped container of the vertical reactor, and (4) ensuring that the aqueous solution of the reaction monomer first comes out, so that The pre-polymerization process reduces the residual needle of the fresh body, and the reaction of excessive rotation and recombination occurs. The anti-fresh water in the pipeline is an important factor in the control-polymerization reaction. If the residence time is long, the pre-polymerization is carried out. The more complete the reaction, the higher the prepolymerization degree and the molecular weight, and the lower the soluble fraction of the finished product, but it is more likely to occur in the pipeline in the phenomenon of over-spinning; such as retention_short, the viscosity of the polymer and the lower molecular weight' The soluble fraction of the finished product is higher, but the chance of excessive polymerization is less. In addition, the reaction monomer solution is silk-fed, and even the mixing uniformity of the spine and the bridging agent before the dissimilarity also affects the occupational reaction and the illuminating reaction. Heavy factor. In order to improve The above fluids are mixed with each other, and generally can be as follows: (1): In the pipeline, an inert gas such as nitrogen, or carbon dioxide, or helium, or nitrogen, or a mixture thereof is used, and the red industry saves costs. And considering easy to obtain, usually use nitrogen or carbon dioxide or a mixture thereof. In addition, the force of the inert gas is higher than the pressure in the pipeline, and the gas can be mixed with the liquid in the monomer solution. The effect, (2) in the addition of Wei Xuan or mixed fruit two fillers such as: (four) ring, or wave earrings, (3) make 贱 (four) to mix 7. Light-based polymerization technology developed sophisticated, applications are also quite extensive, such as : Tu Chang, 200813146 Printing, PCB/LCD process, footwear, etc. The use of photo-initiated polymerization has many advantages, such as: shortening the process, increasing production capacity and saving energy, etc. There are many kinds of light sources, including ultraviolet, infrared, χ ray or 7 ray, etc., generally used in purple = line, it has a shorter wavelength (10).nm), strong penetrating power. It is worth noting that The intensity of the UV light source used is 2 丽/αη, which often causes serious wear on the conveyor belt carrying the work. So: The belt must be replaced frequently and the production cost will increase. Therefore, the ship's light-lighting system has a light age of _, and (10) the front section of the conveyor belt is infra-red in the latter part of the ultraviolet ray. Since the surface material of the general conveyor belt is Nayue^, the heat can be 15G-2GG C, and It has the characteristics of anti-sticking and chemical resistance, but the bath is not light-resistant. The front-end yarn of the present invention uses a penetrating ultraviolet filament to initiate the polymerization of the single liquid from the bottom layer, while the latter stage makes: the penetrating power is weak. However, the infrared light with good heating effect is lucky, and the rest of the conveyor belt is cerebral palsy. Such a work object illuminates the material (4) and the riding strength of the vehicle (10) also reduces the wear of the conveyor belt. What is important is that the infrared light does not need heat medium: far, it can be heated by the thief, and the efficiency is extremely high, so the shortening between the two sides reduces the reaction. Therefore, the sub-point of the irradiation equipment makes the process space too large, and the temperature is The source cake stops heating and is safer. W·1 is easy and fast, and the acid-containing monomer required for the super absorbent resin produced by the present invention can use other water-soluble monomers having unsaturated double bonds in addition to propane acid 200813146, such as: T-acrylic acid, or marolinic acid, or fumaric acid, or 2-propylamine I methyl propyl sulphate or the like. Monomer. Optional non-specific limit · can be made - can also be combined with a variety of monomers - use: can be returned to the injection of Wei Qichun mixed body, such as: acrylamide, methyl propylene _, Acrylic acid 2-hydrocarbyl acetoacetate, methyl acrylic acid 2 _ keto acetonitrile, = dilute acid (tetra), acrylic acid (10), dimethylamine propylene propylene, propylene propylene propyl sulfonate It does not destroy the high water absorption and the physical properties of the silk. ^ Before carrying out the radical polymerization, the concentration of the aqueous monomer solution should be controlled between 20% by weight and 55% by weight of 'the appropriate concentration is between 黯% and 45wt%, and when the concentration is less than 20% by weight, the hydrated body after polymerization is too Soft and sticky. It is processed. 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 pH value of the finished product to make it neutral or slightly acidic, and the neutralizing agent is a hydroxide clock, sodium hydroxide, a hydroxide clock, a post-acid clock, Sodium carbonate, potassium carbonate, hydrogen carbonate clock, sodium hydrogencarbonate, potassium hydrogencarbonate and ammonia. The ketone group containing the acid group monomer is partially neutralized into a clock 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 mol% to 85 mol% / an appropriate concentration is 50 mol. When the percentage of % to 75 mol% of neutralization concentration is below 45 m〇1%, the four values of the finished product will be low. The percentage of the molar concentration of the neutralization concentration is 85 m〇1% or more, and the value of the finished product will be southerly. If it is not neutral or slightly acidic, it is not suitable or safe to contact with the human body. 200813146 Prepolymerization begins with the decomposition of a polymerization initiator to generate free radicals. The polymerization initiator may be selected from a thermal decomposition type initiator, and a suitable thermal decomposition type initiator is a peroxide such as: listening domain, di-tert-butyl peroxide, Weihua or over-heterobiliary salt, Age salt) et al 'and azo compounds such as: 2.2, -azobis(2-cyanopropan) dihydrochloride, 2.2,-azo double-dip dimethyl-isobutyl) di-salt Acid salt; can also make (four) · 'oxidation of silk to the starter, such as: acid sulfite, thiosulfate, anti-bad or ferrous salt; or redox type and thermal decomposition I35 The initial age and the Xiao's oxidative reduction start to react to generate free radicals'. When the radicals are transferred to the monomer, the polymerization reaction is initiated. As the polymerization proceeds, N· releases a large amount of heat and raises the temperature. When the temperature reaches the decomposition temperature of the thermal decomposition type initiator, the decomposition of the second stage thermal decomposition type initiator is caused, and the entire polymerization reaction is more complete. The free-form reaction initiator is generally used as a percentage of 〇·OOlwt% to the weight of the neutralized acrylate, and more suitably in the range of wt. lwt% to 5% by weight. When the percentage 験0. OOlwt% or less, the reaction is too slow, which is unfavorable economical efficiency; when the weight percentage or more is used, the reaction is too fast, the reaction heat is difficult to control, and it is easy to be polymerized excessively to form a gel-like solid. A crosslinking agent should be added to the viscous prepolymer before the photoinitiation polymerization. The crosslinking agent may be a compound having two or more unsaturated double bonds, such as N,N_bis(2-propenyl). An amine, N,N '-methine bis acrylamide, n, n 'monodecyl bis methacrylate, propylene acrylate, ethylene glycol diacrylate vinegar, polyethylene glycol diacrylate vinegar, 12 200813146 Ethylene glycol di-f-acrylate, polyethylene glycol dimethacrylate, glycerol triglyceride, trimethyl propyl glyceride, glycerin plus Ethylene acrylate or glycerin Acrylate, dimethanol, propylene oxide, trisyl acrylate, trimethyl propyl acrylate, trimethyl propylene triacrylate N,N,N-bis(2-propenyl)amine, ethylene glycol diacrylate, dipropylene triethylene glycol, etc., may also have two or more compounds, such as sorbitol polycondensate Manganese, polyglycerol miscible water, ethylene glycol diglycidyl bond, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl , Dipropylene glycerol polyglycidyl under reduced nettle. After the radical reaction, the superabsorbent resin can have an appropriate degree of crosslinking, and the superabsorbent resin colloid can have appropriate processability. The radical polymerization reaction crosslinking agent may be used singly or in combination of two or more. Free radical polymerization cross-linking The appropriate amount of additives is between 5% and 5% by weight of the total weight of the reactants (based on the total solids of the reactants), and the appropriate amount is in the range of 〇· _% to (4) Meanwhile, the amount of the additive is less than or equal to 重量·wt% by weight. The hydrated body is too soft and viscous to be unfavorably mechanically processed, and the amount of the additive is too low in water absorption of 5 wt% or more to lower the resin property. The viscous prepolymer can be subjected to a one-step photoinitiation polymerization on a conveyor belt reactor or a horizontal reaction buckle equipped with a stirring blade, and the prepared superabsorbent gel is first cut into a particle size by a mincer. A small gel of 2 〇 mm or less, preferably having a particle diameter of i 〇 mm or less, and then drying. Drying temperature can be dried at loot: to 25 (TC, drying temperature is 12 〇 13 200813146 C to 18GC for drying s, # drying temperature (10). c ugly dry time • too long not ~ 纟~ Qi effect display 'drying temperature above 180 ° C drying to make the cross-linking agent early to pay the % reaction so that the dry process towel, because the degree of crosslinking is too high, can not effectively remove the residual monomer, to achieve the effect of reducing low residual monomer After drying, it is pulverized, sieved, and then subjected to surface cross-linking agent coating treatment. The fixed particle size is 〇·06mm to ^ 〇〇 between the legs, and it is suitable for 〇·1〇 coffee to 眷Q.85Gmm _0.06 Gu Qiqi improves the finished dust, 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 an insoluble hydrophilic polymer, and the resin has a bridging structure inside. -In order to improve #quality such as: increase the absorption rate, increase the strength of the carcass, anti-caking property of the South, liquid permeability, etc., will further bridge in the resin table (5), the surface cross-linking treatment is able to use Acid-based reactive polyfunctional crosslinker' before There are many specializations; for example, dispersing superabsorbent resin and cross-linking agent for surface cross-linking treatment in organic solvents (JP-A-56-131608, JP+57-44627, IP-A-58-side 2 , JTP-A58-117222) directly mix the crosslinking agent and the crosslinking agent solution into the superabsorbent resin (JP-A6G-163·, PA-6G-255814) using an inorganic powder, and add steam after treatment ( 1P-A-1-113), surface treatment using an organic solvent, water, and a polyol (JP-A-63-270741 > JP-A-64-50707 > JP-A-1-292004) solution, Water, ether compound (JP+2_1539〇3), etc.; these surface treatment methods can increase the absorption rate and increase the water absorption rate under pressure, but it will cause the adverse consequences of the excessive reduction of the holding power of 200814146, reducing the practical application. After screening the fixed particle size, the cross-linking which can be simultaneously treated in the surface treatment according to the present invention may be a polyol such as glycerol, ethylene glycol, diethylene glycol, or the like: Alcohol, propylene glycol, 1,4 butane: alcohol, three can use polyamines such as: ethylenediamine, diethylenediamine, triethylenediamine, polyethylene: can be used with two Two or more base compounds such as: (4) oleic acid, polyglycerol polyglycidyl _, ethylene glycol diglycol _, diol alcohol: oil ether, polyethylene glycol dimer glycidyl ether, double Glycerol polycondensation: Ether Temple; can also use alkylene carbonate for example: glycolic acid, 4~methyl U ^ heterocyclopentan-2-one, 4,5-dimethyldioxy Heterocyclic pentamidine ~ 2 Duo 4' base -!, 3-4 rpm phase, 4_ethyl 3 dioxine phase, '--Rusaki m4,6m,3_dioxane _2-ketone or recorded - suspected tender-2-_. The use of cross-linking agents at the surface can be used alone or in rain (4). The appropriate amount of adhesion at the surface, the amount is between 〇. Xie Weigui (based on the total solids of the reactants), a more appropriate amount 'between 0.005 Λ to 5 wt%, cross-linking at the surface The amount of the additive is not effective when the weight percentage is 〇. 〇 伽 伽 , , , , 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝 丝When the surface cross-linking agent is applied, the surface cross-linking agent may be added as a surface cross-linking straight or hydrazine surface cross-linking agent aqueous solution, or a surface cross-linking agent hydrophilic organic solvent solution may be added, hydrophilicity The organic solvent such as decyl alcohol, ethanol, propanol, 15 200813146 isobutanol, acetone, _, diethyl ether or the like is not particularly limited, and it is preferable to form a solution of m and ethanol. The surface crosslinking agent adds strength. The inert inorganic salt powder is absorbed at a high rate to assist the dispersion of the solution, and the inert inorganic salt powder may be added or dioxolyzed, and the mixture may be etched or mixed. Its towel is like =, the second emulsion frequency is good. The addition of the fine inorganic clock to the weight percentage u, to 1 〇 phase ^ which is preferably 0.01 turtle 4.0. .0 After the surface crosslinking agent coating treatment, 卩 8{rciL 230.匚 Heat treatment, the surface of the parent ship is cross-linked, and the internal cross-linking agent is cross-linked to achieve the effect of the tree. The crosslinking reaction time is too long below the treatment temperature of 8 Gt. When C is used, the resin is easily deteriorated to affect the quality. As for the processing time, it is better to adjust the temperature according to the processing temperature of 2 to 150 minutes. The temperature is high for a short time and the low temperature for a long time. "Because of the high water absorption tree redemption, there is a phenomenon of agglomeration and agglomeration. In order to avoid the use of high-thirty two-use = absorbing the age of the tree, it will be agglomerated, and it will be high. The end of the domain or the surfactant, so that the surface is slightly bisexual and high-enriched _ retaining the occlusion of the secret occlusion, this inert no, or dioxotomy, or oxygen brain, or _, or rod a or A Resident, or phenolic acid, or carbonated town, etc. or a mixture thereof; usually, the surface of the surface of the machine is related to the inorganic particle size, and if it is granules, the surface area of the heat powder is larger. Therefore, the effective inert inorganic salt powder σ car] its sputum gastric inorganic salt powder is added in the range of weight ratio 16 200813146 ( 〇〇〇 5wt turtle 1Q light between, where Q · _. to 嶋 good, inert no powder Its _ is please (10) to (10) • If the granules are less than the size of the i, the cost of the 1 shed is too high for industrial production. If the granules are larger than /M, the amount of the salt is too high. The end of the resin absorption of the resin can be added alone or with the surfactant or with the degree of organic matter added to the person's interface The organic compound having a drilling degree may be selected from a non-ionic surfactant having a brain value of 12 or more, or a water-soluble anionic surfactant, a Lujiexuan type riding agent, or a yin-yang type interface living side, or a mixture thereof, usually an interface The active agent or the viscous organic compound may be glycerin, ethylene glycol,hexaichi, polyoxyethylene alcohol, or polyethylene glycol, or polyethylene glycol stearate, or stearic acid XK ethylene glycol. Ester, or polyoxyethylene nonyl phenyl ether, or polyoxyethylene octyl benzoquinone, or polyoxyethylene dodecyl ether, or polyoxyethylene alkyl ether, or polyethylene oxide laurel, etc. The compound may be formulated as an aqueous solution or added separately, with a suitable surfactant or viscosity organic compound additive amount between 重量·〇〇1 wt% to 5 wt% (based on the total solids of the reactants), A more suitable amount by weight is between 0.Olwt% and 3wt%/〇. 17 200813146 SUMMARY OF THE INVENTION The present invention provides a method for continuously producing a superabsorbent resin having a low soluble content. In the first step, the aqueous solution of the acid-containing monomer and the polymerization initiator are passed through a long pipeline, and the nitrogen and thermal decomposition initiators are introduced at about 1/5 and 1/2 of the long pipeline. Two azo compounds or epoxy compounds are introduced into the urethane at a distance of about 85 cm from the outlet to form a viscous prepolymer. The second step is to mix the prepolymer with the polynuclear compound and continuously add it. To the belt reactor, the upper part of the belt is ultraviolet light; the latter part is infrared light and two different light sources are used to introduce the viscous county to transform and harden into solids. The above production methods provided by the hair ride have the following characteristics: (1) The viscosity of the polymer relative to the liquid reaction material is obviously low. The yak is low, it is easier to match the belt reactor, and the whole τ is considered to be raised, the heat of reaction is not too high, (2) the biliary The line response reads the principle of saving the franc, and more ensures the principle of the first-in-first-out reaction, and achieves the goal of continuous production. (3) The method of using two-stage illumination to reduce the exposure time of ultraviolet rays to the conveyor belt. It consumes her infrared heating efficiency is very good, can save the province, the original and the cost of the ancient pa)) ^ This source of Asia has a simple and safe 'two occupation, (5) shorten the process, shake and Jia A匕古口, such as the promotion of Chera, asks about the amount of shellfish, especially the reduction.
溶物的含量 溶物吸水幽的低可溶物含量之特性，其 g在500_轉速下攪拌—個小時後，以濾紙 18 200813146 遽出SAP萃取液。最後，秤取該萃取液2〇 g，先以〇. in酬滴 定’再使用0. IN HC1進行反滴定以求出SAp可溶物的含量。 【實施方式】 '以下以實施例說明本發明’但本發明之技術及專利範圍不受這 些實施例所限制。 實施例一： # ⑴先於中和槽中加入1·重量份的丙稀酸及獅.7重量份的 卩之後於冰/合下心1476. 3重量份的氫氧化納水溶液(濃度為 )緩緩加人上述丙烯酸水溶液巾。此時得到 38. 6wt%的水溶液，其中有68 _的丙稀酸中和為丙稀酸納二 ⑵中和程序完成後’利用水調溫控制部分中和之丙婦酸納鹽水溶 液為20°C左右。 馨⑶上述單體溶液的流量為⑽公升/小時，使其通過一支直 徑為5公分、總長度為26. 35米的不鏽鋼管。在不鐵鋼管入端 5公分與10公分處側邊分別連接—支餘G. 5與"公分的不 鐵鋼官。前者導入氮氣，流量控制為200公升/小時，後者則 通入過硫酸钟/亞硫酸氫納=1/1(重量比），流量控制為2毫升 々、時。預聚和反應溫度控制在2〇ΐ，最後所得之預聚物黏度 為 80cps 。 ⑷距離管線出口端85公分錢邊麵二支餘G. 9公分的不鏽 19 200813146 鋼管，一支導入偶氮二異庚月青，流量控制為2〇毫升/小時， 另一支則導入丙二醇聚乙二醇三縮水甘油i|(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，傳送帶上方裝置有紫 外線與紅外線燈管，前段利用紫外線照射上述混合液體5秒， 後段則使用紅外線照射30秒，使其硬化成膠體。 (6)利用切式絞碎機切成2mm粒徑以下的凝膠體。 ⑺以130°C溫度乾燥2小時；利用篩網篩選〇·丨麵〜Q.阳腿峡 粒徑，得粉狀高吸水性樹脂。 ⑻秤取此高吸水性樹月旨1Q()g，加人硫酸轉末ig，待混合均勾 後再加入乙二醇碳酸醋/水/曱醇=1/1/1(重量比)溶液超，以 215°C温度加熱處理分鐘。 ⑼冷卻後，加入以碳_(台塑公司生產品名：ns—賴及雇 _ # ’认〜夜2g ’均勻混合後即得高性能高吸水性樹脂。測定保 持力=33. 7g/g，49 ―壓力下吸水倍率=23. _，可溶物 實施例二： (1)重複貫施例_， 秒，結果所得之 壓力下吸水倍率 實施例三： 但刚段照射時間為1Q秒，後段照射時間為30 高吸水性翻旨的保持相4 32· 4g/g，49 g/on2 = 22· 3g/g，可溶物含量=8· 7%。 20 200813146 ⑴重複實施例-，但前段照射時間為+ 持力則為=== 壓力下吸水倍率=22.4g/g，可溶物含量1 實施例四： ° (1)重複貝細例一，但不鏽鋼管長度改 9 度為挪心结果所得之高料之預聚物黏 _g，49g_力下吸水倍率月曰的保持力則為 5屬。 4〜23.9g/g’可溶物含量= 實施例五： ⑴前段照射時間為_、，後段照射時間3〇The content of the dissolved matter is characterized by the low soluble content of the dissolved water, and the g is stirred at 500 rpm for an hour, and then the SAP extract is extracted with a filter paper 18 200813146. Finally, the extract was weighed 2 〇 g, first titrated with in., and then back-titrated using 0. IN HC1 to determine the content of SAp solubles. [Embodiment] The present invention is described below by way of examples, but the technical and patent scope of the present invention is not limited by the embodiments. Example 1: # (1) Adding 1 part by weight of acrylic acid and lion. 7 parts by weight of hydrazine to the neutralization tank, then immersing the ice/closing core 1476. 3 parts by weight of the aqueous sodium hydroxide solution (concentration) Slowly add the above aqueous acrylic acid towel. At this time, 38.6 wt% of an aqueous solution was obtained, in which 68 _ of acrylic acid was neutralized to sodium benzoate (2). After the neutralization procedure was completed, the aqueous solution of sodium benzoate sodium salt partially neutralized by water temperature control was 20 °C or so. The flow rate of the above monomer solution (3) was (10) liters/hour, and it was passed through a stainless steel tube having a diameter of 5 cm and a total length of 26.35 meters. At the entrance of the non-ferrous steel pipe, 5 cm and 10 cm are respectively connected to the side - the branch of the G. 5 and the "cm". The former introduces nitrogen gas, the flow rate is controlled to 200 liters/hour, and the latter is passed through the persulfate clock/hydrogen sulfite = 1/1 (weight ratio), and the flow rate is controlled to 2 ml 々. The prepolymerization and reaction temperature were controlled at 2 Torr, and the resulting prepolymer had a viscosity of 80 cps. (4) From the outlet end of the pipeline, 85 centimeters of money, two sides of the remaining G. 9 cm of stainless steel, 200813146 steel pipe, one imported azo diisoheptane, the flow rate is controlled to 2 〇 ml / hour, and the other is introduced into propylene glycol Polyethylene glycol triglycidyl i| (n = 7), flow control of 15 ml / hour. (5) The reaction fluid described in (4) is added to a conveyor belt. The upper part of the conveyor belt is provided with an ultraviolet and infrared lamp tube, the front stage is irradiated with ultraviolet rays for 5 seconds, and the latter stage is irradiated with infrared rays for 30 seconds to harden it into a colloid. . (6) A gel having a particle size of 2 mm or less was cut by a cutter. (7) Drying at a temperature of 130 ° C for 2 hours; screening the particle size of 〇·丨面~Q. Yangjixia by a sieve to obtain a powdery superabsorbent resin. (8) Weighing this high water absorption tree month 1Q () g, adding human sulfuric acid to the end ig, after mixing and then adding ethylene glycol carbonate / water / sterol = 1 / 1 / 1 (weight ratio) solution Ultra, heat treatment at 215 ° C for a minute. (9) After the cooling, the high-performance superabsorbent resin is obtained by the carbon_(the product name of the plastics company: ns-laid and hired _# 'recognition ~ night 2g'). The retention is determined to be 33. 7g / g, 49 ―Water absorption ratio under pressure=23. _, soluble matter Example 2: (1) Repeating the application _, seconds, the resulting water absorption magnification under pressure Example 3: but the initial irradiation time is 1Q seconds, the latter stage The irradiation time was 30. The retention phase of the high water absorption was 4 32·4 g/g, 49 g/on2 = 22·3 g/g, and the soluble matter content was 8.7%. 20 200813146 (1) Repeated Example - but the previous paragraph The irradiation time is + holding force is === water absorption ratio under pressure = 22.4g / g, soluble content 1 Example 4: ° (1) repeating the shell fine example 1, but the stainless steel tube length is changed to 9 degrees for the heart As a result, the prepolymer of the high material obtained has a viscosity of _g, and the retention capacity of the water absorption ratio of 49 g_ force is 5 genus. 4~23.9 g/g' soluble matter content = Example 5: (1) The irradiation time of the front stage is _,, the rear irradiation time is 3〇
._水___力則為34场，如/on2 屋力下吸水倍率=23.5g/g，可溶物含量H 實施例六： G)重複=細’但前卿㈣⑽，咖射時間為別 ^ Mlj 4 32> ?g/g, 4q 壓力下吸水倍率=23. 8g/g，可溶物含量，9%。 實施例七： ⑴時間為!秒~^ 狀祕性樹脂的保持力則為35.1的，仙Μ ι下及水倍率= 24.lg/g，可溶物含量1糨。 21 200813146 實施例八： ⑴重複實施例七，但前段照射時間為1移、，後段照射時間為40 秒，結果所得之高吸水性樹脂的保持力則為36.的，糾心2 壓力下吸水倍率= 23.8g/g，可溶物含量叫辦。 貫施例九· ⑴重但祕難_為丨秒，後段闕時間為5〇 办，果所狀高吸水性細旨的保持力則為37场，*心2 壓力下吸水倍率=23.2g/g，可溶物含量m 實施例十： (1)重複實施例七，但不鏽鋼管長度為52半 盔91〜· 木，出料之預聚物黏度 為210CPS，、!σ果所得之高吸水性樹月旨的保持 49 g/cm2壓力下吸水倍率=24 〇 /g ，、、' . Η ^ h合物含量=4·3%。 實施例十一 ·· _ (1)重複實施例十，但前段照射時間為 & 朴处里t後段照射時間為40 果所狀高吸水性樹脂的保持力則為打輪，糾心2 壓力下吸水倍率= 23. lg/g，可溶物含量叫伙。 實施例十二： ⑴重複^例十，但前段照射時間為丨秒，後触射時間為5〇 果所得之高吸水性樹脂的保持力則為3δ场，49 — 壓力下吸水倍率= 22.4g/g，可溶物含量^屬 22 200813146 比較例一： ’ （1)重4^只鈀例，但僅使用前段紫外線照射2〇秒，結果所得之 • 回吸水樹脂的保持力為30.5g/g，49g/cm2壓力下吸水倍率> 22· lg/g，可溶物含量= ι〇· 。 比較例二·· )重鈸只化例，但不鏽鋼管長度改為Μ米，出料之預聚物黏 度為21〇cps，而前段僅使用紫外線照射2〇秒，結果所得之‘ • D及水樹脂的保持力為32.阶，49g/cm2壓力下吸水倍率= 23· 9g/g，可溶物含量=& 7%。 【圖式簡單說明】 無0 【主要元件符號說明】 無。 23._水___力为34场, such as /on2 house suction capacity = 23.5g / g, soluble content H Example 6: G) repeat = fine 'but before Qing (four) (10), the time of the coffee is别^ Mlj 4 32> ?g/g, 4q under water pressure absorption ratio = 23. 8g / g, soluble content, 9%. Example 7: (1) The time is !second~^ The retention property of the secretive resin is 35.1, the immortality and water ratio = 24.lg/g, and the soluble content is 1糨. 21 200813146 Example 8: (1) Example 7 is repeated, but the irradiation time of the first stage is 1 shift, and the irradiation time of the back stage is 40 seconds. The retention of the obtained super absorbent resin is 36. The water absorption under the pressure of the correction 2 Magnification = 23.8g / g, soluble content called. Example 9 (1) Heavy but difficult _ is a leap second, the latter period is 5 ,, the retention of the superabsorbent essence of the fruit is 37, * heart 2 under water pressure override = 23.2g / g, soluble content m Example 10: (1) Repeat Example 7, but the length of the stainless steel tube is 52 half helmet 91~· Wood, the prepolymer viscosity of the discharge is 210 CPS, and the high water absorption of the σ fruit The retention rate of the sexual tree was maintained at a pressure of 49 g/cm 2 = 24 〇 / g , , , ' . Η ^ h content = 4.3%. Example 11·· _ (1) The tenth embodiment is repeated, but the irradiation time in the previous stage is & the irradiation time in the back part of the t-section is 40. The holding power of the superabsorbent resin is the wheel, the correction 2 pressure The lower water absorption ratio = 23. lg / g, the soluble content is called a partner. Example 12: (1) Repeating Example 10, but the pre-irradiation time is leap seconds, and the retention time of the superabsorbent resin obtained by the post-shot time of 5 capsules is 3δ field, 49 - the water absorption ratio under pressure = 22.4g /g, soluble content^genus 22 200813146 Comparative Example 1: '(1) Heavy 4^ palladium case, but only using the front-stage ultraviolet irradiation for 2 sec seconds, the result obtained is: Resilience of the back-absorbent resin is 30.5 g/ g, water absorption ratio under pressure of 49 g/cm 2 > 22 · lg / g, soluble matter content = ι〇·. Comparative Example 2··) The sputum is only a chemical, but the length of the stainless steel tube is changed to glutinous rice, and the viscosity of the prepolymer of the discharge is 21 〇 cps, while the anterior segment is only irradiated with ultraviolet light for 2 〇 seconds, and the result is ' D and The retention of the water resin was 32. The water absorption ratio under the pressure of 49 g/cm 2 = 23.9 g/g, and the soluble matter content = & 7%. [Simple description of the diagram] No 0 [Description of main component symbols] None. twenty three