201100474 .六、發明說明： 【發明所屬之技術領域】 本發明係關於一種製造高吸水性樹脂之方法，特別是一種粉 狀、不溶於水、可吸收水或尿液及血液具有低殘存未反應單體、 高保持力及高壓力下吸水倍率的高吸水性樹脂之製造方法。 【先前技術】 高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中釋出。由於 具有上述之特性，所以最早使用於農森林業的土壤保水劑，近年 因向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生用品的吸水劑以及 保存食物用的保鮮用品等。 曰'衣以同夂不性树舳的材料的技術，例如已有遇水分解型 的澱粉丙騎(hytolyzed stareh卿lc論峨财合物（日本專 __昭49(叫43,395)、中和之澱粉丙烯酸接枝聚合物 專利公開公報昭51(1976>125,468)、4化乙稀醋酸丙稀醋 物或：=Τ=(:Γ_、水解_共聚 (日本專利公報昭53(·)·15,959)以及部 目〜口，丙烯酸（日本專利公開公報昭％(觸㈣辦）等專利。 别从使用丙烯酸及丙烯酸鹽 ▲ 佔最大邱於a县θ 丁又聯聚口所侍之兩吸水性樹脂 大*也最具經濟效益，其原因為丙稀酸可迅速由市售取 3 201100474 得、製得時縣性樹脂具有較高的吸水能力、製造成本低廉且 最具經濟效益以及不會引起腐爛性的分解，故丙稀酸及丙稀酸鹽 成為最普遍化的高吸水性樹脂製造材料。 聚合丙烯酸及__戦高财性繼的絲已被多方面 的開發成功，対多配應胁4界生產。絲合方法有鑄膜 聚合反應（日本專利公報昭和48_)·42,466)、於輸送帶上進行 聚合反應（日本專利公開公報昭和58(1983)_49,714)、具粉碎之授 拌刀片的捏拌基中進行聚合反應（日本專利公開公報昭 57(19_，1〇1)、進行逆向懸浮液聚合反應（日本專利公開公報 昭59(1984>37,〇〇3)或將單體噴灑或塗覆於纖維基質上進行聚合 反應（日本專利公開公報昭62⑽⑽’期）等專利。 一1 又而§ ’吸水性翻旨粉末在長時間之儲存下，會因為吸水 性樹醋聚合物的分解而有變色(黃色和掠色）的傾向。更甚於，熱 帶或亞熱帶®家因驗潮濕，吸水性_旨粉末變色(黃色和掠色） 的If形會加速進仃（大約四至六月），因此維持吸水性翻旨的贿 時效及延遲變㈣時間成為當今生產業者努力解決的目標。 吸水性樹S旨的變色雖然對於其_旨之物理特性並不會有太大 的改變’但直接影響到製成衛生用品後，變色的吸水性細旨會讓 使用者感糾魅用品受污染、品f不好的觀感，轴影響生產 廠商的彳。譽。因此，在保存時間内，會變色的吸水性細旨製品就 會大大地降低其作為商品的價值。對此具有變色防止效果之吸水 r生樹月曰問題’已知有例如，日本】A_A备觀51號專利認為其中 201100474 的因素是在於吸水性樹酯的分解和聚合物鏈的斷裂隨時間而著 色，因此建議使用有機磷酸化合物或其鹽之高吸水性聚合體組合 物，但加入有機磷酸化合物會使製作方法複雜化且有安全問題。 JA-A-2000-230129號，JA- 2000-327926號及在含金屬螯合劑之 吸水性樹脂凝膠體，乾燥前或乾燥中添加〇 〇〇1〜6重量份之還元 劑或氧化劑（台灣專利第200306987號）以及使用過氧化物（美國專 利4,959, 060號)吸水性樹脂在高溫高濕下長期保存時，無法發揮 〇 充分令人滿意之變色防止效果。 由於吸水性樹脂為對水不溶解之親水性聚合體，一般樹脂内 部具有均勻性的架橋結構。就改善吸水性樹脂的品質而言，為了 提高吸收速率、提高膠體強度、提高抗結塊性以及液體滲透性等 物理性質，都在篩選固定粒徑後會在樹脂的表面再作進一步架 橋。此種絲交聯處理即_具有能與酸基反應之多官能基交聯 劑’目則已有許多專利被揭露，例如：分散吸水性樹脂與交聯劑 〇於有機溶劑中進行表面交聯處理（JP-A-56-131608、 JP-A-57-44627、JP_A_58_伽2、jp姐 117222)、使用無機粉直 接將交聯劑與交聯劑溶液混入吸水性樹脂處理（Jp_A6(M6罵、 JP-A.255814)、添加交聯劑後以蒸氣處理（jpn.H遍）、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、爪从纖⑷、使用有機溶液、水及喊（ethe〇 化口物（JP-A-2-153903)等。這些表面處理的方法雖能提高樹脂 的吸收速率或提高壓力下之吸水倍率，但將造成其储力下降過 5 201100474 多的不良後果，降低實際應用之性能。 聚合丙烯酸及丙婦酸鹽生成高吸水性樹脂的方法可由數種 已知的方法製得’如水溶㈣合反應、逆相鮮液聚合反應、乳 化聚合反應或將單體魏或塗覆於雜基質找行聚合反應等 方法。在24些方法t ’逆械浮絲合反應以及乳化聚合反應必 須使用有機溶劑，但若無法有效的控制聚合反鱗的溫度，有機 ;谷劑將造成反應系統溫度以及壓力的增加，產生起火現象甚至引 發***’進域_操作現場人㈣安全以及造成環境污染等問 題’其成品也有有機溶劑殘留的疑慮。 在高吸水輯闕製針，為麵脂錯翻乾燥效果，通 常先利用切碎機、切條機、押出多孔機、螺旋切片機或絞碎機切 成直桎20mm以下小凝膠體，直徑i〇mm以下更佳，再進行烘乾， 但切成小凝賴時，因小_體具錄性將會造錢膠體互相凝 結’此相互凝_現象會使在烘乾時之熱氣無法義凝膠體層， 致使無法讓每個水凝膠體均勻受熱，而影響烘乾的結果。至今倘 有許夕科學豕一直為增加水凝膠體的分散性以提高乾燥效率而 努力，技業界亦已有鮮提高水凝賴的分散性龄法被開發出 來’如:利用界面活性劑與單體水溶液混合，並將聚合引發劑進行 聚合反應，或是添加交聯劑與界面活性劑的混合溶液於酸性型單 體水溶液中增加水凝膠體分散性，以提高乾燥效率的方法（美國 專利4,286,082號；台灣專利11509(H虎），在押出機多孔板内加刀， 201100474 • 以協助跋1的絞碎及分散（日本專利特許公開公報昭54 (1979)-32，176)、在押出機多孔板内加刀，並添加石夕膠乳化劑以協 助明1的絞碎及分散(日本專利特許公開公報昭59 (1984)-119，172 號）、控制gel溫度45-90度及多孔板孔徑為6 5_18mm時押出（日 本專利特許公開公報平5 (1994)-70,597號)，添加纖維素衍生物或 界面活性劑於水凝膠體表面，以增加水凝膠體分散性(美國專利 4,818,464號），更有添加幾丁質_聚按類化合物於水凝膠體， Ο 以提高吸水性樹脂的物理性質(美國公開專利0050090586號）。 上述利用界面活性劑與單體水溶液混合以提高水凝勝體分散 性的方式’會造成高吸水性猶财力降低；使賭環熱風乾燥 裝置提祕乾效率，容胃因為烘乾溫度過高或是烘乾時間過長， 導致及水树月曰產生劣化現象，以致於吸水性樹脂殘存單體含量 過高；添加纖維素衍生物歧界面活_於水凝賴表面，雖然 可以提高水郷體分散性’但容易在烘乾過程造成吸水性樹脂顏 色變肓’利用在押出機多孔板内加刀以協助凝勝體的絞碎及分 散’其改善錢雜齡散絲不甚理想；在押出機纽板内加 刀’並添加石夕膠乳化劑以協助凝膠體的絞碎及分散，雖然可相當 有效的改善絞碎及分散性’但因添加之石夕膠乳化劑為低親水性界 面活性劑，所时造歧水性纽變，致舰水性翻旨的吸水速 率及吸水倍數降低;利用控制凝膠體溫度45_9〇度及多孔板孔徑為 6.5彻m時押出則有凝膠體溫度控制不易，及降低凝膠體難效 7 201100474 果亦相當有限；使用幾丁質-聚胺類化合物噴灑於水凝膠體表面的 方法亦會有成本過高以及添加過量烘乾效率不佳的問題產生等缺 點。 【發明内容】 馨於以上的各種缺點與問題，本發明的主要目的在於提供一 種粉狀、不溶於水，可吸收水液或尿液及血液具有極佳之耐黃化 性質及低殘存單體含量的高吸水性樹脂之製造方法，藉以解決先 前技術所揭露之方法，雖然能提高高吸水性樹的分散性，但卻改 變了向吸水性樹脂的顏色，導致消費使用者實際應用性能不佳的 問題。 本發明，一種粉狀、不溶於水，可吸收水液或尿液及血液具 有極佳之耐黃化性質及低殘存單體含量的高吸水性樹脂之製造方 法’係包括；於凝膠體上添加塗覆分散劑，其分散劑之鐵離子含 量小於30pPm(partS per million，百萬分之）、鎘離子含量不超過 20ppm，或不飽和單體水溶液中的過渡金屬離子合計含量小於 50Ppm然後再將塗覆分散劑之凝膠體乾燥、粉碎及篩選固定粒 徑，以及添加表面交聯劑後進行加熱處理。 依照本發明，粉狀、不溶於水，可吸收水液或魏及血液具 有極佳之耐黃化性質及低殘存單體含量的高吸水性樹脂之製造方 法，其在添加表面交聯劑步驟之前，更可以添加惰性無機鹽粉末 以幫助表面交聯綱方散。惰性無機鹽粉末以反應物總_份為 基準’添加量範圍為重量百分比〇.〇〇5至1〇.〇。而使用的惰性無機 201100474 鹽粉末為她s、二氧切、氧他、氧傾或上述群組之混合 物。 在加熱處理之後更可進行抗結塊性處理。此抗結塊性處理之 ^驟^括’先添加水不溶性微粉縣加黏著劑使林溶性微粉黏 者於高吸水性樹脂表面。水不溶性微粉以反應物總固形份為基 準’其添加量為重量百分比〇.〇〇1至1〇.〇而黏著劑以反應物總固 形份為基準，添加量範圍為重量百分比α⑻丨至100。 ❹ 本發狀不飽和單體水溶液之漠度為重量百分比2G至55。 不飽和單體水祕㈣酸或具有義基_雜和雙鍵的水 溶性單體或上述群組中之混合單體。不飽和單體水溶液亦可視情 況添加具有不飽和雙鍵其他親水性的單豸，或添加水溶性高分子 以降低成本。 本發明所添加之作_怖錢和物水鎌，其中和濃 〇 度為莫耳百分比45至％。所使用的中和劑為氣氧化銅、氮氧化 钟、碳酸納、碳酸鉀、魏氫鈉、碳酸氣卸、氨類化合物或上述 群組之混合物。 本發明之㈣交賴以反應__份為鲜，其添加劑量 為重量百分比0规至5。所使_㈣交聯料具有兩個或兩個 以上不飽和雙賴化合物或具有_—上環氧基的化合物 或上述群組之混合物。 本發明之__巾和含酸基單體勤轉基準，其添加劑量 為重量百分比G雇至10。所使關起始_熱分解型起始劑、 201100474 氧化還原型起始舰上述群組之混合物。熱分解_始劑為過氧 化物或偶氮化合物。氧化還制起始劑輕性亞硫_、硫代硫 酸鹽、抗壞血酸或亞鐵鹽。 本發明表較麵的添加型式可為錢添加、概水溶液添 加或調成親水㈣機關水溶液添加。其添加·為重量百分比 0.001至10。所使用的表面交聯劑為多元醇、多元胺、具有兩個或 兩個以上環氧基的化合物、碳酸亞烴s旨或上述群組之混合物。 本發明加熱處理的溫度為攝氏90至23G度，時間為2至15〇 分鐘。 誠如上述，本發明係藉限制分散劑鐵離子、錄離子或過渡金 屬離子之含量所製成的高吸水性樹脂，具有極佳之物理性質，例 如耐黃化性質及低殘存單體含量。 軸本敵槪_嫩_㈣糾有低殘存 早體含量及料雌質㈣性，所以可提高使用上的安全性，因 ^發明之紋水性樹脂將能更適用做為各_式_㈣品、「 晨業,用及食品保鮮用的吸水劑。 、) 有關本發日⑽舰触果，喊佳實關純詳細說明如下。 10 201100474 • 【實施方式】 本發明所提供之一種粉狀、不溶於水，可吸收水液或尿液及 血液具有極佳之耐黃化性質及低殘存單體含量的高吸水性樹脂， 係為一種限制過渡金屬離子含量製造高吸水性樹脂之方法，包括 部分中和不飽和單體水溶液的含酸基單體成為含酸基單體鹽類， 再於不飽和單體水溶液添加内部交聯劑；之後，於不飽和單體水 溶液添加起始綱始自由絲合反應；將自絲聚合反應所得之 〇 凝膠體切碎，並添加錄級_财，使其分散狀鐵離子含 罝小於30Ppm(parts per million，百萬分之）、鎘離子含量不超過 2〇Ppm ’或分散劑中過渡金屬離子合計含量小於50Ppm;再進行乾 燥、粉碎及轉固絲鮮工序；最後添加表岐聯劑後進行加 熱處理’即得高吸水性樹脂。 本㈣之餘、秘於水，可核或驗及血液具有極 佳之耐汽化性質及低殘存單體含量的高吸水性樹脂之製造方法， 〇在添加表面交聯劑前，可添加惰性無機鹽粉末，以幫助表面交聯 劑的分散’而在加祕理之步雜更可做—抗結舰處理，使高 吸水性樹脂具有吸濕後不易結塊之特性。此抗結塊性處理之^ 驟’包括先添加水不灘微粉混合均勻後再添加轉劑。抗結塊 處理之目的在增加高财樹脂顆粒之肺猶，使高吸水樹月旨在 吸收渔氣後健有毅祕；水秘錄粉之祕方式為直接於 加’再利雌著獅水不雜微錄著於純水触表面。 上述惰性無機鹽粉末以反應物總固形份為基準，添加量為重 201100474 量百分比_5至_，更可為重量百分比·至4.0。所使用之 惰性無機鹽粉末為硫_、二氧切、氧化銘、氧化鎮或 組之混合物。 上述水不溶性微紗反應物總固雜為基準，添加量為重量 百分比_1至_，更可為重量百分比_至仏水不溶性微 粉之粒徑為10絲以下，更可為G 6縣町。林雜微粉為 無機鹽粉末、有機粉末或上述群組中之混合粉末。域鹽粉末為 ▲鋁硫酉文鎮、氧化紹、氧化鎮、氧化辞、碳酸舞、填酸弼、 Θ酸鋇、梦藻土、軟土、黏土、滑石粉、沸石、高嶺土、膨土、 活性碳、二氧切或二氧化鈦。有機粉末為纖維素粉末、聚醋、 聚乙烯、聚氣乙烯或聚苯乙烯。 上述黏著劑以反應物總固形份為基準，添加量為重量百分比 0.001至1G.G，更可為重量百分比議5至5。其中，當黏著劑之 添加!量在重量百分比0.001以下時，無法使水不溶性微粉完全黏 著於高吸水樹脂表面；而當黏著劑之添加劑量在重量百分比1〇以 上時，會使高吸水樹脂之吸水性太低，降低樹脂性能。所使用的 黏著劑為丙二醇、聚乙二醇、山梨醇、聚乙烯亞胺或上述群組中 之混合物。 上述不飽和單體水溶液之濃度範圍為重量百分比2〇至55， 更可為重量百分比30至45。其+，不飽和單體水溶液濃度在重量 百分比20以下時，自由基聚合反應後的高吸水性樹脂之凝膠體太 軟且有黏性，不利機械加工，而不飽和單體水溶液之濃度在重量 12 201100474 ， 百分比55以上時，過於接近飽和濃度，會有不易調配的問題且反 應太快反賴過多科緒做應。獨和單财驗，包括丙 烯酸或具有酸性基團的不飽和雙鍵的水溶性單體或上述群組中之 混合單體。具有酸性基團的不飽和雙鍵的水溶性單體為甲基丙烯 酸、馬林酸、富馬酸、2_丙職_2·甲基雜、順丁婦二酸、 順丁烯二酸酐、反丁烯二酸或反丁烯二酸酐。 上述不飽和單體水溶液亦可視情況添加具有不飽和雙鍵其他 〇 親水性的單體，其添加量以不破壞高吸水性樹脂之物性為原則。 具有不餘和雙鍵其他親水性的單體例如為丙烯_、f基丙_ 胺、丙稀酸2-羧基乙醋、甲基丙烯酸續基乙醋、丙稀酸甲醋、 丙烯酸乙g旨、二曱胺丙稀丙烯醯胺或氯化丙烯丙_胺基三甲錢 或上述群組中之混合單體。 上述不飽和單體水溶液更可利用添加水溶性高分子，以降低 成本。不飽和單體水溶液含水溶性高分子的量為重量百分比2〇以 〇下，更可為重量百分比10以下，尤可為重量百分比5以下。但是， 當添加超過重量百分比20以上時'，會使高吸水性樹脂之物性變 差。可用來添加的水溶性高分子為部份皂化或完全皂化的聚乙烯 醇、聚乙二醇、聚丙稀酸、聚丙烯醯胺、澱粉、殿粉衍生物或上 述群組之混合物。而澱粉衍生物為曱基纖維素，丙烯酸甲基纖維 素或乙基纖維素等等聚合物。此些水溶性高分子的分子量並不特 別限疋，其中較吊使用的水溶性咼分子為殿粉、部份皂化或完全 皂化的聚乙烯醇等等單獨或混合使用。 13 201100474 上述中和射和残和單體水溶_怖紐翻為莫耳百 分比45至85’更可為莫耳百分比如至乃。其中，怖劑部份中 和不飽和單體水絲”含酸基單體之麵顧為_、卸鹽或 銨鹽等等，以控制成品之_(酸驗度），使呈中性或微酸性。當 中和濃度莫耳百分比_%)為45以下時，成品之阳值會偏低。 當中和濃度莫耳百分比為85以上時，成品之阳值會偏高。若成 品pH值非呈中性或微酸性時，其不慎與人體接觸時不太適合也較 不安全。所使用財和_職表中鹼金族紐土金族之氮氧化 物或碳酸化物，.錢氧化納、氫氧化鉀、碳義、碳酸卸、 碳酸氫納、碳酸氫鉀、氨·合物料，可·制—種或多種 混合使用。 上述内部交咖以反應物總固形份為基準，添加劑量為重量 百刀比0.001至5 ’更可例如為重量百分比〇〇1至3。添加内部交 聯劑，在進行自·聚合反應後就可使高吸水⑽脂具有適當交 聯度，而使高吸雜翻旨膠體有適當的加1性。其t，當内部交 聯劑之添加劑量在重量百分比〇.撕以下時，聚合反應後:高吸水 性樹脂太軟林祕，不利於機械加卫。#添加劑量在重量百分 比5以上時，會使高吸水性樹脂吸水性太低，降低樹脂性能。所 使用的内部交聯劑為具有兩個或兩個以上不飽和雙鍵的化合物或 具有兩個或兩個以上魏基的化合物或上述群組之混合物。 上述具有兩個或兩個以上不飽和雙鍵的化合物為N，N-雙(2_ 丙烯土）胺N，N -次曱基雙丙浠醯胺、次曱基雙甲基丙稀醢 14 201100474 胺、丙烯酸丙烯輯、乙二醇二丙烯酸醋、聚乙二醇二丙烯_旨、 乙二醇二曱基丙烯_旨、聚乙二醇二曱基丙稀酸酉旨、甘油三丙婦 義、甘油三甲基丙軸旨、甘油附加環氧乙烧之三丙馳旨或 三曱基丙烯酸自旨、三甲醇丙貌附加環氧乙烧之三㈣_旨或三甲 基丙稀_旨、三甲醇丙燒三甲基丙婦酸醋、三曱醇丙燒三丙稀酸 酉曰、N，N，N-二(2-丙稀基)胺、二丙稀酸乙二醇酯、三丙騎聚氧乙 烯甘油酯、三丙烯酸二乙基聚氧乙烯甘油酯、或二丙烯三甘醇酯。 ° 上述具有兩個或兩他上環氧基的化合物為山_聚縮水甘 _、聚丙三g辣縮水甘_、乙二醇二縮水甘_、二乙二醇 -縮水甘綱、聚乙二醇二縮水甘祕或雙丙三醇軸水甘油鍵。 上述起始劑以中和含酸基單體鹽類為基準，添加劑量為重量 百分比0.001至10，更可為重量百分比0.1至5。其中，添加起始 劑在重量百分比議丨以下時，反應太慢不·濟效益，而添加重 量百分比10以上時，反應太快反應熱不易控制。所使用的起始劑 〇 為…、刀解i起始剤、氣化還原型起始劑或上述群組之混合物。當 使用氧化還原型起始劑和熱分解型起始劑之混合物時，氧化還原 起始劑會先進行反應產生自由基。當自由基轉移至含酸基單體上 寺立即引發聚合反應的進行。纟於自由基聚合反應進行時會釋 放出大量的缝而使溫度升S，當溫朗達齡_起始劑的分 解酿度時’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。 上述氧化還原型起始劑為酸性亞硫酸鹽、硫代硫酸鹽、抗壞 血fee或亞鐵鹽。熱分解型S始劑為過氧化物或偶氮化合物。其中， 15 201100474 過氧化物為過氧化氫、二_第三丁基過氧化物、過氧化酿胺、過琉 酸鹽、過硫酸錢鹽或過硫酸驗金屬鹽。偶氣化合物例如為U，•偶201100474. 6. Description of the Invention: [Technical Field] The present invention relates to a method for producing a superabsorbent resin, in particular, a powdery, water-insoluble, absorbable water or urine, and blood having low residual unreacted A method for producing a superabsorbent resin having a monomer, a high holding power, and a water absorption ratio under high pressure. [Prior Art] The super absorbent resin has a strong water retention capacity, can absorb water hundreds of times or even thousands of times its own weight, and can be swollen after being absorbed to maintain a non-flowing state, even if pressure is applied, it does not leak, and is The absorbed water can be slowly released in the atmosphere. Due to the above characteristics, the soil water retaining agent which was first used in the agricultural forestry industry has been widely used in the production technology of water-absorbent resins in recent years, so it is also widely used in sanitary products such as diapers, adult incontinence products and women's health. Water absorbing agent for products and fresh food for food preservation. The technique of 曰 衣 衣 材料 夂 夂 夂 夂 夂 , , , hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy hy Starch Acrylic Graft Polymer Patent Publication No. 51 (1976) 125, 468, 4-diethyl acetate propylene acetate or: = Τ = (: Γ _, hydrolysis _ copolymerization (Japanese Patent Publication No. 53 (·)·15,959 ) and the part of the mouth, the acrylic (Japanese Patent Publication No. Sec. (Twist (four) Office) and other patents. Do not use acrylic acid and acrylate ▲ accounted for the largest water-absorbing resin of the Qiu A County θ Ding and the junction Big* is also the most economical, because the acrylic acid can be quickly obtained from the market. 3 201100474, the county resin has high water absorption capacity, low manufacturing cost and most economic benefits, and will not cause decay. Sexual decomposition, so acrylic acid and acrylate acid are the most common materials for the manufacture of superabsorbent resins. Polymeric acrylic acid and __戦 high-yield silk have been successfully developed in many aspects. 4 production. The silk bonding method has a cast film polymerization reaction (Japanese Patent Gazette) Showa 48_)·42,466), a polymerization reaction is carried out on a conveyor belt (Japanese Patent Publication No. Sho. 58 (1983) _49, 714), and a kneading reaction with a pulverized mixing blade is carried out (Japanese Patent Publication No. 57) (19_,1〇1), performing reverse suspension polymerization (Japanese Patent Laid-Open Publication No. 59 (1984), 〇〇3) or spraying or coating a monomer on a fibrous substrate to carry out polymerization (Japanese Patent Laid-Open Publication) Zhao 62 (10) (10) 'period' and other patents. 1 and § 'Water-absorbing powder, under long-term storage, will have a tendency to change color (yellow and grazing) due to the decomposition of water-absorbing tree vinegar polymer. In the tropical or subtropical zone, the moisture content of the powder is changed. The shape of the powder discoloration (yellow and grazing) accelerates the sputum (about four to six months), thus maintaining the brittleness and delay of the water absorption. Time has become the goal that today's manufacturers are striving to solve. The discoloration of the water-absorbing tree S does not change much for its physical properties, but it directly affects the water-absorbing properties of discoloration after the preparation of sanitary products. Will make The sense of enchantment is contaminated, the appearance of the product is not good, and the axis affects the manufacturer's ambiguity. Therefore, the water-absorbing fine-grained product that will change color during storage time will greatly reduce its value as a commodity. In this case, there is a problem of water absorption and rejuvenation of the effect of discoloration prevention. 'For example, Japan, A_A, the No. 51 patent considers that the factor of 201100474 is that the decomposition of the water-absorbing resin and the breakage of the polymer chain with time. Since it is colored, it is recommended to use a superabsorbent polymer composition of an organic phosphoric acid compound or a salt thereof, but the addition of an organic phosphoric acid compound complicates the production method and has a safety problem. JA-A-2000-230129, JA-2000-327926, and a water-absorbent resin gel containing a metal chelating agent, adding 1 to 6 parts by weight of a reductant or an oxidizing agent before drying or drying (Taiwan When the water-absorbent resin using the peroxide (U.S. Patent No. 4,959,060) is stored for a long period of time under high temperature and high humidity, it is not possible to exhibit a sufficiently satisfactory discoloration preventing effect. Since the water-absorbent resin is a hydrophilic polymer which is insoluble in water, it generally has a bridge structure with uniformity inside the resin. In order to improve the quality of the water-absorbent resin, in order to improve the absorption rate, increase the strength of the colloid, and improve the physical properties such as anti-caking property and liquid permeability, the surface of the resin is further bridged after screening the fixed particle diameter. Such a silk cross-linking treatment is a multi-functional cross-linking agent capable of reacting with an acid group. Many patents have been disclosed, for example, dispersing a water-absorbent resin and a cross-linking agent in an organic solvent for surface crosslinking. Treatment (JP-A-56-131608, JP-A-57-44627, JP_A_58_Gam 2, jp sister 117222), directly mixing the crosslinking agent and the crosslinking agent solution into the water-absorbent resin using an inorganic powder (Jp_A6 (M6)骂, JP-A.255814), after adding a crosslinking agent, steam treatment (jpn.H times), surface treatment using an organic solvent, water and polyol (JP-A-63-270741, JP-A-64- 50707, claws from the fiber (4), using organic solution, water and shouting (ethe phlegm (JP-A-2-153903), etc. These surface treatment methods can increase the absorption rate of the resin or increase the water absorption rate under pressure. However, it will cause its storage capacity to drop more than 5 201100474, which will reduce the performance of practical applications. The method of polymerizing acrylic acid and proacetate to form superabsorbent resin can be obtained by several known methods such as water-soluble (four) Reaction, reverse phase fresh liquid polymerization, emulsion polymerization or application of monomer to Wei or The method of finding the polymerization reaction of the heterogeneous matrix. In the 24 methods, the counter-mechanical floatation reaction and the emulsion polymerization reaction must use an organic solvent, but if the temperature of the polymerization anti-scale is not effectively controlled, the organic solvent will cause the reaction system. The increase in temperature and pressure causes a fire phenomenon and even causes an explosion. 'Incoming _ operation site personnel (4) safety and environmental pollution problems. The finished product also has the doubt of organic solvent residue. In the high water absorption series, the needle is turned into a dough. The drying effect is usually first cut into a small gel of 20 mm or less by a chopper, a slitter, a squeezed porous machine, a spiral slicer or a mincer, and the diameter is preferably less than or equal to the diameter of i〇mm, and then dried, but When cut into small condensate, the small colloid will make the colloids condense with each other. 'This mutual condensation _ phenomenon will make the hot gas in the drying process unable to resolve the gel layer, making it impossible to make each hydrogel Evenly heated, which affects the results of drying. So far, if Xu Xi Science has been working hard to increase the dispersion of hydrogels to improve drying efficiency, the technology industry has also improved the dispersion of water condensation. The ageing method has been developed, such as: mixing a surfactant with an aqueous monomer solution, and polymerizing the polymerization initiator, or adding a mixed solution of a crosslinking agent and a surfactant to increase the condensation of the aqueous solution of the acidic monomer. Colloidal dispersibility to improve drying efficiency (U.S. Patent No. 4,286,082; Taiwan Patent No. 11509 (H Tiger), knife in the perforated plate of the extruder, 201100474 • To assist in the grinding and dispersion of the crucible 1 (Japanese Patent Laid-Open) Bulletin Sho 54 (1979)-32, 176), adding a knife to the perforated plate of the extruder, and adding a Shiki gum emulsifier to assist in the grinding and dispersion of Ming 1 (Japanese Patent Laid-open Publication No. 59 (1984)-119 , No. 172), controlling the gel temperature of 45-90 degrees and the pore size of the perforated plate is 6 5_18 mm (Japanese Patent Laid-Open Publication No. Hei 5 (1994)-70,597), adding a cellulose derivative or a surfactant to the hydrogel The surface of the body is used to increase the dispersibility of the hydrogel (U.S. Patent No. 4,818,464), and the addition of chitin-poly compound to the hydrogel, Ο to improve the physical properties of the water-absorbent resin (U.S. Patent No. 0500090586) . The above method of using a surfactant to mix with a monomer aqueous solution to improve the dispersibility of the water-condensing body will result in a decrease in high water absorption and a lowering of the fuel; the efficiency of the gambling ring hot air drying device is improved, and the stomach is too high in drying temperature or It is because the drying time is too long, which leads to the deterioration of the water tree stagnation, so that the residual monomer content of the water-absorbent resin is too high; the addition of the cellulose derivative is effective on the surface of the water condensate, although the water sputum dispersion can be improved. Sexually 'but it is easy to change the color of the water-absorbent resin during the drying process' by using a knife in the perforated plate of the extruder to assist in the grinding and dispersing of the condensate body. It is not ideal for improving the bulk of the loose thread; Adding a knife to the new plate and adding Shishi gum emulsifier to assist in the grinding and dispersing of the gel, although it can effectively improve the mincing and dispersibility', but the added Shishi gum emulsifier is a low hydrophilic interface. The active agent is used to change the water absorption rate and the water absorption ratio of the ship. The temperature of the gel is 45_9 〇 and the pore size of the porous plate is 6.5 pm. Control is not easy, and the gel is ineffective. 7 201100474 is also quite limited; the method of spraying chitin-polyamines on the surface of hydrogels is also costly and the drying efficiency is poor. Problems and other shortcomings. SUMMARY OF THE INVENTION The main object of the present invention is to provide a powdery, water-insoluble, absorbable aqueous liquid or urine and blood with excellent yellowing resistance and low residual monomers. The method for producing a superabsorbent resin in order to solve the method disclosed in the prior art, although the dispersibility of the superabsorbent tree can be improved, but the color to the water-absorbent resin is changed, resulting in poor practical application performance of the consumer user. The problem. The present invention relates to a method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water or urine and has excellent yellowing resistance and low residual monomer content, and includes a gel. Adding a coating dispersant having a dispersing agent having an iron ion content of less than 30 pPm (partS per million), a cadmium ion content of not more than 20 ppm, or a total amount of transition metal ions in the unsaturated monomer aqueous solution of less than 50 Ppm The gel coated with the dispersant is dried, pulverized, and sieved to a fixed particle size, and a surface cross-linking agent is added and then heat-treated. According to the present invention, a method for producing a superabsorbent resin which is powdery, insoluble in water, absorbs water or Wei and blood, has excellent yellowing resistance and low residual monomer content, and has a step of adding a surface crosslinking agent. Previously, inert inorganic salt powders could be added to help surface cross-linking. The inert inorganic salt powder is based on the total amount of the reactants. The amount added is in the range of 〇. 5 to 1 〇. The inert inorganic 201100474 salt powder used is her s, dioxo, oxox, oxo or a mixture of the above. An anti-caking treatment can be performed after the heat treatment. This anti-caking treatment is preceded by the addition of a water-insoluble micronized powder plus an adhesive to make the forest-soluble fine powder adhere to the surface of the superabsorbent resin. The water-insoluble fine powder is based on the total solid content of the reactants, and is added in an amount of 〇1 to 1 〇. 〇 and the adhesive is based on the total solid content of the reactant, and the amount is added in the range of α(8) 丨 to 100% by weight. .漠 The indifference of the aqueous solution of the hair styling unsaturated monomer is from 2G to 55% by weight. The unsaturated monomer is a water-soluble monomer or a water-soluble monomer having a meaning-hetero- and double bond or a mixed monomer in the above group. The aqueous solution of the unsaturated monomer may also optionally be added with a hydrophilic group having an unsaturated double bond or a water-soluble polymer to reduce the cost. The invention is added as _ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The neutralizing agent used is a gas oxidized copper, a nitrous oxide clock, sodium carbonate, potassium carbonate, sodium hydrogen hydride, carbonic acid gas off, an ammonia compound or a mixture of the above groups. The (4) of the present invention relies on the reaction to be fresh, and the amount of the additive is from 0 to 5. The _(iv) crosslinked material has two or more unsaturated double lysine compounds or a compound having _-perepoxy group or a mixture of the above groups. The __ towel and the acid-containing monomer of the present invention are diligently benchmarked, and the amount of the additive is 10% by weight. A mixture of the above-mentioned groups of the start-_thermal decomposition type initiator, 201100474 redox type starter. The thermal decomposition _ starter is a peroxide or an azo compound. Oxidation also produces a light sulfite, thiosulfate, ascorbic acid or ferrous salt. The addition type of the surface of the invention may be added by money, added to an aqueous solution or adjusted to a hydrophilic (four) aqueous solution. It is added in a percentage of 0.001 to 10 by weight. The surface crosslinking agent to be used is a polyol, a polyamine, a compound having two or more epoxy groups, an alkylene carbonate or a mixture of the above groups. The heat treatment temperature of the present invention is 90 to 23 G degrees Celsius and the time is 2 to 15 minutes. As described above, the present invention is a superabsorbent resin prepared by limiting the content of dispersant iron ions, recorded ions or transition metal ions, and has excellent physical properties such as yellowing resistance and low residual monomer content. The axis of the enemy 嫩 _ _ _ (four) corrects the low residual content of the early body and the material female (four) sex, so it can improve the safety of use, because the invention of the water-based resin will be more suitable as a _ type _ (four) "Water-repellent agent for morning industry, food and food preservation.") For the purpose of this issue (10), the ship touches the fruit and calls Jiashiguan Pure as detailed below. 10 201100474 • [Embodiment] The present invention provides a powdery, A water-absorbent resin that is insoluble in water and absorbs water or urine and has excellent yellowing resistance and low residual monomer content. It is a method for producing superabsorbent resin by limiting the content of transition metal ions, including The acid group-containing monomer partially neutralizing the aqueous solution of the unsaturated monomer becomes an acid group-containing monomer salt, and the internal crosslinking agent is added to the unsaturated monomer aqueous solution; after that, the initial content is added to the unsaturated monomer aqueous solution. Filtration reaction; the ruthenium gel obtained from the silk polymerization reaction is chopped, and the recording grade is added to make the dispersed iron ion containing less than 30 Ppm (parts per million) and the cadmium ion content is not More than 2 〇 Ppm ' or dispersant The total content of transition metal ions is less than 50Ppm; the process of drying, pulverizing and turning the fresh silk is further carried out; after the addition of the surface crosslinking agent, the heat treatment is carried out, that is, the super absorbent resin is obtained. The remainder, the secret water, the core or To test the method for producing superabsorbent resin with excellent vaporization resistance and low residual monomer content, and to add inert inorganic salt powder to help disperse the surface crosslinking agent before adding the surface crosslinking agent. In addition, the addition of the secret principle can be done - anti-snaking treatment, so that the super absorbent resin has the characteristics of not easy to agglomerate after moisture absorption. The anti-caking treatment process includes the first addition of water and beach powder mixed After adding evenly, the agent is added. The purpose of anti-caking treatment is to increase the lungs of high-yield resin particles, so that the high-absorbency tree month is designed to absorb the fishery and has a mystery; the secret way of water secret recording powder is directly 'The lion's water is not recorded on the surface of pure water. The above inert inorganic salt powder is based on the total solids of the reactants, and the amount added is 201100474% by weight _5 to _, more preferably by weight. 4.0. Used The inert inorganic salt powder is a mixture of sulfur, dioxo, oxidized, oxidized or a mixture of the above. The water-insoluble micro-yarn reactant is based on the total solid content, and the added amount is 1/3 to _ by weight, and more preferably _To the water-insoluble micropowder has a particle size of 10 or less, and may be a G 6 county town. The forest micropowder is an inorganic salt powder, an organic powder or a mixed powder in the above group. The domain salt powder is ▲ aluminum sulphide town , oxidation, oxidized town, oxidation, carbon dance, acid strontium, strontium citrate, dream algae, soft soil, clay, talcum powder, zeolite, kaolin, bentonite, activated carbon, dioxate or titanium dioxide. Organic The powder is cellulose powder, polyester, polyethylene, polyethylene or polystyrene. The above adhesive is based on the total solids of the reactants, and is added in an amount of 0.001 to 1 G.G, or more by weight. To 5. Wherein, when the addition amount of the adhesive is less than 0.001 by weight, the water-insoluble fine powder cannot be completely adhered to the surface of the superabsorbent resin; and when the additive amount of the adhesive is more than 1% by weight, the superabsorbent resin is The water absorption is too low to lower the resin properties. The adhesive used is propylene glycol, polyethylene glycol, sorbitol, polyethyleneimine or a mixture of the above groups. The concentration of the above aqueous unsaturated monomer solution ranges from 2 〇 to 55, more preferably from 30 to 45, by weight. When the concentration of the unsaturated monomer aqueous solution is less than 20% by weight, the gel of the superabsorbent resin after the radical polymerization reaction is too soft and sticky, which is unfavorable for mechanical processing, and the concentration of the unsaturated monomer aqueous solution is Weight 12 201100474, when the percentage is above 55, it is too close to the saturation concentration, there will be problems that are difficult to deploy and the reaction is too fast. The monovalent test includes a water-soluble monomer of acrylic acid or an unsaturated double bond having an acidic group or a mixed monomer of the above group. The water-soluble monomer having an unsaturated double bond having an acidic group is methacrylic acid, marinic acid, fumaric acid, 2-propenyl-2-methyl hetero, cis-butanic acid, maleic anhydride, Fumaric acid or fumaric anhydride. The above unsaturated monomer aqueous solution may optionally contain a monomer having an unsaturated double bond and other hydrophilicity, and the addition amount thereof is based on the principle of not impairing the physical properties of the superabsorbent resin. The monomer having other hydrophilicity of the double bond and the double bond is, for example, propylene, f-propyl-amine, 2-hydroxyethyl acrylate, methacrylic acid, ethyl acetonate, acrylic acid, and acrylic acid. , dimethylamine propylene decylamine or chlorinated propylene propyl aminyl triacetate or a mixed monomer in the above group. The aqueous solution of the above unsaturated monomer can be further added with a water-soluble polymer to reduce the cost. The aqueous solution of the unsaturated monomer contains the water-soluble polymer in an amount of 2 重量 by weight, more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less. However, when the addition exceeds 20% by weight or more, the physical properties of the superabsorbent resin are deteriorated. The water-soluble polymer which can be used for addition is a partially saponified or fully saponified polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, starch, a powder derivative or a mixture of the above groups. The starch derivative is a polymer of fluorenyl cellulose, methyl cellulose or ethyl cellulose. The molecular weight of such water-soluble polymers is not particularly limited, and the water-soluble cerium molecules used in suspension are used alone or in combination as a powder, partially saponified or fully saponified polyvinyl alcohol. 13 201100474 The above-mentioned neutralization shot and residual monomer and water-soluble _ 纽 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻 翻Wherein, the agent partially neutralizes the unsaturated monomer water filament "the acid-containing monomer is treated as _, unloading salt or ammonium salt, etc., to control the finished product _ (acidity test), making it neutral or When the neutralization concentration percentage is less than 45, the positive value of the finished product will be lower. When the concentration of the neutral concentration is 85 or more, the positive value of the finished product will be higher. Neutral or slightly acidic, it is not suitable and less safe when it is inadvertently in contact with the human body. The oxynitride or carbonate of the alkali gold family of the gold family in the financial and _ job table, Potassium hydroxide, carbon, carbonic acid, sodium bicarbonate, potassium bicarbonate, ammonia, combined materials, can be used in combination or in combination. The above internal coffee is based on the total solids of the reactants. The ratio of 10,000 to 5' can be, for example, 1/3 to 3% by weight. The internal crosslinking agent is added, and after the self-polymerization reaction, the highly water-absorbing (10) fat can be appropriately cross-linked, and the high-passing is caused. The colloid has a suitable additive. Its t, when the amount of the internal crosslinking agent is in the weight percentage When the following is torn off, the superabsorbent resin is too soft, which is not conducive to mechanical reinforcement. #Additive amount of 5 or more by weight, the water absorption of the superabsorbent resin is too low, and the performance of the resin is lowered. The internal crosslinking agent used is a compound having two or more unsaturated double bonds or a compound having two or more Wei groups or a mixture of the above groups. The above having two or more unsaturated doubles The compound of the bond is N,N-bis(2-propene) amine N,N-decyldipropionamide, decyl dimethyl propyl hydride 14 201100474 amine, acrylic propylene series, ethylene glycol diacrylate Vinegar, polyethylene glycol dipropylene, ethylene glycol dimercaptopropene, polyethylene glycol dimercapto acrylate, glycerol triglyceride, trimethyl propyl glycerol, glycerin Ethylene triacetate or tridecyl acrylate, trimethyl methacrylate, propylene oxide, tris(4) _ or trimethyl propyl hydride, trimethyl methacrylate, trimethyl propylene glycol Vinegar, tridecyl alcohol, propylene triacetate, N, N, N-bis(2-propenyl)amine, diacetyl acid B Alcohol ester, tripropylene riding polyoxyethylene glyceride, diethyl polyoxyethylene glyceryl triacrylate, or dipropylene triethylene glycol ester. ° The above compound having two or two upper epoxy groups is mountain _ polycondensation Gan _, poly propylene three g Spicy water shrinkage _, ethylene glycol diced water _, diethylene glycol - glycidyl, polyethylene glycol dihydrate or glycerin glycerol. The amount of the additive is 0.001 to 10 by weight, and more preferably 0.1 to 5 by weight, based on the neutralization of the acid group-containing monomer salt. The reaction is too slow when the amount of the initiator is added below the weight percentage. The benefit is obtained, and when the weight percentage is 10 or more, the reaction is too fast, and the heat of reaction is not easy to control. The initiator used is ..., 刀 i initial 剤, gasification reduction initiator or a mixture of the above groups. When a mixture of a redox type initiator and a thermal decomposition type initiator is used, the redox initiator first reacts to generate a radical. When the radical is transferred to the acid-containing monomer, the polymerization is initiated immediately. When the free radical polymerization reaction is carried out, a large amount of slits are released to raise the temperature by S, and when the decomposition age of the initiator is started, the decomposition of the second stage thermal decomposition type initiator is caused. And the entire polymerization reaction is more complete. The above redox type initiator is an acidic sulfite, thiosulfate, anti-bad blood fee or ferrous salt. The thermally decomposable S initiator is a peroxide or an azo compound. Among them, 15 201100474 peroxide is hydrogen peroxide, di-tert-butyl peroxide, peroxylated amine, perrhenate, persulfate money salt or persulfate metal salt. Odor compounds such as U, • even
亂基雙(2_脒基秘鹽酸鹽、2,2，.基雙帅.二伸曱基異 二鹽酸鹽。 W β本發明之自由絲合反射於傳統批次反應容 器中反應，或 疋於輸送V式反應☆上進行反應。而自由絲合反應所得之凝膠 體可先利用紅碎機切碎成為直徑2〇厘求以下之凝膠體，更可切 碎為成為直徑10厘米以下之凝膠體。其中，凝膠體直徑以2〇〇 厘米以下為宜，更可以介於⑽厘米至i 5Q厘米間，而直徑大於 細厘米之凝膠體則重新送回絞碎機進行再次切碎。當直徑_ 厘=以:之凝膠體進行烘乾、粉碎處理後，易使成品細粉量提高， 而田直UGG厘米以上之凝膠體進行賊時，則容易因為熱傳導 效果不佳’導致成^的殘存賴含i偏高，以及具有其他物性表 現不佳之缺點。 ^本發月之土、曰加凝膠體分散性以提高乾燥效率，係利用控制分 政^之鐵料含量小於3Gppm、絲传量不超過％鹏，或分 $劑中過渡金屬離子合計含量小於5_;其中，分散劑以凝踢體 ⑽基準，添加㈣為重量百分比_1至1G，更可為重量百分比 八 5而起始劑之添加在重量百分比0.001以下或添加重量百 、上夺均不利乾燥效率之提升，導致經濟效益的降低。 匕分上述之分散劑可為陰離子型界面活性劑，如：硬脂酸鈉、硬 月曰酸1、硬脂酸鎂、硬脂酸約、月桂酸納、十二絲石黃酸納、二 〜酉夂琥涵酸鋼、績酸基琥J白酸月桂醋二納、續酸基破站酸月 16 201100474 • 維氧乙烯·旨二鈉、十二烷基磺酿氨乙酸鋼 活性劑，為：聚氧乙烯⑽失水山梨醇月桂酸酉旨、聚氧 = =梨醇月她旨、聚氧乙_失水山梨醇月桂軸、聚氧乙稀 j)失水山_早硬輸旨、聚氧乙购失水山轉單硬嶋旨、 ^氧乙烯㈣失水山梨醇單油㈣、失水山梨醇月桂酸醋 SP肪，、失水山_月桂_(Sp則G)、失水山卿月桂酸醋 pan-80)，_子型界面活性劑，例如：索羅明a(s。職⑹八）、 〇薩帕明A(S聊⑻A)、十八燒基二^基烴乙基硝顧、十八烧基 二T基烴乙基過氯酸銨、十八燒基二甲基烴乙基月桂酸納鹽。土 依據本發明，凝膠體的顆粒大小分佈越窄，不僅可使凝膠體 在烘乾後物性表現達到越良好的狀態，而且有利於控制後續之烘 乾的時間及溫度。 、上述凝膠體之烘乾’以在1(Krc至⑽。c間的溫度下進行洪乾 為宜。當烘乾溫度在100t以下，烘乾時間太久，不具經濟效益。 而當供乾溫度在180。(：以上，將使内部交聯劑提早進行交聯反應， 〇使得後續的乾燥過程中，因交聯度過細無法有效的去除殘存單 體’達到降低殘存單體之效果。 上述凝膠體之乾燥、粉碎及筛選固定粒徑過程中，薛選凝膠 體之固疋粒徑分布範圍可為〇 至loo厘米，更可為ο ι。至ο %。 厘米，而平均粒徑範圍為〇·2至〇 6毫米；粒子長度與寬度比例在 1,5至20範圍内，粒子長度為100至lOOOOum(微米)範圍内，寬度 為10至200〇um範圍内。而凝膠體的顆粒大小分佈越窄越好。其 中’當筛選高吸水性樹脂之固定粒徑範圍在粒徑0〇6公厘以下 17 201100474 ; 時，細粉將使成品粉塵提高，而當粒徑範圍在1〇〇公厘以上時， 粒子將使成品吸水速率變慢。依據本發明，自由基聚合反應後產 物的顆粒大小分佈越窄越好。 〜 上述之表面交聯劑以反應物總固形份為基準，添加劑量為重 量百分比0.001至10，更可為重量百分比〇 〇〇5至5。其中，交聯 劑添加劑量在重量百分比0.001以下時無法顯出效果，表面交聯劑 添加劑量在錢百分比urn上時，吸樣太低，降鋪脂性能。 表面交聯_添加赋為直接添加、調成水溶液添加或調成親水 性有機溶劑水溶餘加。在職親水性有機溶劑水溶液添加時， 所使用的親水性有機溶劑為曱醇、乙醇、丙醇、異丁醇、丙嗣、 甲醚或***等沒有特殊限制，可形成溶液即可，以甲醇或乙醇較 吊使用。所使用之表面交聯劑例如為多元醇、多元胺、具有兩個 或兩個以上魏基的化合物、碳酸亞烴喊_L述群組之混合物。 上述之多元醇為丙三醇、乙二醇、二乙二醇、三乙二醇'聚 乙二醇、丙二醇、M 丁二醇、三烴基曱基丙烷或山梨醇。多元胺 例如為乙一胺、二乙二胺、三乙二胺或聚乙二胺。具有兩個或兩 個以上環氧基的化合物為山梨醇聚縮水甘油醚、聚丙三醇聚縮水 甘油醚、乙二醇二縮水甘油醚、二乙二醇二縮水甘油醚、聚乙二 醇二縮水甘油醚或雙丙三醇聚縮水甘油醚。碳酸亞烴酯例如為乙 二醇碳酸酯、4·曱基-U-二氧雜環戊烷-2-酮、4,5-二曱基-1，3-二氧 雜％戊烷-2-酮、4,4-二曱基-1，3-二氧雜環戊烷酮、4-乙基·1，3-一氧雜環戊烷-2-酮、l，3-二氧雜環己烷_2-酮、4,6-二甲基-1，3-二氧 18 201100474 雜架己燒-2,或1，3-二氧雜環庚烧_2_剩。 理可行絲交·塗祕理後再進行加_理，此加熱處 表較聯舰均勻絲速地進行_反應，並使内部交 Z亦進行《反應而達到本發明之效果。進行加熱處理之裝置 為乾無器、加熱爐、隨道式混合乾燥器、轉鼓式乾燥器 燥㈣化床乾燥II、氣流式乾燥器或紅外線編。加熱處理 的恤度圍為攝氏9G至23G度，加熱處理的時間為2至15〇分鐘。 其中，加熱處理溫賴氏9〇度以下败聯反應時間太久不具經濟 效益’加熱處理溫度概230度以上則樹脂易劣化影響品質。本 發明可依照欲獲得_表面處理效果來做熱處理溫度調整，若處 理溫度高卿需時職短，若處理溫度侧所糾間較長。 為顯示本發明之吸水性樹脂具有良好的抗變色能力，本發明係 利用中國專利99103660.3號說明書第27頁所描述的方法略作修改 的方法來測定；將3.〇〇〇g吸水性樹酯(粒怪介於6〇〇_3〇〇#m的乾乱基双(2_脒基秘HCl, 2,2,.基双帅.二伸曱基异二HCl. W β The free silk of the invention reflects in a conventional batch reaction vessel, Or the reaction can be carried out by transporting the V-type reaction ☆. The gel obtained by the free silk reaction can be first chopped by a red crusher to obtain a gel having a diameter of 2 〇, and can be chopped to a diameter of 10 a gel having a diameter of less than 2 cm, wherein the diameter of the gel is preferably 2 cm or less, more preferably between (10) cm and i5 Q cm, and the gel having a diameter larger than the fine centimeter is returned to the mincer The chopping is carried out again. When the diameter _ PCT = drying and pulverizing the gel, the amount of fine powder of the finished product is easily increased, and when the gel of the UGG cm or more is thief, it is easy to conduct heat. The poor effect 'causes the residual of the ^ to be high, and has the disadvantage of other physical properties. ^The soil of the month, the gel dispersion of the gel to improve the drying efficiency, the use of control The iron content is less than 3Gppm, the wire throughput is less than 5%, or the transition metal ion is divided into $. The total content is less than 5 _; wherein the dispersing agent is based on the condensing body (10), adding (4) is 1/3 to 1 G by weight, more preferably 8% by weight, and the initiator is added at 0.001 or less by weight or adding weight The increase in unfavorable drying efficiency leads to a decrease in economic efficiency. The above dispersing agent may be an anionic surfactant such as sodium stearate, hard lauric acid 1, magnesium stearate, or stearic acid. , sodium laurate, sodium sulphate, sulphate, succinic acid, acid acid, succinic acid, white lauric acid, vinegar, vinegar, sodium, vinegar, vinegar, vinegar, vinegar, vinegar, vinegar, vinegar Sodium, dodecyl sulfonyl acetic acid steel active agent, is: polyoxyethylene (10) sorbitan lauric acid, polyoxygen = = pear alcohol, her purpose, polyoxyethylene _ sorbitan laurel axis, Polyoxyethylene j) lost water mountain _ early hard drive, polyoxyethylene purchase lost water mountain turn single hard, ^ oxyethylene (four) sorbitan single oil (four), sorbitan lauric acid vinegar SP fat, , Lost Water Mountain _ Yue Gui _ (Sp G), Lost Mountain Qing lauric acid vinegar pan-80), _ sub-type surfactant, for example: Solowing a (s (6) VIII), 〇sapamine A (S Talk (8) A), octadecyl sulphate ethyl sulphate, octadecyl di-t-hydrocarbyl ethyl perchlorate, octadecyl Methyl hydrocarbon ethyl laurate sodium salt. According to the present invention, the narrower the particle size distribution of the gel, not only allows the gel to exhibit a better physical property after drying, but also facilitates control of the time and temperature of subsequent drying. The drying of the above gel is preferably carried out at a temperature of 1 (Krc to (10).c. When the drying temperature is below 100t, the drying time is too long, and it is not economical. The temperature is 180. (: The above, the internal crosslinking agent will be cross-linked early, and the enthalpy will make the effect of reducing the residual monomer because the degree of crosslinking is too fine to remove the residual monomer in the subsequent drying process. In the process of drying, pulverizing and screening the gel, the solid particle size distribution of the Xuexue gel can range from 〇 to loo cm, and can be from ο ο to ο %. cm, and the average particle size range 〇·2 to 〇6 mm; particle length to width ratio in the range of 1,5 to 20, particle length in the range of 100 to 100 um (micrometer), width in the range of 10 to 200 um. The narrower the particle size distribution, the better. 'When the fixed particle size range of the superabsorbent resin is selected to be below 0〇6 mm 17 201100474; fine powder will increase the finished dust, while the particle size range When 1 〇〇 or more, the particles will change the water absorption rate of the finished product. According to the present invention, the particle size distribution of the product after the radical polymerization is as narrow as possible. ~ The above surface crosslinking agent is based on the total solid content of the reactant, and the amount of the additive is 0.001 to 10 by weight, more preferably by weight. 〇〇〇 5 to 5. Among them, the amount of the cross-linking agent additive is not effective when the weight percentage is 0.001 or less, and the amount of the surface cross-linking agent additive is too low, and the fat-absorbing property is lower than that of the 5% of the urn. _Additional addition is added directly, adjusted to an aqueous solution, or adjusted to a hydrophilic organic solvent, water-soluble addition. When adding a hydrophilic organic solvent aqueous solution, the hydrophilic organic solvent used is decyl alcohol, ethanol, propanol, and isobutylene. The alcohol, propylene glycol, methyl ether or diethyl ether is not particularly limited, and a solution may be formed, and it may be used in a suspension of methanol or ethanol. The surface crosslinking agent used is, for example, a polyol or a polyamine, and has two or more. Weiji's compound, alkylene carbonate, is a mixture of the above-mentioned polyols. The above polyols are glycerol, ethylene glycol, diethylene glycol, triethylene glycol 'polyethylene glycol, propylene glycol. , M butanediol, trihydrocarbylmercaptopropane or sorbitol. The polyamine is, for example, ethylamine, diethylenediamine, triethylenediamine or polyethylenediamine. Compounds having two or more epoxy groups are Sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether or diglycerol polyglycidyl ether. The alkylene carbonate is, for example, ethylene glycol carbonate, 4·decyl-U-dioxol-2-one, 4,5-dimercapto-1,3-dioxo-pentane-2 -ketone, 4,4-dimercapto-1,3-dioxolone, 4-ethyl·1,3-monooxol-2-one, l,3-dioxa Cyclohexane 2-ketone, 4,6-dimethyl-1,3-dioxo 18 201100474 Miscellaneously calcined-2, or 1,3-dioxane-2. After the feasible silking and coating, the heat treatment is carried out, and the heating is performed evenly on the joint ship, and the internal reaction Z is also subjected to the reaction to achieve the effect of the present invention. The heat treatment device is a dry device, a heating furnace, an on-channel mixing dryer, a drum dryer, a four-bed drying II, an air flow dryer or an infrared ray. The heat treatment range is from 9G to 23G Celsius and the heat treatment time is from 2 to 15〇 minutes. Among them, the heat treatment temperature is less than 9 〇 degrees below the failure reaction time is not economical. When the heat treatment temperature is more than 230 degrees, the resin is easily deteriorated and affects the quality. According to the invention, the heat treatment temperature adjustment can be performed according to the effect of obtaining the surface treatment, and if the processing temperature is high, the time is short, and if the processing temperature side is long, the correction is long. In order to show that the water-absorbent resin of the present invention has good resistance to discoloration, the present invention is determined by a method slightly modified by the method described on page 27 of the specification of Chinese Patent No. 99103660.3; 3. 〇〇〇g water-absorbing resin (Peace is between 6〇〇_3〇〇#m
燥粉末），平鋪到玻璃培養皿底部，該容器内怪為55mm、高25腿。 並且在沒有加蓋的情況下，置入恆溫恆濕箱（HSINCHIENXIANGCc). LTD. AJH-80)内保持該吸水性樹酯粉末在65°C、90%RH的環境中 二周。二周後，將容器中所有的吸水性樹酯以光譜色差儀(Color analyzer Tokyo Denshoku Co. LTD. Topscan model TC-1800MKII) 測量吸水性樹酯表面色度，並計算黃化指數(％)。 黃化指數(％)=(暴露置在恆溫恆濕下的色度)/(暴露前的色度）x 100 高吸水性樹脂的黃化指數高於85%，表示高吸水性樹脂具有 19 201100474 良好的抗著色能力 脂抗著色能力尚可 變色能力不佳。 ;黃化指數介於70至85%時，表示高吸水性樹 ;若黃化指數低於70%，表示高吸水性樹脂的抗 本發明之保持力係利用茶袋試驗法測定，並以五次量測結 果，去除最高值以及最低值後，取平均值。其測定步驟包括；^ 將〇.2g的高吸水性樹月旨裝在茶袋裡，並浸泡於〇 9%㈣们水溶 液20分鐘，然後將此浸泡後的茶袋置於直徑心、轉速 1400rpm(revoluti〇nperminute，每分轉數），離心機中離心，三分 鐘後秤重，麟之數值先減絲高吸水輯脂啦白組^ 重(以相时聽作)再除崎泡前高吸水性樹财即得保持力數 值。 ' 本發明之賊存單齡狀是獅軸層析儀分析，先精科 取〇.500g高吸水性樹脂於^(毫升)錐形瓶中，加人〇5鳩 NaCI水溶液l〇〇g及2cm的授拌子一顆，以5〇〇啊轉速餅ι 小時’加入20%硫酸銘(A12(S04)3)水溶液5g，再利用2㈣微米） 遽紙將濾液打人液相層析儀内分析’把所得之訊號和校正 曲線相比對即可得到殘存單體量。 以下以參考工作實驗例酬本發％ ;但本發日聰圍不受這些 實驗例所限制。Dry powder), spread to the bottom of the glass culture dish, the inside of the container is 55mm, 25 feet high. Further, in the absence of capping, the water-absorbing resin powder was placed in a constant temperature and humidity chamber (HSINCHIENXIANGCc). LTD. AJH-80) in an environment of 65 ° C and 90% RH for two weeks. Two weeks later, all the water-absorbing resin in the container was measured for the surface color of the water-absorbing resin by a color spectrometer (Color analyzer Tokyo Denshoku Co. LTD. Topscan model TC-1800MKII), and the yellowing index (%) was calculated. Yellowing index (%) = (chromaticity exposed to constant temperature and humidity) / (chromaticity before exposure) x 100 The yellowing index of the superabsorbent resin is higher than 85%, indicating that the super absorbent resin has 19 201100474 Good anti-staining ability Lipid resistance to coloring ability is still poorly discolored. When the yellowing index is between 70 and 85%, it means a superabsorbent tree; if the yellowing index is less than 70%, it means that the retention of the superabsorbent resin against the present invention is determined by the tea bag test method, and is five times. After the measurement results are removed, the highest value and the lowest value are removed, and the average value is taken. The measuring steps include: ^ Putting a high-absorbency tree of 〇.2g in a tea bag and immersing it in an aqueous solution of 9% (four) for 20 minutes, and then placing the soaked tea bag at a diameter of 1400 rpm (revoluti) 〇nperminute, revolutions per minute), centrifuged in a centrifuge, weighed after three minutes, the value of Lin first reduced the high water absorption, the fat white group, the weight, the weight, and the high water absorption. Tree wealth has to maintain the strength value. The singularity of the thief of the present invention is analyzed by the lion axis chromatograph, and the first fine sputum is taken. 500g of super absorbent resin is placed in a (ml) conical flask, and the 〇5鸠NaCI aqueous solution l〇〇g and 2cm are added. One of the spices, 5 rpm rpm ι hour 'Add 20% sulfuric acid (A12 (S04) 3) aqueous solution 5g, and then use 2 (four) micron) crepe paper to analyze the filtrate in liquid chromatograph 'Compatate the obtained signal with the calibration curve to obtain the residual monomer amount. The following is a reference to the working example of the remuneration of the work; however, this is not limited by these experimental examples.
分散劑A 201100474 濃度10%的聚氧乙烯(60)失水山梨醇月桂酸酯水溶液 (Tween-60 ’ 京群公司提供)，以];CP-MS(Inductively Coupled Plasma Mass Spectrometry)測定鐵離子、鎘離子以及過渡金屬離子合計含 里分別為 2.87 ppm，0.65 ppm 以及 15.31 ppm。Dispersant A 201100474 A 10% polyoxyethylene (60) aqueous solution of sorbitan laurate (available from Tween-60 'Kyoto Co., Ltd.) to determine iron ions by CP-MS (Inductively Coupled Plasma Mass Spectrometry) The total contents of cadmium ions and transition metal ions were 2.87 ppm, 0.65 ppm, and 15.31 ppm, respectively.
分散劑B 濃度10%的磺酸基琥珀酸月桂酯二鈉水滲液(LS-50,台新公 司提供）’以ICP-MS測定鐵離子、鎘離子以及過渡金屬離子合計 含里分別為 2.17 ppm，1.54 ppm 以及 19.33 ppm。Dispersant B 10% concentration of lauryl sulfosuccinate disodium sulphate (LS-50, supplied by Taixin)'s determination of iron, cadmium and transition metal ions by ICP-MS is 2.17 ppm , 1.54 ppm and 19.33 ppm.
分散劑C 濃度10%的二壬基磺酸琥珀酸鈉水溶液(290MH，中日合成 公司提供）’以ICP-MS測定鐵離子、鎘離子以及過渡金屬離子合 計含罝分別為1.27 ppm，1.34 ppm以及15.71 ppm。Dispersant C 10% aqueous solution of sodium dimercaptosulfonate succinate (290 MH, supplied by Sino-Japan Synthetic Co., Ltd.) ICP-MS determined total iron, cadmium and transition metal ions containing ruthenium 1.27 ppm, 1.34 ppm And 15.71 ppm.
分散劑D 濃度10%的十八烷基二甲基烴乙基月桂酸鈉鹽水溶液(中曰 合成公司提供）’以ICP-MS測定鐵離子、鎘離子以及過渡金屬離 子合計含量分別為3.49 ppm，2.34 ppm以及18.47 ppm。 實驗例一 1)取48%氫氧化鈉水溶液729g緩慢加入置有900g丙烯酸及972g 的水的5000c.c圓錐瓶中’氫氧化納與丙烯酸的滴加比率在〇 21 201100474 ‘ 至0.95範圍内’滴加時間為2小時’並保持瓶内中和反應系統 的溫度在20°C至40°C範圍内；此時得不飽合單體水溶液濃度 42wt/i>(重1百分比）’其中70mol%(莫耳比)丙稀酸部份中和為 丙烯酸納。 2) 再加入1.38g的N，N’-次曱基雙丙烯醯胺於部分中和的丙稀酸溶 液，並維持溫度於20°C左右。 3) 加入0. 48g雙氧水’ 6.0g亞硫酸氫鈉及6.〇g過硫酸錢以起始自 由基聚合反應生成吸水性樹脂水凝膠。 4) 利用切式粉碎機將反應後的水凝膠切碎，並篩選出粒徑大小為 2mm(厘米)直徑以下的凝膠體，並添加3〇g的分散劑a。 5) 以130°C溫度乾燥2小時；利用篩網篩選〇.imm~〇.85mm固定 粒徑，得粉狀南吸水性樹脂。 6) 秤取此兩吸水性樹脂3〇〇g，加入硫酸鋁粉末3g，待混合均勻後 再加入乙二醇碳酸g旨:水:曱醇二丨:丨:丨(重量比)溶液12g，以 C溫度加熱處理1〇分鐘。 7) 冷部後’秤取此高吸水性樹脂1〇〇g，加入水不溶性微粉氧化錢 粉末lg，待混合均句後再加入聚乙稀亞胺:水=1:3(重量比)容液 1¾ ’進行抗結绳處理，即得高性能高吸水性樹脂。 測疋保持力為29杨，黃化減為97 52%，殘存單體含量 28ppm。 22 201100474 實驗例二 重覆κ驗例一，但在分散劑a中加入2克ι〇〇/〇的氯化鐵溶液， 利用ICP-MS測定鐵離子以及過渡金屬離子合計含量分別為 ppm，以及34.52 ppm，將其作為分散劑，其餘步驟同實驗例—， 即得南吸水性樹脂。 測定保持力為28.64g/g，黃化指數為87.63%，殘存單體含量 36.7ppm ° 〇 實驗例三 重覆實驗例一’但使用分散劑B替代分散劑a ’其餘步驟同 實驗例一，即得高吸水性樹脂。 測定保持力為28.75g/g ’黃化指數為98.12%，殘存單體含量 62.17ppm。 Q 實驗例四 重覆實驗例三，但在分散劑B中加入2克10%的氣化鎮溶 液，利用ICP-MS測定鎘離子以及過渡金屬離子合計含量分別為 9.17ppm ’以及42.16ppm，將其作為分散劑，其餘步驟同實驗例 一’即得高吸水性樹脂。 測定保持力為29.79g/g，黃化指數為84.16%，殘存單體含量 62.84ppm 〇 23 201100474 實驗例五 重覆實驗例- ’但使用分散劑c替代分散劑A，將其作為分 散劑’其餘步驟同實驗例―，即得高吸水性樹脂。 測定保持力* 28.52g/g，黃化指數為9S. 37%，殘存單體含量 72.55ppm ° 實驗例六 1) 取娜氫氧化鈉水溶液吻緩慢加入置有_g丙稀酸及卿 的水的5_e.e _瓶中’氫氧化鈉與丙稀_滴加比率在0.85 至0.95範圍内，滴加時間為2小時，並保持瓶内中和反應系統 的溫度在20°C至40°C範圍内；此時得不飽合單體水溶液濃度 42wt%(重量百分比）’其中7〇福％(莫耳比)丙烯酸部份中和為 丙烯酸納。 2) 再加入1.3 8g的N，N’ -次曱基雙丙烯醯胺於部分中和的丙烯酸溶 液，並維持溫度於2(TC左右。 3) 加入0. 48g雙氧水，6.0g亞硫酸氫鈉及6 〇g過硫酸銨以起始自 由基聚合反應生成吸水性樹脂水凝膠。 4) 利用切式粉碎機將反應後的水凝膠切碎，並篩選出粒徑大小為 2mm(厘米)直徑以下的凝膠體，並添加30g的分散劑A。 5) 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。 24 201100474 - 6)秤取此高吸水性樹脂3〇〇g，加入硫酸紹粉末3g，待混合均勻後 再加入乙二醇碳酸酯:水:甲醇=1:1:1(重量比)溶液12g，以215 °C溫度加熱處理1〇分鐘。 7)冷卻後’秤取此高吸水性樹脂1〇〇g，加入水不溶性微粉氧化鎂 粉末lg ’待混合均勻後再加入聚乙烯亞胺:水=1:3(重量比你液 12g ’進行抗結塊處理，即得高性能高吸水性樹脂。 測定保持力為28.5g/g，黃化指數為93.81%，殘存單體含量 ^ 35.88ppm。 實驗例七 重覆實驗例六，但水不溶性微粉為碳酸鮮，其餘步驟同實驗例 六’即得高吸水性樹脂。 測疋保持力為28.28g/g，黃化指數為92. 71%，殘存單體含量 45.67ppm ° 〇 實驗例八 重覆實驗例―，但使用分散劑D替代分散劑A，將其作為分 散劑’其餘步驟同實驗例一，即得高吸水性樹脂。 測疋保持力為如她，黃化餘為，鱗單體含量 68.49ppm ° 比較例一 25 201100474 ^ 重覆實驗例一’但分散劑A中加入6克10%的氯化鐵溶液， 利用ICP-MS測定鐵離子以及過渡金屬離子合計含量分別為 34.56 ppm，以及84.17 ppm，將其作為分散劑，其餘步驟同實驗 例一，即得高吸水性樹脂。 測定保持力為28.94g/g，黃化指數為61. 78%，殘存單體含量 273ppm ° 比較例二 重覆實驗例一，但分散劑A加入8克1〇%的氣化鎘溶液，利 用ICP-MS測定錦離子以及過渡金屬離子合計含量分別為％ π ppm，以及92.44ppm，將其作為分散劑，其餘步驟同實驗例_， 即得高吸水性樹脂。 測定保持力為27.48g/g，黃化指數為55. 47%，殘存單體含量 197 ppm。 比較例三 重覆實驗例三’但分散劑B加入1〇克1〇%的氯化鐵溶液， 利用ICP_MS測定鐵離子以及過渡金屬離子合計含量分別為 35.33 ppm，以及99.76 ppm，將其作為中和劑，其餘步驟同實驗 例一，即得南吸水性樹脂。 測定保持力為30.01g/g，黃化指數為58.16%，殘存單體含量 26 201100474 ， 238ppm ° . 比較例四 重覆實驗例三，但分散劑B加入克20%的氣化鎳溶液， 利用ICP-MS測定鎳離子以及過渡金屬離子合計含量分別為 Π.13 ppm，以及137.4 ppm，將其作為中和劑，其餘步驟同實驗 例一’即得高吸水性樹脂。 測定保持力為29.77g/g，黃化指數為51. 68%，殘存單體含量 339ppm ° 比較例五 重覆比較例五，但水不溶性微粉為礙酸約，其餘步驟同比較 例五，即得高吸水性樹脂。Dispersant D concentration 10% octadecyl dimethyl hydrocarbon ethyl laurate sodium salt solution (provided by Zhonghao Synthetic Co., Ltd.) The total content of iron ions, cadmium ions and transition metal ions was 3.49 ppm by ICP-MS. , 2.34 ppm and 18.47 ppm. Experimental Example 1) 729 g of a 48% aqueous sodium hydroxide solution was slowly added to a 5000 c.c conical flask containing 900 g of acrylic acid and 972 g of water. The dropping ratio of sodium hydroxide to acrylic acid was in the range of 〇21 201100474 ' to 0.95'. The dropping time is 2 hours' and the temperature of the neutralization reaction system in the bottle is kept in the range of 20 ° C to 40 ° C; at this time, the concentration of the unsaturated monomer aqueous solution is 42 wt / i > (weight 1 percentage) '70 mol of which The % (mole ratio) acrylic acid moiety is neutralized to sodium acrylate. 2) Further, 1.38 g of N,N'-decyldiacrylamide was added to the partially neutralized acrylic acid solution, and the temperature was maintained at about 20 °C. 3) Adding 0.54 g of hydrogen peroxide' 6.0 g of sodium hydrogen sulfite and 6. 〇g of persulfate to initiate free radical polymerization to form a water-absorbent resin hydrogel. 4) The hydrogel after the reaction was chopped by a cutter mill, and a gel having a particle size of 2 mm (cm) or less was selected and 3 g of a dispersant a was added. 5) Drying at a temperature of 130 ° C for 2 hours; using a sieve to screen a fixed particle size of 〇.imm~〇.85 mm to obtain a powdery south water-absorbent resin. 6) Weigh 3 〇〇g of the two water-absorbent resins, add 3 g of aluminum sulfate powder, and add ethylene glycol carbonate after mixing. Water: sterol oxime: 丨: 丨 (weight ratio) solution 12 g, Heat treatment at C temperature for 1 minute. 7) After the cold part, weigh 1 〇〇g of this super absorbent resin, add water-insoluble micro-powder to oxidize the money powder lg, and then add the polyethyleneimine after mixing the sentence: water = 1:3 (weight ratio) The liquid 13⁄4 ' is subjected to an anti-knot treatment to obtain a high-performance superabsorbent resin. The retention of the test was 29 yang, the yellowing was reduced to 97 52%, and the residual monomer content was 28 ppm. 22 201100474 Experimental Example 2 Repeated κ test example 1, but adding 2 g of lanthanum/niobium chloride solution to dispersant a, and measuring the total content of iron ions and transition metal ions by ppm by ICP-MS, respectively, and 34.52 ppm, which was used as a dispersant, and the remaining steps were the same as in the experimental example, that is, the south water-absorbent resin was obtained. The measurement retention was 28.64 g/g, the yellowing index was 87.63%, and the residual monomer content was 36.7 ppm °. Experimental Example Triple Replica Example 1 'But Dispersant B was used instead of Dispersant a' The remaining steps were the same as Experimental Example 1, ie A highly water-absorbent resin is obtained. The measurement retention was 28.75 g/g, the yellowing index was 98.12%, and the residual monomer content was 62.17 ppm. Q Experimental Example 4 repeated experiment example 3, but adding 2 g of 10% gasification town solution to dispersant B, using ICP-MS to determine the total content of cadmium ions and transition metal ions are 9.17 ppm ' and 42.16 ppm, respectively. As a dispersing agent, the remaining steps were the same as in Experimental Example 1 to obtain a highly water-absorbent resin. The measurement retention was 29.79 g/g, the yellowing index was 84.16%, and the residual monomer content was 62.84 ppm. 201123 201100474 Experimental Example Five Repetitive Experimental Example - 'But dispersant C was used instead of dispersant A as a dispersant' The remaining steps are the same as in the experimental example, that is, a highly water-absorptive resin is obtained. Determination of retention * 28.52g / g, yellowing index of 9S. 37%, residual monomer content of 72.55ppm ° Experimental example 1) Take Na sodium hydroxide solution kiss slowly added with _g acrylic acid and Qing water The ratio of sodium hydroxide to propylene in the 5_e.e _ bottle is in the range of 0.85 to 0.95, the dropping time is 2 hours, and the temperature of the neutralization reaction system in the bottle is kept at 20 ° C to 40 ° C. Within the range; at this time, the concentration of the aqueous solution of the unsaturated monomer was 42 wt% (% by weight), wherein the neutral portion of the acrylic acid was neutralized as sodium acrylate. 2) Add 1.3 8g of N,N'-indenyl bis acrylamide to the partially neutralized acrylic acid solution and maintain the temperature at 2 (TC or so. 3) Add 0. 48g of hydrogen peroxide, 6.0g of sodium hydrogen sulfite And 6 〇g ammonium persulfate to initiate radical polymerization to form a water-absorbent resin hydrogel. 4) The hydrogel after the reaction was chopped by a cutter mill, and a gel having a particle size of 2 mm (cm) or less was selected, and 30 g of Dispersant A was added. 5) Drying at a temperature of 130 C for 2 hours; using a sieve to screen a fixed particle size of 〇.imm~〇.85 mm to obtain a powdery superabsorbent resin. 24 201100474 - 6) Weigh 3μg of this super absorbent resin, add 3g of sulfuric acid powder, and mix it evenly and then add ethylene glycol carbonate: water: methanol=1:1:1 (weight ratio) solution 12g Heat treatment at 215 °C for 1 minute. 7) After cooling, 'weigh 1 〇〇g of this superabsorbent resin, add water-insoluble fine powder magnesia powder lg' to be mixed evenly, then add polyethyleneimine: water = 1:3 (weight is 12g for your liquid) Anti-caking treatment, which is a high-performance superabsorbent resin. The measured retention is 28.5g/g, the yellowing index is 93.81%, and the residual monomer content is 35.88ppm. Experimental Example 7 Repeats Experimental Example 6, but water-insoluble fine powder It is carbonated fresh, and the other steps are the same as in the experimental example VIII. The high water-absorbent resin is obtained. The enthalpy retention is 28.28 g/g, the yellowing index is 92.71%, and the residual monomer content is 45.67 ppm ° 〇 Experimental example eight-fold experiment Example-, but using Dispersant D instead of Dispersant A, as a dispersant', the remaining steps are the same as Experimental Example 1, that is, a highly water-absorptive resin is obtained. The retention of the test is as she is, the yellowing residue is, and the content of the squamous monomer is 68.49 ppm. ° Comparative Example 1 25 201100474 ^ Repeated Example 1 - but 6 grams of 10% ferric chloride solution was added to Dispersant A, and the total content of iron ions and transition metal ions was determined by ICP-MS to be 34.56 ppm and 84.17 ppm, respectively. , as a dispersant, the remaining steps As in the first experimental example, the superabsorbent resin was obtained. The measurement retention was 28.94 g/g, the yellowing index was 61.78%, and the residual monomer content was 273 ppm. The second example was repeated, but the dispersant A was added. 8 g of 1% by weight of cadmium vapor solution, using ICP-MS to determine the total content of Jin ion and transition metal ion are % π ppm, and 92.44 ppm, respectively, as a dispersant, the remaining steps are the same as the experimental example _, that is high Water-absorbent resin. The measured retention was 27.48 g/g, the yellowing index was 55.47%, and the residual monomer content was 197 ppm. Comparative Example Triple Test Example 3 'But Dispersant B added 1 gram of 1% chlorine The iron solution was determined by ICP_MS to determine the total content of iron ions and transition metal ions to be 35.33 ppm and 99.76 ppm, respectively, as a neutralizing agent, and the remaining steps were the same as those in the experimental example, that is, the south water-absorbent resin was obtained. The determination retention was 30.01. g/g, yellowing index is 58.16%, residual monomer content is 26 201100474, 238ppm ° . Comparative example 4 repeated experiment example 3, but dispersant B is added with 20% nickel vapor solution, and nickel is determined by ICP-MS Total content of ions and transition metal ions Do not use 13.13 ppm, and 137.4 ppm, as a neutralizing agent, the other steps are the same as in the experimental example, that is, the superabsorbent resin is obtained. The measured retention is 29.77 g/g, and the yellowing index is 51.68%. Residual monomer content 339 ppm ° Comparative Example 5 is repeated with Comparative Example 5, but the water-insoluble fine powder is about acid, and the remaining steps are the same as in Comparative Example 5, that is, the super absorbent resin is obtained.
測定保持力為3G.16g/g，黃化指數為 371ppm ° 53. 33%，殘存單體含量 27The measured retention is 3G.16g/g, the yellowing index is 371ppm ° 53.33%, and the residual monomer content is 27