201200543 六、發明說明： 【發明所屬之技術領域】 高吸水性樹脂廣泛地·於農魏園藝方面的水保持劑、建 築材料中的抗露珠凝結劑以及移除石油中水份的除水劑，或是電 纜線中的外層防水包覆劑以及衛生用品如尿布、婦女衛生用品、 拋棄式的擦巾等，尤其使用於尿布上最為大宗。 超薄型尿布為目前主要的發展方向，由於超薄型尿布必須具 鲁備高密度的吸收層，此種吸收層中高吸水性樹脂與紙漿纖維混合 物就必須具備更高的吸收能力，為了充分利用吸收層儲存液體的 能力，所以液體在吸收層中的分佈情形就變得十分重要。一般而 言，吸收層中紙漿纖維的減少對液體在吸收層中的分佈情況會有 負面的影響。 當吸收層中的高吸水性樹脂或紙漿纖維在吸收液體後，會由 於迅速膨脹而造成高吸水性樹脂與紙漿纖維的空隙空間或高吸水 Φ性樹脂内的孔洞被封閉，因而抑制了液體的傳導，導致之後的液 體不能再穿透已經吸收液體而膨脹的區域，此一現象稱之為膠俨 阻塞(Gel- blocking);當此一現象發生後，之後的液體不能再穿 透吸收體，而向邊緣流動，導致洩露的情況發生。 此外’由於接近膨脹區域的高吸水性樹脂發生了膠體阻塞的 現象，其餘的液體無法到達更深層的部份，使得吸收層健存液俨 的能力大幅降低。 201200543 【先前技術】 在本技藝領域已知降低膠體阻塞的方法是改變高吸水性樹 脂的吸收速率（美國專利4,548,847號），該專利揭示使用所謂的 陽離子螯合劑(Cationic Complexing Agent)如：六偏磷酸鈉、乙二 胺四乙酸二納鹽或構酸氫敍等水溶性化合物，與含有至少一個二 價金屬離子所形成的水凝膠體，以減低水凝膠體中之交聯密度的 方式，使高吸水性樹脂更容易吸收液體。 EP0631 768A1提到了一種吸收體，該吸收體是利用不同粒 牷分佈的高吸水性樹脂(類型1的粒徑範圍為6〇〇_85〇um，類型2 的粒徑範圍為小於250um)，進一步產生具有不同吸收速度的吸收 體’但其吸收速度的差異並不大。 美國專利5，115,011號提到一種吸收血液及液體的吸收劑， 4吸收劑使用了高吸水性樹脂與具有峨酸基、亞硫酸根或硫酸根 的鹵素化合物的混合物。此類混合物稱之為水溶性混合物，以流 動粉末的狀態存在於室溫中，對生物體無害；將此混合物溶於不 飽和單體進行聚合反應，可以提高液體的擴散速度。此專利亦提 到使用具有鋁、鈣、鎂的硫酸鹽、醋酸鹽或硝酸鹽化合物與亞硫 酸的單價金屬鹽或銨鹽化合物以小於1〇重量。/。進行混合，可以降 低膠體阻塞現象的發生。 另外，美國專利5,578,318號使用具有羧酸基、磺酸基及磷 酸基的水溶性陰離子化合物與價數至少為3價之多價金屬，如： 録(Antimony)所製得之物質，也可以降低膠體阻塞現象的發生。 201200543 【發明擬解決的課題】 超薄型尿布必須具備高密度的吸收層’尤其是具有多層吸收 層的吸收體預防膠體阻塞現象的發生，是一項十分重要的技術課 題。解決此一課題的方法之一就是在高吸水性樹脂吸收體中滲入 可使高吸水性樹脂吸水速度較慢的化合物，然而，上述的美國專 利方法均無法提供令人滿意的慢速高吸水性樹脂。 使用檸檬酸根或是硫酸根的多價金屬鹽溶液與高吸水性樹 鲁脂混合，雖然可製得低吸收速度的高吸水性樹脂，但是，由於必 眉經由一次加工才能獲得使用，導致大幅降低生產效率提高製造 成本(美國專利 6,433,058、6,579,958 號）。 【解決課題之技術手段】 有鑑於此，本案發明人等經由長期的研究、試驗及工作上的 經驗發現，在尚吸水性樹脂的表面再作進一步表面交聯反應處 理，添加具有含胺基或羥基的化合物時能製得具有緩慢吸收水速 馨度的高吸水性樹脂，進而完成本發明。 本發明的目的即在提供製備一種具有緩慢吸收速度的高吸 水!·生樹脂’更進一步的說’由本發明所製造的高吸水性樹脂對合 成尿液具有緩慢的吸收速度，其合成尿㈣魏速率指數至少為5 刀在里。上述合成尿液的吸收速率指數(Abs_i〇nRateIndex A即 ^美國專利6,433,〇58號說明書第7頁中所描述的ARJ檢驗方法 所測定的吸收速率指數。 本發明一種具有緩慢吸收速度的高吸水性樹脂之製造方 201200543 法’口至少包括：使中和率45莫耳百分比_%)至85m〇i%之含酸 基單體水溶液，與聚合反應引細進行自由絲合反應生成高吸 水性樹脂水_體’此含酸基單體水溶_單體係選自丙婦酸或 F基丙稀Sx或2_丙烯n甲基丙烧績酸或上述群組之混合物。再 將上述凝膠體剪切成為小水凝膠體後以溫度觸。^至25G°C熱風進 行乾燥、粉碎、_，製得高吸水性樹脂(本段為本項技術領域公 知製造高吸水性樹脂的通常先·術），再於此㈣水性樹脂的表 面進行表面交聯反應處理。 本發明在此所提有別於現有技術共有的必要技術特徵的一 種具有緩慢吸收速度的高吸水性樹脂及其製法，其技術方案之特 徵在於將上賴公知先前技紗鋪成絲面交聯處理之高吸水 性樹脂的表©再作進—步架橋(表面交聯反應），即添加具有含胺 基或羥基化合物去進行表面交聯反應，此含胺基或羥基化合物的 添加方式是可以：（a)與表面交聯劑水溶液混合後，塗覆於高吸水 性樹脂表面以進行表面交聯反應；（b)於添加表面交聯處理前加入 於高吸水性麟表面進行表面交聯處理；（e)於添加表面交聯處理 後加入於高吸水性樹脂等三種方式添加。 【發明内容】 製造高吸水性樹脂所使用的水溶性不飽和單體，除丙稀酸 外，尚可使用其它具有含酸基團不飽和雙鍵的水溶性單體，如曱 基丙烯酸、馬林酸、富馬酸、2_丙烯胺_2_曱基丙烷磺酸、順丁烯 二酸、順丁烯二酸酐、反丁烯二酸、反丁烯二酸酐等。單體之選 201200543 用不限定只可使用一種，亦可合併多種單體一齊使用，亦可視情 況需要添加具有不飽和雙鍵其他親水性的單體，如:丙稀醯胺、曱 基丙烯醯胺、丙烯酸2-羧基乙酯、曱基丙烯酸2-羧基乙酯、丙烯 酸甲酯、丙烯酸乙酯、二曱胺丙浠丙烯醯胺、氣化丙烯丙烯醯胺 基三曱銨’但其添加量以不破壞高吸水性樹脂之物性為原則。 在進行自由基聚合反應時’單體水溶液的濃度並沒有特別的 限制，但較佳濃度宜控制在重量百分比20重量％至55重量％之 間’適當濃度為30重量％至45重量％之間。濃度控制在重量百分 比20重量％以下時，聚合後之水凝膠太軟且有黏性不利機械加 工’添加濃度在重量百分比55重量％以上，接近飽和濃度，不易 調配且反應太快反應熱不易控制。不飽和單體水溶液的值最好 控制不低於5.5，若pH低於5.5時’聚合後水凝膠體内殘存單體 含量過高，導致高吸水性樹脂之物性不佳。 在進行自由基聚合反應前，單體水溶液中亦可添加水溶性高 分子化合物以降低成本，此等水溶性高分子化合物如：部份皂化 或完全皂化的聚乙烯醇、聚乙二醇、聚丙烯酸、聚丙烯醯胺、澱 粉或澱粉衍生物如甲基纖維素，丙烯酸曱基纖維素，乙基纖維素 等聚合物；此等水溶性高分子化合物的分子量並不特別限定，其 中較佳的水溶性高分子化合物為澱粉、部份皂化或完全皂化的聚 乙烯醇專可卓獨或混合使用。高吸水性樹脂含此等添加有水溶性 高分子化合物的適當重量百分比為0至20重量％，以〇至1〇重量 201200543 重量％時會影響物性 %車父佳，0至5重量％尤佳，添加劑量超過 使物性變差。 在進仃自由基聚合反應前，應先添加自由基聚合反應交聯劑 於未反應早體溶液中’此自由基聚合反應交軸可選狀有兩個 或兩個以上猶和魏軌合物，如:Ν，Ν，却·叫基)胺、關， 次甲基雙丙烯醯胺、Ν，『次甲基雙甲基丙_胺、丙稀酸丙烯 酯、乙二醇二丙烯酸酯、聚乙二醇二丙烯醆酯、乙二醇二甲基丙 烯酸醋、聚乙二醇二甲基丙烯酸s|、甘油三叫㈣、甘油三甲 基丙稀_、甘油附加環氧乙烧之三丙稀動旨或三甲基_酸 _、三甲醇丙烧附加環氧⑽之三丙稀㈣或三甲基丙稀酸醋、 三曱醇丙烧三甲基丙稀酸醋、三曱醇丙烧三丙烯酸酿、N，N,N_三(2· 丙烯基)胺、二丙烯酸乙二醇醋、三丙烯酸聚氧乙烯甘油醋、三丙 缚酸二乙基聚氧乙烯甘油g旨、二丙烯三甘。亦可選用具有 兩個或兩個以上環氧基的化合物，如山梨㈣縮水甘細、聚丙 三醇聚縮水甘油醚、乙二醇二縮水甘_、二乙二醇二縮水甘油 喊、聚乙二醇二縮水甘細、雙丙三醇雜水甘油㈣。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，其 適當的添加劑量在重量百分比〇.001重量％至5重量％之間(以反應 物總固形份為基準），更適當的用量重量百分比在〇〇1重量％至3 201200543 重量。/。之間。添加劑量在重量百分比α〇〇1重量0/。以下，聚合後之 水合體太軟且擁性不職械加工，添加锻在重量百分比° 5重 量％以上，吸水性太低而降低樹脂性能。 含酸基單體之賴基是以中和劑控制成品之阳值，使其呈 中性或微酸性’中和綱職表中驗金域紅_氫氧化物或 是碳酸化合物，如：氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸钟、碳 si錢、魏氫鉀錢類化合物。巾和财單獨使㈣多種混合 使用。含酸基單體之麟基部份中和成_或鉀鹽或銨鹽，中和 濃度的莫耳百分比為45m〇1%至85m()1%，宜為至 75mol%。中和濃度莫耳百分比為45m〇1%以下時成品之阳值偏 低’中和漢度莫耳百分比為85mol%以上時成品之pH值偏高，成 品pH值非呈中性或微酸性時，若不慎與人體接觸均不太適合，也 較不安全。 • 製造咼吸水性樹脂的過程之一的預聚合反應，是由聚合引發 劑的分解產生自由基開始。聚合引㈣可選賴分解型起始劑， 適合的熱分解型起始劑有過氧化物，如：過氧化氫、二-第三丁美 過氧化物、過氧化醯胺或過硫酸鹽(銨鹽、驗金屬鹽)等，及偶氮化 合物如：2.2，-偶氮基雙(2_胨基丙烷)二鹽酸鹽、2.2，_偶氮基雙(N，N_ 二伸甲基異丁牌)二鹽酸鹽；亦可使用還原劑使其成為氧化還原型 起始劑，如：酸性亞械鹽、硫代韻鹽、抗壞血酸或亞鐵鹽； 或將氧化還原型起始劑和熱分解型起始劑合併使用。首先，氧化 201200543 還原起始劑是先進行反應產生自由基，當其自由基轉移至單體上 即引發聚合反應的進行，由於進行聚合反應時會釋放出大量的熱 量而使溫度升高，當溫度到達熱分解型起始劑的分解溫度時，又 會引發第二段熱分解型起始劑的分解，而使整個聚合反應更臻於 完全。一般自由基聚合反應起始劑適當用量為重量百分比〇 〇〇1 至10重量％(以中和丙烯酸鹽重量為基準），更適當用量則在重量 百分比0.1至5重量％之間，使用重量百分比0 001重量％以下時， 反應太慢不利經濟效益；使用重量百分比10重量％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。 本發明之聚合反應可於傳統批次反應容器中，或於輸送帶式 反應器上進行反應。反應所得之凝膠體，先利用絞碎機切成直徑 20mm以下的小凝膠體，直徑以下更佳，再進行篩選。 綿選固疋粒徑之凝膠體直徑以2.00 mm以下為宜’以〇.〇5 mm至1.50 mm間較佳。由於粒徑〇 〇5mm以下之凝膠體進行烘 乾、粉碎處理，易產生成品細粉量之提高，粒徑2 〇〇mm以上之凝 膠體進行烘乾，容易因為熱傳導效果不佳，導致成品之殘存單體 偏向，物性表現不佳；是故粒徑大於2 〇〇inm以上及小於〇 〇5mm 之凝膠體則重新送回反應器中進行再次反應、絞碎。 烘乾溫度以溫度loot：至180°C進行烘乾為宜，烘乾溫度 iooc以下，烘乾時間太久不具經濟效益，烘乾溫度180°c以上會 使交聯劑提早進行交聯反應，後續的乾燥過程因交聯度過高而無 201200543 法有效的去除殘存單體，達到降低殘存單體之效果。 乾燥後進行粉碎、筛選固定粒徑，再進行表面交聯劑塗覆處 理。篩選固定粒徑以0.05mm至J 〇〇mm間為宜，以〇 1〇峨至 0.850mm間較佳。粒徑__以下細粉使成品粉塵提高，粒徑 1.00mm以上粒子使成品吸水速率變慢。依據本發明，丙稀酸鹽聚 合物的顆粒大小分佈越窄越好。 ^ 【實施方式】 尚吸水性樹脂為一種不溶解化之親水性聚合體，樹脂内部具 有均勻性的架橋結構，—般為了改善品質，如提高吸收速率、提 高膠體強度、提高抗結舰、液蹄雜都會销簡表面再作 進-步架橋，此種表面交聯處理，即湘具有能與酸基反應之多 官能基交聯劑’目前已有許多專利被公開如：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_1316〇8、 • JP-A-57-44627、JP-A-58-42602、JP-A58-117222)，使用無機粉直 接將交聯劑與交聯劑溶液混入高吸水性樹脂處理 (JP-A60-163956、JP-A-60-255814)，添加交聯劑後以蒸氣處理 (JP-A-1-113406)，使用有機溶劑、水及多元醇進行表面處理 (JP-A-1-292004、美國專利6346569號），使用有機溶液、水、醚 (ether)化合物（jp-A-2-153903)等這些表面處理的方法雖能提 咼吸收速率，提高壓力下吸水倍率，但將造成保持力下降過多的 不良後果’降低了實際應用之性能。 11 201200543 元醇如：丙三醇、乙二醇 乙二醇、三乙二醇、聚乙二醇、丙 才據本發明’於表面處理時能同魏行反應的交聯劑可為多 'p ' ^ - m . r ~ ^ ___ 二醇專，或多元胺如：乙二胺、二乙二胺、三乙二胺；或具有兩 個或兩個以场的化合物如：山梨醇雜水甘_、聚丙三 酵聚縮水甘鱗、乙二醇二縮水甘油醚、二乙二醇二縮水甘_、 聚乙二醇二縮水甘㈣H醇聚縮水甘油鱗；亦有碳酸亞 乙—醇破_、4·ψ基]，3_二氧雜環戊坑m5_二甲 ㈣-二氧轉戊紋务认二曱基必二氧雜環戊龄科 乙基=二氧雜環姐_2,、以二氧雜環己烧摘、μ·二甲基 -u-一乳雜環己烷_2’或以二氧雜環庚烷1酮等。 上述表面交聯劑_法可單獨使用或兩種以上混合使用。交 聯劑的適當添加劑量在重量百分比_重量％至iq重量％之間 (:反應物總_份為基準）’更適當_量在議重量％至5重 里％之間又聯劑添加劑量在重量百分比議1重量％以下時無法 顯出效果，在重量百分fc[_ ] Λ 里里白刀比10重置％以上時，吸水性太低，降低 脂性能。 _ >本發明表面交聯劑在塗覆處理時之添加方式則是依據表面 =聯β的麵’分絲面交聯劑直接添加，或調絲面交聯劑水 冷液添加 <峨表面交聯舰水財機溶劑水溶液添加。親水 ϋ有機洛劑為如甲醇、乙醇、丙醇、異丁醇、丙酮、曱_、⑽ 等/又有特殊限制，只要可形成溶液即可，其中以曱醇、乙醇較佳(美 12 201200543 國專利6849665號）。 ’用之於本發明之具有含胺基 為充分顯示本 或羥基化合物通式為： (1)201200543 VI. Description of the Invention: [Technical Fields of the Invention] Superabsorbent resins are widely used in water retaining agents for agricultural and horticultural horticulture, anti-dew beads coagulating agents in building materials, and water removing agents for removing moisture from petroleum. Or the outer layer of waterproof coating agent in the cable and sanitary articles such as diapers, feminine hygiene products, disposable wipes, etc., especially used in diapers. Ultra-thin diapers are currently the main development direction. Since ultra-thin diapers must have a high-density absorbent layer, the superabsorbent resin and pulp fiber mixture in this absorbent layer must have higher absorption capacity, in order to make full use of The ability of the absorbent layer to store liquids, so the distribution of liquid in the absorbent layer becomes very important. In general, the reduction of pulp fibers in the absorbent layer can have a negative impact on the distribution of liquid in the absorbent layer. When the superabsorbent resin or the pulp fiber in the absorbent layer absorbs the liquid, the void space in the superabsorbent resin and the pulp fiber or the pore in the highly water-absorbent Φ resin is closed due to rapid expansion, thereby suppressing the liquid. Conduction, causing the subsequent liquid to no longer penetrate the area that has absorbed the liquid and expanded. This phenomenon is called Gel-blocking; when this phenomenon occurs, the subsequent liquid can no longer penetrate the absorber. The flow to the edge causes a leak to occur. In addition, since the superabsorbent resin close to the expanded region is colloidally clogged, the remaining liquid cannot reach the deeper portion, so that the ability of the absorbent layer to hold the liquid helium is greatly reduced. 201200543 [Prior Art] It is known in the art to reduce the rate of colloidal clogging by changing the rate of absorption of the superabsorbent resin (U.S. Patent No. 4,548,847), which discloses the use of so-called Cationic Complexing Agents such as: a water-soluble compound such as sodium phosphate, ethylenediaminetetraacetic acid di-nanoate or chlorinated hydrogen, and a hydrogel formed by containing at least one divalent metal ion to reduce the crosslinking density in the hydrogel To make the superabsorbent resin absorb liquid more easily. EP 0 631 768 A1 mentions an absorbent body which is a superabsorbent resin which is distributed using different particle sizes (type 1 has a particle size range of 6 〇〇 _ 85 〇 um, type 2 has a particle size range of less than 250 um), further An absorber having different absorption velocities is produced 'but the difference in absorption speed is not large. U.S. Patent No. 5,115,011 discloses an absorbent for absorbing blood and liquid, and the fourth absorbent uses a mixture of a superabsorbent resin and a halogen compound having a decanoic acid group, a sulfite group or a sulfate group. Such a mixture is referred to as a water-soluble mixture, which is present in the state of a flowing powder at room temperature and is harmless to the living body; the polymerization of the mixture in an unsaturated monomer can increase the diffusion rate of the liquid. This patent also teaches the use of a monovalent metal or ammonium salt compound having a sulfate, acetate or nitrate compound of aluminum, calcium or magnesium and a sulfuric acid of less than 1 Torr. /. Mixing can reduce the occurrence of colloidal blockage. In addition, U.S. Patent No. 5,578,318 uses a water-soluble anionic compound having a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and a polyvalent metal having a valence of at least trivalent, such as a substance obtained by Antimony, can also be reduced. Colloidal blockage occurs. 201200543 [Problems to be solved by the invention] Ultra-thin diapers must have a high-density absorbing layer, especially an absorber with multiple layers of absorbing layers to prevent colloidal clogging, which is a very important technical topic. One of the methods for solving this problem is to infiltrate a highly water-absorbent resin absorber into a compound which can make the superabsorbent resin absorb water slowly. However, none of the above-mentioned U.S. patent methods can provide satisfactory slow superabsorbency. Resin. The polyvalent metal salt solution using citrate or sulfate is mixed with the highly water-absorbable resin, although a highly absorbent resin having a low absorption rate can be obtained, but since the eyebrow can be used through one process, it is greatly reduced. Production efficiency increases manufacturing costs (US Patent 6,433,058, 6,579,958). [Technical means for solving the problem] In view of this, the inventors of the present invention discovered through the long-term research, test, and work experience that further surface crosslinking treatment is performed on the surface of the water-absorbent resin, and an amine group-containing group or In the case of a hydroxy compound, a highly water-absorptive resin having a slow absorption of water scent can be obtained, and the present invention is completed. The object of the present invention is to provide a high water absorption with a slow absorption rate. · Raw resin. Further, the super absorbent resin produced by the present invention has a slow absorption rate for synthetic urine, and its synthetic urine (four) Wei The rate index is at least 5 knives. The absorption rate index of the above synthetic urine (Abs_i〇nRateIndex A is the absorption rate index determined by the ARJ test method described in the U.S. Patent No. 6,433, No. 5, page 7 of the specification. The present invention has a high absorption rate with a slow absorption rate. Resin manufacturer 201200543 The method includes at least: a neutralization rate of 45 mole % _% to 85 m 〇 i% of an acid-based monomer aqueous solution, and a free-filament reaction with a polymerization reaction to form a high water absorption Resin water_body' This acid-containing monomer water-soluble system is selected from the group consisting of propyl benzoate or F-propyl propylene Sx or 2- propylene n-methyl propyl acid or a mixture of the above groups. The gel was then sheared into a small hydrogel and exposed to temperature. ^ to 25G ° C hot air drying, pulverization, _, to obtain a highly water-absorbent resin (this paragraph is generally known in the art for the manufacture of superabsorbent resins), and then (4) the surface of the surface of the water-based resin Cross-linking reaction treatment. The invention provides a superabsorbent resin having a slow absorption speed and a preparation method thereof, which are different from the necessary technical features common in the prior art, and the technical solution thereof is characterized in that the prior art yarn is paved and crosslinked. The treatment of the super absorbent resin is further carried out - step bridging (surface crosslinking reaction), that is, adding an amine group-containing or hydroxy compound to carry out surface crosslinking reaction, and the addition method of the amine group or the hydroxy compound is : (a) after being mixed with the aqueous surface crosslinking agent, applied to the surface of the superabsorbent resin for surface crosslinking reaction; (b) added to the highly water-absorbing lining surface for surface crosslinking treatment before the surface crosslinking treatment is added. (e) It is added in three ways such as addition of a superabsorbent resin after addition of a surface crosslinking treatment. SUMMARY OF THE INVENTION A water-soluble unsaturated monomer used for producing a super absorbent resin, in addition to acrylic acid, other water-soluble monomers having an unsaturated double bond containing an acid group, such as mercaptoacrylic acid, horse, can be used. Linic acid, fumaric acid, 2-propenylamine 2_mercaptopropanesulfonic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, and the like. The monomer selection 201200543 is not limited to one type, and may be used in combination with a plurality of monomers. It is also possible to add other hydrophilic monomers having unsaturated double bonds, such as acrylamide or mercapto propylene. Amine, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, methyl acrylate, ethyl acrylate, diamine propylene acrylamide, gasified propylene acrylamide ruthenium triammonium 'but the addition amount thereof The principle is that the physical properties of the superabsorbent resin are not destroyed. The concentration of the aqueous monomer solution is not particularly limited in carrying out the radical polymerization reaction, but the preferred concentration is preferably controlled between 20% by weight and 55% by weight by weight, and the appropriate concentration is between 30% by weight and 45% by weight. . When the concentration is controlled to be less than 20% by weight, the hydrogel after polymerization is too soft and sticky. Unfavorable mechanical processing 'Addition concentration is more than 55% by weight, close to saturation concentration, difficult to mix and react too fast. Reacting heat is not easy. control. The value of the aqueous solution of the unsaturated monomer is preferably controlled to be not less than 5.5. If the pH is lower than 5.5, the residual monomer content in the hydrogel after polymerization is too high, resulting in poor physical properties of the superabsorbent resin. The water-soluble polymer compound may be added to the aqueous monomer solution to reduce the cost before the radical polymerization reaction, such as partially saponified or fully saponified polyvinyl alcohol, polyethylene glycol, poly a polymer such as acrylic acid, polypropylene decylamine, starch or a starch derivative such as methyl cellulose, decyl cellulose acrylate or ethyl cellulose; the molecular weight of the water-soluble polymer compound is not particularly limited, and among them, preferred The water-soluble polymer compound is starch, partially saponified or fully saponified polyvinyl alcohol, which may be used alone or in combination. The superabsorbent resin containing such a water-soluble polymer compound in an appropriate weight percentage of 0 to 20% by weight, which affects the physical property % of the 201200543% by weight, affects the physical property of the car, preferably 0 to 5% by weight. The amount of the additive exceeds the physical properties. Before the radical polymerization, the free radical polymerization crosslinker should be added to the unreacted early solution. 'This free radical polymerization cross-link can be used to have two or more hep- and Wei-orbitals. Such as: Ν, Ν, · 叫 )) amine, off, methine bis acrylamide, hydrazine, "methine dimethyl propyl amide, propylene acrylate, ethylene glycol diacrylate, Polyethylene glycol dipropylene oxime ester, ethylene glycol dimethacrylate vinegar, polyethylene glycol dimethacrylate s |, glycerol tris (four), glycerol trimethyl propylene _, glycerol plus epoxy ethene Propylene or trimethyl-acid _, trimethyl methacrylate propylene (10) tripropylene (tetra) or trimethyl acrylate vinegar, trimethyl alcohol propyl trimethyl acrylate vinegar, triterpene alcohol Acrylic triacetin, N, N, N_tris(2·propenyl)amine, ethylene glycol vinegar diacetate, polyoxyethylene glycerin triacetate, tributyl polyoxyethylene glycerol Dipropylene triglyceride. Compounds having two or more epoxy groups may also be used, such as Yamanashi (four) glycosaminoglycan, polyglycerol polyglycidyl ether, ethylene glycol dihydrated glycine, diethylene glycol diglycidyl shunt, polyethyl b Glycol dimethyl condensate, diglycerol diglycidyl (IV). 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 crosslinking agent may be used singly or in combination of two or more, and the appropriate amount of the additive is between 0.001% by weight and 5% by weight based on the total solids of the reactants, more appropriate. The weight percentage is from 〇〇1% by weight to 3 201200543 by weight. /. between. The added dose is in the weight percentage α〇〇1 weight 0/. Hereinafter, the hydrated body after polymerization is too soft and has no mechanical processing, and the forging is added in a weight percentage of more than 5% by weight, and the water absorption is too low to lower the resin property. The base of the acid-containing monomer is controlled by a neutralizing agent to control the positive value of the finished product to make it neutral or slightly acidic. In the neutralization table, the gold field red hydroxide or carbonate compound, such as hydrogen Sodium oxide, potassium hydroxide, sodium carbonate, carbonic acid clock, carbon si money, Wei hydrogen potassium money compound. Towels and money alone make (4) a mixture of various uses. The thiol moiety of the acid group-containing monomer is neutralized to a potassium salt or an ammonium salt, and the concentration of the molar concentration in the neutralization concentration is 45 m 〇 1% to 85 m () 1%, preferably to 75 mol%. When the percentage of neutralization concentration is 45m〇1% or less, the positive value of the finished product is low. When the percentage of neutralization and molarity is 85mol% or more, the pH value of the finished product is high, and when the pH value of the finished product is not neutral or slightly acidic, If it is not suitable for contact with the human body, it is not suitable and it is not safe. • The prepolymerization of one of the processes for producing a water-absorbent resin begins with the decomposition of a polymerization initiator to generate a radical. The polymerization initiator (4) may be selected as a decomposition initiator, and the suitable thermal decomposition initiator is a peroxide such as hydrogen peroxide, di-t-butyrate peroxide, guanidinium peroxide or persulfate ( Ammonium salts, metal salts, etc., and azo compounds such as: 2.2, -azobis(2-amidinopropane) dihydrochloride, 2.2,_azobis(N,N_diexexylmethyl) Ding) dihydrochloride; may also use a reducing agent to make it a redox initiator, such as: acidic mesogenic salt, thio-salt salt, ascorbic acid or ferrous salt; or redox-type initiator and Thermally decomposable initiators are used in combination. First, the oxidation of 201200543 reduction initiator is to carry out the reaction to generate free radicals. When the free radicals are transferred to the monomers, the polymerization reaction is initiated. As the polymerization reaction is carried out, a large amount of heat is released to raise the temperature. When the temperature reaches the decomposition temperature of the thermal decomposition type initiator, decomposition of the second stage thermal decomposition type initiator is caused, and the entire polymerization reaction is more complete. Generally, the radical polymerization initiator is used in an amount of from 〇〇〇1 to 10% by weight (based on the weight of the neutralized acrylate), and more suitably in an amount of from 0.1 to 5% by weight, based on the weight percentage. When the ratio is less than 0 001% by weight, the reaction is too slow to be economically advantageous; when the weight percentage is 10% by weight or more, the reaction is too fast, the heat of reaction is not easily controlled, and the polymerization is excessively easy to form a gel-like solid. The polymerization of the present invention can be carried out in a conventional batch reaction vessel or on a conveyor belt reactor. The gel obtained by the reaction is first cut into small gels having a diameter of 20 mm or less by a mincer, and the diameter is preferably less than the diameter, and then subjected to screening. The diameter of the gel of the solid-grained particle size is preferably 2.00 mm or less, preferably between mm5 mm and 1.50 mm. Since the gel having a particle size of 〇〇5 mm or less is subjected to drying and pulverization treatment, the amount of fine powder of the finished product is easily increased, and the gel having a particle diameter of 2 〇〇 mm or more is dried, which is liable to cause poor heat conduction effect. The residual monomer of the finished product is biased and the physical properties are not good; therefore, the gel body having a particle diameter of more than 2 〇〇inm and less than 〇〇5 mm is returned to the reactor for re-reaction and mincing. The drying temperature is preferably dried at a temperature of loot: to 180 ° C. The drying temperature is below iooc. The drying time is too long and has no economic benefit. The drying temperature of 180 ° C or more will cause the crosslinking agent to crosslink earlier. In the subsequent drying process, the crosslinking degree is too high and the 201200543 method is effective to remove residual monomers, thereby reducing the residual monomer. After drying, it is pulverized, sieved to a fixed particle size, and subjected to a surface crosslinking agent coating treatment. The screening fixed particle diameter is preferably between 0.05 mm and J 〇〇 mm, and preferably between 〇 1 〇峨 and 0.850 mm. The fine powder below the particle size __ improves the finished dust, and the particle size of 1.00 mm or more makes the water absorption rate of the finished product slow. According to the present invention, the narrower particle size distribution of the acrylic acid polymer is preferably as small as possible. ^ [Embodiment] The water-absorbent resin is an insoluble hydrophilic polymer with a bridge structure with uniformity inside the resin, generally for improving the quality, such as increasing the absorption rate, improving the strength of the colloid, and improving the anti-soil and liquid. The hoof will be pinned to the surface and then stepped into the bridge. This surface cross-linking treatment, that is, the polyfunctional cross-linking agent capable of reacting with the acid group, has been disclosed in many patents such as: dispersing superabsorbent resin Surface cross-linking treatment with a crosslinking agent in an organic solvent (Jp_A_56_1316〇8, • JP-A-57-44627, JP-A-58-42602, JP-A58-117222), using an inorganic powder directly to crosslink the crosslinking agent The mixture is mixed with a superabsorbent resin (JP-A60-163956, JP-A-60-255814), and a cross-linking agent is added, followed by steam treatment (JP-A-1-113406), using an organic solvent and water. Surface treatment with a polyol (JP-A-1-292004, U.S. Patent No. 6,346,569), using an organic solution, water, an ether compound (jp-A-2-153903), etc.咼 absorption rate, increase the water absorption rate under pressure, but will cause the retention to decrease Many adverse consequences' degrades the performance of the practical application. 11 201200543 Non-alcohols such as glycerol, ethylene glycol glycol, triethylene glycol, polyethylene glycol, and C. According to the present invention, the cross-linking agent capable of reacting with Weixing during surface treatment may be more p ' ^ - m . r ~ ^ ___ diol, or polyamines such as: ethylenediamine, diethylenediamine, triethylenediamine; or compounds with two or two fields such as: sorbitol Gan _, poly propylene three polycondensation sugar scales, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl _, polyethylene glycol dimethyl condensate (tetra) H alcohol polyglycidol scale; also ethylene carbonate - alcohol broken _,4·ψ基],3_dioxolane m5_dimethyl(tetra)-dioxo-transpentaquinone bismuth-diethylidene-dioxacyclopentylethyl-dioxydiene , by dioxane calcination, μ· dimethyl-u-mono-heterocyclohexane 2′ or dioxepane 1 ketone. The above surface crosslinking agent_method may be used singly or in combination of two or more. The appropriate amount of the additive of the crosslinking agent is between 重量% by weight and iq% by weight (based on the total amount of the reactants) 'more appropriate _ between 5% by weight and 5% by weight. When the weight percentage is less than 1% by weight, the effect cannot be exhibited. When the white knife is more than 10% by weight in the weight percentage fc[_ ] Λ, the water absorption is too low, and the grease performance is lowered. _ > The surface cross-linking agent of the present invention is added in the coating treatment according to the surface of the surface of the β-side surface of the cross-linking agent, or the surface of the surface-crosslinking agent is added to the water-cooling liquid. The cross-linked ship water machine solvent aqueous solution is added. The hydrophilic hydrazine organic granules are, for example, methanol, ethanol, propanol, isobutanol, acetone, hydrazine _, (10), etc., and have special restrictions, as long as a solution can be formed, among which decyl alcohol and ethanol are preferred (US 12 201200543) National Patent No. 6,846,665). The amine-containing group used in the present invention is a fully-displayed or hydroxy compound having the formula: (1)
X-R-Y 式中；R表示碳原子數不小於4具有直鏈或支_絲(_化 合物；X、γ為絲或經基。 就本心月而。’利用具有滿足通式⑴的化合物與交聯化合物 的混合水溶液魏於高則^咖旨進行交聯聽，然經溫度⑽t 30 C,’’、風處理’即可製成具有緩慢吸收速度的’在較高的壓力 下具有杈而吸收倍率的高吸水性樹脂為本發明之最大技術特徵。 用來製造合於上述步驟的高吸水性樹脂並無特殊之限制， 只要經 由本發明之方法製造所得之高吸水性娜，雜適用於各種型式 的衛生用、農業用及食品保鮮用的吸水用品。 用之於本發明具有含胺基或羥基的化合物為例如：1,2-丁二 醇、1,3-丁二醇、ι，4-丁二醇、❻戊二醇、μ.戊二醇、以戊二 醇、2,4-戊二醇、l，2-己二醇、^庚二醇、^辛二醇、Μ_丁二 胺、2-胺基-1-丁醇、2-胺基_1_戊醇、2_胺基-1-己醇、2-胺基-2-甲 基-1-内醇、2-胺基-3-曱基·1_丁醇、2_胺基_4_曱基_ι_戊醇等。此含 胺基或經基化合物的用法可單獨使用或兩種以上混合使用其適當 的添加劑量在重量百分比〇 · 〇 〇 1重量％至5重量。/。之間（以反應物總 13 201200543 固形份為基準），更為適當的用量在_5重量％至3重量％之間。 含胺基或祕化合物的添加劑量，在重量百分比〇施重量％以下 時無法顯出效果，在重量百分比5重量％以上時，吸水性太低，降 低樹脂性能。 本發明製備-種具有緩慢吸收速度的高吸水性樹脂之方 法，係凡以公知製法製成的高吸水性樹脂表面，再作進一步架橋 (表面交聯反應），即添加塗覆具有含職或織化合物於高吸水 性樹脂顆粒上進行表面交聯反應，此含胺基或化合物的添加 方式是以：（a)與表面交聯水溶液混合後，塗覆於高吸水性樹脂表 面以進打表面交聯反應；（b)於添加表面交聯劑處理前加入於高吸 水性樹脂表面進行表面交聯處理；或(e)於添加表面交聯劑處理後 再加入於高吸水性樹脂等三種方式添加。 本發明之目的在提供一種粉狀、不溶於水，可吸收水液或尿 液及血液的高吸水性樹脂，具有緩慢的吸收速度，且在較高的壓 力下具有較高吸收倍率特性。其製造方法至少包括： (a) 使用一種含有丙稀酸（鹽）與/或丙稀酿胺（鹽）的水溶性不 飽和單體，中和比率在45至85莫耳％之範圍内，不飽和單體 水溶液的濃度在20至55重量％之範圍進行聚合反應； (b) 反應後生成的凝膠體切碎，在溫度i〇〇°Ci丨⑽充範圍的熱 風乾燥、粉碎、篩選； (c) 將篩選出的高吸水性樹脂以交聯化合物與含胺基或羥基化 201200543 合物的混合水溶液再進行表面交聯塗覆處理；及 (d)溫度120 C至230°C加熱處理。 上述之特徵’係利用含胺基或羥基化合物與高吸水性樹脂進 仃表面父聯聚合反應’當表面交卿合反應完成，高吸水性樹脂 的表面即會產生疏水基gj，藉此達珊低吸收速度的結果，並且 在咼壓力下具有較高吸收倍率之功效特性。 ^ 就本發明而言，經由本發明所製造的高吸水性樹脂，由於具 有緩慢的吸收速度，以及在較高的壓力下具有較高吸收倍率之特 性’則經由本發明所製得之高吸水性樹脂將能更適用於各種型式 的衛生用、辰業用及食品保鮮用的吸水用品。 為顯不本發明之高吸水性樹脂的壓力下吸水倍率，本發明的 保持力係絲試驗法測定’並以五次制結果，去除最高值 以及最低值後取平均值，將0.2g的高吸水性樹脂裝在茶袋裡，並 _反泡於0.9%的NaCl水溶;夜20分鐘’然後將此浸泡後的茶袋置於 離心機中離心(直徑23cm、轉速MOOrpm)三分鐘後秤重。所得之 數值先減去未充填高吸水性樹脂的空白組茶袋重(以相同步驟操作) 再除以聚合物重即得保持力數值。 本發明之高吸水性樹脂的壓力下吸水倍率，是利用受壓吸收 重(壓力負荷·· 2〇g/Cm2及49g/cm2)來測定，受壓吸收量係根據歐洲 專利0339461 A f虎說明書第七頁中所描述的方法；即將初始重量 的间吸水性樹脂放在依據有篩網底部的圓柱體中，對粉體加以 15 201200543 20g/cm2及49g/cm2的壓力，接著將此圓柱體置於吸收性需求測試 器上’讓此咼吸水性樹脂吸收0.9%的氯化鈉水溶液一小時，再將 測吸水重量將所得數值除以高吸水性樹脂的重量，即得受壓吸收 重數值。 以下以參考例及實施例，詳細說明本發明；但本發明範圍不 受這些實施例所限制。 參考例：（本技術領域的習知高吸水性樹脂製造方法） 1) 取48%氫氧化鈉水溶液218.7g緩慢加入於置有27〇g丙烯酸及 291.6g的水的500C.C圓錐瓶中’氫氧化鈉/丙烯酸的滴加比率在 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；此時得單體濃度42重量％ 水溶液，其中70md%(莫耳比)之丙烯酸部份中和成為丙烯酸鈉。 2) 添加入0.414 g的N，N’-次曱基雙丙烯醯胺於水溶性不飽和單體 溶液中，溫度維持於20。(：左右。 3) 再加入〇.144g雙氧水，1.8g亞硫酸氫鈉及Ug過硫酸銨起始 劑進行聚合反應。 4) 將反應生成的凝膠體以切式粉碎機切碎，並篩選出粒徑大小為 2mm直徑以下的凝膠體。 5) 再以13(TC溫度乾燥2小時後利用〇.lmm〜〇85麵固定粒徑筛 網筛選，得粉狀高吸水性樹脂。測定得保持力為41 9g/g，2〇g/cm2 201200543 壓力下吸水倍率6.5g/g，49g/cm2壓力下吸水倍率&2g/g。 實施例一： 秤取參考例所製得的高吸水性樹脂100g，加入乙二醇、1，4-丁二醇(台灣塑膠公司製造)及曱醇1蘭.5混合的水溶液2,5g，以 150 C/JHL度加熱處理丨小時，冷卻後，即得高性能高吸水性樹脂。 測定得保持力為31.9g/g，20g/cm2壓力下吸水倍率28.7g/g，49g/cm2 籲壓力下吸水倍率丨9#々，咖值為8分鐘。 實施例二： 重覆貫施例一，但以180°C溫度加熱處理1〇分鐘，其餘同 貫例一’得高性能高吸水性樹脂。測定得保持力為32 7g/g，2〇g/cm2 壓力下吸水倍率28.1g/g，49g/cm2壓力下吸水倍率18 5g/g，ARI 值為9.5分鐘。 φ 實施例三： 重覆實施例一，但使用1，4-丁二胺(Fhka公司製造，商名號： 32790)替代i，4·丁二醇’其餘同實例一，得高性能高吸水性樹脂。 測疋得保持力為32.5g/g’20g/cm2壓力下吸水倍率28.9g/g，49g/cm2 壓力下吸水倍率19.4g/g，ARI值為8.4分鐘。 17 201200543 實施例四: 重覆實施例三，但以190°C溫度加熱處理10分鐘，其餘同 頁例二’可仔向性此南吸水性樹脂。測定得保持力為32.1 g/g， 20g/cm壓力下吸水倍率29.4g/g，49g/cm2壓力下吸水倍率 19.1g/g，ARI 值為 9.6 分鐘。 實施例五： 重覆實施例一，但使用2-胺基-1_丁醇(Fluka公司製造，商名 號：7176)替代1,4-丁二醇，其餘同實例一’得高性能高吸水性樹 脂。測定得保持力為31.5g/g，20g/cm2壓力下吸水倍率28.2g/g， 49g/cm2壓力下吸水倍率18 3g/g，ARI值為15 7分鐘。 實施例六： 重覆實施例一，但使用1，2·辛二醇(Sigma_Aldrich公司製造， 商名號：213期)替代1，4_丁二醇，其餘同實例一，得高性能高吸 水性樹脂。測定得保持力為3Ug/g，2〇g/cm2壓力下吸水倍率 29.5g/g，49g/cm2壓力下吸水倍率18 9g/g，ARI值為23 5分鐘。 實施例七： 重覆實施例一，但使用乙二醇碳酸酯替代乙二醇，其餘同實 例一’得高性能高吸水性樹脂。測定得保持力為32地 ，20g/cm2XRY wherein R represents a carbon atom number of not less than 4 and has a straight chain or a branch-filament (-compound; X, γ is a silk or a mercapto group. In the present case, 'using a compound having the formula (1) and cross-linking The mixed aqueous solution of the compound is high in the case of cross-linking, but after temperature (10) t 30 C, '', wind treatment' can be made to have a slow absorption speed with a higher pressure and a absorption ratio. The super absorbent resin is the most technical feature of the present invention. The superabsorbent resin used to produce the above steps is not particularly limited as long as the resulting highly water-absorbent Na is produced by the method of the present invention, and is suitable for various types. Absorbent articles for sanitary, agricultural and food preservation. The compounds having an amine group or a hydroxyl group in the present invention are, for example, 1,2-butanediol, 1,3-butanediol, ι,4- Butanediol, pentylene glycol, μ. pentanediol, pentanediol, 2,4-pentanediol, 1,2-hexanediol, heptanediol, octanediol, cesium-butane Amine, 2-amino-1-butanol, 2-amino-1-pentanol, 2-amino-1-hexanol, 2-amino-2-methyl-1-lactam, 2-amine Base-3-曱· 1-butanol, 2-amino- 4-fluorenyl-I-p-pentanol, etc. The use of the amine-containing or trans-base compound may be used singly or in combination of two or more kinds thereof in an appropriate amount by weight. · 〇〇1% by weight to 5% by weight (based on total reactants of 201200543 solids), more suitably between _5% by weight and 3% by weight. Amine-containing or secret compound The amount of the additive does not show an effect when the weight percentage is less than or equal to the weight%, and when the weight percentage is 5% by weight or more, the water absorption is too low to lower the resin property. The present invention produces a superabsorbent resin having a slow absorption rate. The method is a surface of a highly water-absorbent resin produced by a known method, and further bridged (surface cross-linking reaction), that is, a surface-crosslinking reaction is carried out by coating a high-absorbent resin particle with a coating or a compound. The amine group-containing compound or the compound is added in such a manner that: (a) is mixed with the surface cross-linking aqueous solution, and is applied to the surface of the super-absorbent resin to carry out surface cross-linking reaction; (b) treatment with addition of surface crosslinking agent Pre plus The surface of the superabsorbent resin is subjected to surface crosslinking treatment; or (e) is added to the superabsorbent resin after addition of the surface crosslinking agent, and the like. The object of the present invention is to provide a powdery, water-insoluble, A superabsorbent resin that absorbs aqueous liquid or urine and blood, has a slow absorption rate, and has a high absorption rate characteristic at a relatively high pressure. The manufacturing method includes at least: (a) using a kind of acrylic acid a water-soluble unsaturated monomer of (salt) and/or acrylamide (salt) having a neutralization ratio in the range of 45 to 85 mol% and a concentration of the aqueous unsaturated monomer solution in the range of 20 to 55 wt% (a) the gel formed after the reaction is chopped, dried, pulverized, and screened at a temperature of i〇〇°Ci丨(10) in a full range; (c) cross-linking the selected superabsorbent resin The mixed aqueous solution of the compound and the amine group-containing or hydroxylated 201200543 compound is subjected to surface crosslinking coating treatment; and (d) heat treatment at a temperature of 120 C to 230 °C. The above-mentioned feature 'is the use of an amine-containing or hydroxy compound and a superabsorbent resin to enter the surface of the parent-side polymerization. When the surface cross-linking reaction is completed, the surface of the superabsorbent resin will generate a hydrophobic group gj, thereby The result of low absorption rate and high absorption efficiency at helium pressure. For the purpose of the present invention, the superabsorbent resin produced by the present invention has high water absorption by the present invention due to its slow absorption speed and high absorption ratio at a higher pressure. The resin will be more suitable for various types of absorbent products for sanitary, medicinal and food preservation. In order to show the water absorption ratio under pressure under the pressure of the super absorbent resin of the present invention, the retention force of the present invention is measured by the test method of the wire and is obtained by the fifth-order result, and the highest value and the lowest value are removed, and the average value is taken, and the average value is 0.2 g. The water-absorbent resin was placed in a tea bag, and was immersed in 0.9% NaCl water-soluble; 20 minutes in the night. Then, the soaked tea bag was centrifuged in a centrifuge (diameter 23 cm, rotation speed MOO rpm) for three minutes, and then weighed. The obtained value is first subtracted from the weight of the blank group tea bag which is not filled with the super absorbent resin (operating in the same step) and then divided by the weight of the polymer to obtain the retention value. The water absorption capacity under pressure of the superabsorbent resin of the present invention is measured by the pressure absorption weight (pressure load··2〇g/cm 2 and 49 g/cm 2 ), and the pressure absorption amount is according to the European Patent No. 0339461 A The method described on page 7; placing the initial weight of the water-absorbent resin in a cylinder according to the bottom of the screen, applying 15 201200543 20g/cm2 and 49g/cm2 to the powder, and then applying the cylinder Placed on the absorbent demand tester's 'This water-absorbing resin absorbs 0.9% sodium chloride aqueous solution for one hour, and then the measured water-absorbent weight is divided by the weight of the superabsorbent resin. . The invention is described in detail below with reference to the examples and examples; however, the scope of the invention is not limited thereto. Reference Example: (Preparation method of a conventional superabsorbent resin in the art) 1) A solution of 218.7 g of a 48% aqueous sodium hydroxide solution was slowly added to a 500 C.C conical flask containing 27 g of acrylic acid and 291.6 g of water. The dropping ratio of sodium hydroxide/acrylic acid 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 maintained in the range of 20 ° C to 40 ° C; A 42% by weight aqueous solution in which 70 md% (mole ratio) of the acrylic acid portion was neutralized to sodium acrylate. 2) 0.414 g of N,N'-decyldiacrylamide was added to the water-soluble unsaturated monomer solution at a temperature of 20. (: Left and right. 3) Further polymerization was carried out by adding 144.144 g of hydrogen peroxide, 1.8 g of sodium hydrogen sulfite and Ug ammonium persulfate initiator. 4) The gel formed by the reaction was chopped by a cutter mill, and a gel having a particle size of 2 mm or less was selected. 5) After drying at 13 °C for 2 hours, the sieve was sieved with a fixed size sieve of 〇.lmm~〇85 to obtain a powdery superabsorbent resin. The retention was determined to be 41 9g/g, 2〇g/ Cm2 201200543 Under water pressure absorption ratio 6.5g / g, water absorption ratio under pressure of 49g / cm2 & 2g / g. Example 1: Weighing 100g of superabsorbent resin prepared in the reference example, adding ethylene glycol, 1, 4 - 2,5g of a mixture of butanediol (made by Taiwan Plastics Co., Ltd.) and decyl alcohol 1 lan. 5, heated at 150 C/JHL for 丨 hours, and after cooling, a high-performance superabsorbent resin is obtained. The force is 31.9g/g, the water absorption ratio is 28.7g/g under the pressure of 20g/cm2, and the water absorption ratio is 々9#々 under the pressure of pressure, and the coffee value is 8 minutes. Example 2: Repeating the first example, but The heat treatment was carried out at a temperature of 180 ° C for 1 〇 minutes, and the rest of the same example was obtained as a high-performance superabsorbent resin. The retention was determined to be 32 7 g/g, and the water absorption ratio under pressure of 2 〇g/cm 2 was 28.1 g/g, 49 g. The water absorption ratio under pressure of /cm2 was 18 5 g/g, and the ARI value was 9.5 minutes. φ Example 3: Example 1 was repeated, but 1,4-butanediamine (manufactured by Fhka, trade name: 32790) was used. Generation i, 4 · butanediol 'the rest of the same example 1 to obtain a high performance super absorbent resin. The measured retention force is 32.5g / g '20g / cm 2 under the pressure absorption rate of 28.9g / g, 49g / cm2 under pressure The water absorption ratio was 19.4 g/g, and the ARI value was 8.4 minutes. 17 201200543 Example 4: Example 3 was repeated, but heat treatment was carried out at a temperature of 190 ° C for 10 minutes, and the rest of the same page was used to describe the south water absorption. The resin was measured to have a holding force of 32.1 g/g, a water absorption ratio of 29.4 g/g under a pressure of 20 g/cm, a water absorption ratio of 19.1 g/g under a pressure of 49 g/cm2, and an ARI value of 9.6 minutes. Example 5: Repetitive Example First, the use of 2-amino-1-butanol (manufactured by Fluka, trade name: 7176) instead of 1,4-butanediol, the rest of the same example - a high performance superabsorbent resin. The measured retention is 31.5 g/g, water absorption ratio under pressure of 20 g/cm 2 was 28.2 g/g, water absorption ratio under pressure of 49 g/cm 2 was 18 3 g/g, and ARI value was 15 7 minutes. Example 6: Example 1 was repeated, but 1, 2.······················· Holding force 3Ug / g, water absorption capacity under 2〇g / cm2 pressure of 29.5g / g, water absorption ratio 18 9g / g, ARI value of from 49g / cm2 pressure of 235 minutes. Example 7: Example 1 was repeated except that ethylene glycol carbonate was used instead of ethylene glycol, and the rest was the same as the example of a high performance superabsorbent resin. The measured retention force is 32 ground, 20g/cm2
壓力下吸水倍率29.1g/g，49g/em2壓力下吸水倍率19 4g/g，ARI 201200543 值為10.4分鐘。 實施例八： 重覆實施例六，但使用乙二醇碳酸酯替代乙二醇，其餘同實 例六，得高性能高吸水性樹脂。測定得保持力為32 2g/g，2〇g/cm2 壓力下吸水倍率29.4g/g，49g/cm2壓力下吸水倍率19 5g/g，ARI 值為26.7分鐘。 φ 比較例一： 重覆實例一，但乙二醇和曱醇1/0.5混合的水溶液15g，不 添加1，4-丁二醇，其餘同實例一，得高性能高吸水性樹脂。測定得 保持力為32.5g/g，20g/cm2壓力下吸水倍率29 lg/g，49g/cm2壓力 下吸水倍率19.4g/g，ARI值為1.3分鐘。 比較例二： * 重覆比較例一，乙二醇和曱醇1/0.5混合的水溶液2.5g，其 餘同比較例一’得高性能高吸水性樹脂。測定得保持力為32 9g/g， 20g/cm壓力下吸水倍率28.7g/g，49g/cm2壓力下吸水倍率 19.8g/g，ARI 值為 1.6 分鐘。 比較例三： 重覆比較例二’但以乙二醇碳酸酯替代乙二醇，其餘同比較 例二’得高性能高吸水性樹脂。測定得保持力為32.ig/g，2〇g/cm2 19 201200543 壓力下吸水倍率29.4g/g，49g/cm2壓力下吸水倍率19.5g/g，ARI 值為1.1分鐘。 【圖式簡單說明】 【主要元件符號說明】The water absorption ratio under pressure was 29.1 g/g, the water absorption ratio under the pressure of 49 g/cm2 was 19 4 g/g, and the ARI 201200543 value was 10.4 minutes. Example 8: Example 6 was repeated, but ethylene glycol carbonate was used instead of ethylene glycol, and the rest was the same as Example 6, and a high-performance superabsorbent resin was obtained. The retention was determined to be 32 2 g/g, the water absorption ratio at a pressure of 2 〇g/cm 2 was 29.4 g/g, the water absorption ratio at a pressure of 49 g/cm 2 was 19 5 g/g, and the ARI value was 26.7 minutes. φ Comparative Example 1: Example 1 was repeated, except that 15 g of an aqueous solution of ethylene glycol and decyl alcohol 1/0.5 was mixed without adding 1,4-butanediol, and the same as in the first example, a high-performance superabsorbent resin was obtained. The retention was measured to be 32.5 g/g, the water absorption ratio under a pressure of 20 g/cm 2 was 29 lg/g, the water absorption ratio under a pressure of 49 g/cm 2 was 19.4 g/g, and the ARI value was 1.3 minutes. Comparative Example 2: * By repeating Comparative Example 1, 2.5 g of an aqueous solution of ethylene glycol and decyl alcohol 1/0.5 was mixed, which was the same as Comparative Example 1 to obtain a high-performance superabsorbent resin. The retention was determined to be 32 9 g/g, the water absorption ratio at a pressure of 20 g/cm was 28.7 g/g, the water absorption ratio at a pressure of 49 g/cm 2 was 19.8 g/g, and the ARI value was 1.6 minutes. Comparative Example 3: The comparative example 2 was repeated, but the ethylene glycol carbonate was used instead of the ethylene glycol, and the other was compared with the comparative example 2 to obtain a high-performance superabsorbent resin. The retention was determined to be 32. ig/g, 2 〇 g/cm 2 19 201200543 The water absorption capacity under pressure was 29.4 g/g, the water absorption ratio under pressure of 49 g/cm 2 was 19.5 g/g, and the ARI value was 1.1 minutes. [Simple diagram description] [Main component symbol description]
2020