TW200900441A - The processes of high efficient of disperse the wet gel - Google Patents

Abstract

According to the method, the hydrogels are dried at low temperature. The temperature is controlled below 100DEG C. Not only the energy is saved, but also the fine powders are decreased.

Description

6 200900441 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種對水溶液吸收良好的吸水物，此言吸尺 性樹脂廣泛地運用於農業或園藝方面的水保持劑、建華材料中的 、拋莱式的擦巾 抗露珠凝結劑以及移除石油中水份的材料，或是電鐵線中的外肩 防水包覆劑以及衛生用品如尿布、婦女衛生用 等。 上述的高吸水性樹脂因直接與人體接觸，所以高吸水性樹 脂的安全性變得十分重要…般而言，高吸水性樹脂所須具備二 物理性質包括吸收速率、吸收力、壓力Τσ錄料、低單體殘留 量以及吸收後的凝膠力。優㈣高吸极樹脂不僅要滿足^列的 物理性質外，尚需具備良好的安全性，更重要岐必須低汗毕以 及省能源。 【先前技術】 技藝界6知的高吸雜雛的成分材猶，财分解型的两 粉-丙稀腈接枝聚合物（日本專利公開公報昭卿叫a叫 中和之殿粉-丙烯酸接枝聚合物（日本專利公開公報昭51 剛娜⑻，4化乙稀醋酸，烯_共聚物（日本專利公開公 報昭呵叫聊）’水解丙歸腈絲物或⑽軸共 本專利公報昭53(測及部份中和聚_酸（ 利公開公告昭___。其_接枝聚合 物’因為含有天然的高分子—殿粉，會弓i起腐爛性的分解，所以 7 200900441 *法長_的保存；再者，其製造方法又十分複雜，所以現今高 吸水性柯脂之製備均以使用丙烯酸及丙烯酸鹽進行交聯聚合所 製付之而吸水性樹脂佔最大部份也最為經濟，其原因為丙烯酸鹽 共聚物原料—丙烯酸可迅速由商場上購得，且製得的高吸水性樹 月曰具有南的吸水能力，及具有製造成本低廉且最具經濟效益以及 不5 ?丨起_性的分解，故成為最普遍化的高吸水性樹脂。 水合丙烯酸及丙烯酸鹽形成高吸水性樹脂的方法可由數種 已头的方去y得，如水溶液聚合反應、逆相懸浮液聚合反應、乳 化小σ反駐料體喷駐塗覆於纖絲質上進行聚合反應等方 法。在這轉法t，逆蝴浮妓合反細及乳錄合反應必須 使用j有機岭劑’但右無法有效的控制聚合反應時的溫度，有機 溶劑將造成反麟、統之溫度以及壓力的增加，會產线火現象甚 至β引發_，躺射到操作現場人㈣安全以及造成環境污染 問題，其成品也有有機溶劑殘留的疑慮。 製造高吸水性樹脂無論是以水溶液聚合反應、逆相懸浮液 聚合反應、·聚合反麵將單體儒或鍵於纖質上進行 聚合反鱗方法，最終都必_過乾燥這個細，而—般都是利 用卿rc高溫鍋方式需要蝴能源，而京 零零五年二月十六日正式生效，能源價格的域是必離 果，因此近年來要求降低能源的消耗已成為重要之-種趨勢Γ 200900441 至今仍有許多科學家一直為節省能源、提高高吸水性樹脂物 生而努力，技勢界已有許多方法被開發出來，如：將％重量％ 以上的高濃度丙稀酸鹽水溶液進行聚合，一舉得到吸水性樹醋的 乾燥固體方法（日本特昭開紙⑽7、日本特昭開洲犯）； 將3〇重務以上的稱_水溶錢行聚合，—舉得到吸水性 樹酉旨的乾燥固體方法（美國專利侧5】8);不使用交聯劑，在 ⑽〜16G°C溫度聚合，所得之其乾燥_的水分含量很少（日本 特開平55-58208);將45〜80重量％的中和率㈣莫耳％的單 體進行水溶液聚合，得到基本乾燥態吸水性樹醋的方法（曰本特 開平1.22)。但是，這些方法都存在著可溶份較高的缺點。 另有將單體溶液直接注入熱爐加熱（日本特開昭 55、147512、特開昭糾侧9、特開昭63個〇7、特開昭 1275608)或加熱迴轉筒（日本特開平卜165⑽）上，一舉得 的統物’但是，這些方法也都存在著可溶份較高 的缺點。 + •另外’利用單體的中和熱升溫後的單體水溶液在氣相中進行 =聚合（日私销平純_)，在3秒左絲合就已完成， 乂方法存在者聚合難以控制的缺點。 ]用低’里進仃^熱聚合的方法（日本特開平9-67404、美國 6187828)，由於不進行除熱，存在著單體水溶液的濃度不能 200900441 込门π遠日守間文長專缺點，而高溫洪乾的方式普遍都存在著細 粉生成量較高的缺點。 ' 【發明内容】6 200900441 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a water absorbing material which absorbs well in an aqueous solution, and the term absorbing resin is widely used in agricultural or horticultural water retaining agents and Jianhua materials. , Lai-style wipes anti-dew beads coagulant and materials to remove moisture in petroleum, or outer shoulder waterproof coating agent in electric iron wire and sanitary products such as diapers, women's hygiene and so on. Since the above superabsorbent resin is in direct contact with the human body, the safety of the superabsorbent resin becomes very important. Generally, the superabsorbent resin is required to have two physical properties including absorption rate, absorption force, and pressure Τ , low monomer residual amount and gel strength after absorption. Excellent (4) high-impact resin not only needs to meet the physical properties of the column, but also needs to have good safety. More importantly, it must be low-sweating and energy-saving. [Prior Art] The material of the high-absorbent chicks known in the art world is a two-powder-acrylonitrile graft polymer of the financial decomposition type (Japanese Patent Publication No. ZHAO Qing called a Zhonghe Temple Powder - Acrylic Branch polymer (Japanese Patent Laid-Open Publication No. 51, Ganga (8), 4-diethylacetic acid, olefin-copolymer (Japanese Patent Laid-Open) (hydrolyzed acrylonitrile or (10) axis, common patent publication 53 (Measured and partially neutralized poly-acid (Lin public announcement ___. Its _ grafted polymer' because it contains natural polymer - temple powder, will bow down the decomposition of decay, so 7 200900441 * French long _ preservation; in addition, the manufacturing method is very complicated, so the preparation of high-absorbent grease is now made by cross-linking polymerization using acrylic acid and acrylate, and the most water-absorbing resin is also the most economical. The reason for this is that the acrylic copolymer raw material-acrylic acid can be quickly purchased from the market, and the obtained highly water-absorbent tree sap has the south's water absorption capacity, and has the advantages of low manufacturing cost and most economical efficiency. _ Sexual decomposition, it becomes the most common The ubiquitous superabsorbent resin. The method of forming hydrated acrylic acid and acrylate to form a superabsorbent resin can be obtained by several kinds of methods, such as aqueous solution polymerization, reverse phase suspension polymerization, emulsified small σ anti-retaining body. Spraying on the filaments for polymerization, etc. In this method t, the anti-floating and anti-freshing and milk-receiving reactions must use the j-organic agent, but the right can not effectively control the polymerization reaction. Temperature, organic solvent will cause anti-colon, temperature and pressure increase, will produce line fire phenomenon or even β induced _, lying to the operating site (4) safety and environmental pollution problems, the finished product also has the doubt of organic solvent residue. The method for producing superabsorbent resin is to carry out the polymerization of the aqueous solution, the reverse phase suspension polymerization, the polymerization of the reverse side, and the polymerization of the monomeric ruthenium or the bond on the fiber, and finally the method of drying the fine, and - Generally, the use of the rc hot pot method requires the energy source, and Beijing officially took effect on February 16th, 2005. The energy price field is a must-have, so in recent years, it is required to reduce energy. Consumption has become an important trend - 200900441 There are still many scientists who have been working hard to save energy and improve the properties of superabsorbent resins. There have been many methods developed in the technical world, such as: high %% or more The concentration of the aqueous solution of the acrylic acid is polymerized, and the dry solid method of the water-absorbing tree vinegar is obtained in one step (Japan Special Show Paper (10) 7, Japan's Special Zhao Kaizhou); the 3 〇 heavy duty or more _ water-soluble money is polymerized, A dry solid method for obtaining a water-absorbing tree (U.S. Patent No. 5) 8); polymerization at a temperature of (10) to 16 G ° C without using a crosslinking agent, and the obtained moisture content of the drying_ is small (Japanese Patent Laid-Open No. 55) -58208); 45 to 80% by weight of a neutralization rate (tetra) mol% of a monomer is subjected to aqueous solution polymerization to obtain a substantially dry state water-absorbing vinegar (曰本特开平1.22). However, these methods all have the disadvantage of having a higher soluble fraction. In addition, the monomer solution is directly injected into a hot furnace to be heated (Japanese Patent Laid-Open No. 55, 147512, Special Kaizhao Correction Side 9, Special Kaizhao 63 〇7, Special Open No. 1275608) or a heated rotary cylinder (Japanese Special Kaiping 165 (10) ), on the one hand, but the above methods also have the disadvantage of higher soluble content. + • In addition, the monomer aqueous solution after the neutralization heat of the monomer is used in the gas phase = polymerization (daily flat _), the left-handed wire is completed in 3 seconds, and the polymerization method is difficult to control. Shortcomings. ] The method of low-input 仃^ thermal polymerization (Japanese Unexamined 9-67404, US 6187828), because there is no heat removal, there is a concentration of monomer aqueous solution can not be 200900441 込 π far-day defensive Wenlong special defects However, the method of high-temperature flooding generally has the disadvantage of a high amount of fine powder. 'Content of the invention】

製造本發明之高吸水性樹脂所需的水溶性不飽和單體，除了 丙稀酸外’尚可使料它具縣_不飽和雙鍵的水溶性翠 月且如‘甲基丙埽酸、馬林酸、富馬酸、2_丙烯胺·2_甲基丙貌石普酸、 順丁烯二酸、順獨二酸酐、反谓二酸、反丁烯二酸酐等。單 _用不特定限制只可使用—種，亦可合併多種單體—齊使用， 亦可視情況需要添加具有不飽和魏其他親水性的單體，如:丙稀 酿胺、曱基丙_胺、丙_2德“、f基丙職2·絲乙 酉旨、丙烯酸曱i旨、丙烯酸乙醋、二甲胺丙歸丙_胺、氯化丙稀 丙稀贿基三曱_添加量料破壞高吸雜細旨之物性為原 本4¾明在進仃自由絲合反鱗，單體水溶液濃度並沒有特 別的限制，但紐濃度__量叫b2Gwt%U5wt%間， 適當濃度為勤t%至偏％之間，濃度在重量百分比偏％以下 時’聚合後水轉太軟且有黏性不顺械加卫，添加濃度在重量 百分比55wt%以上，接近飽和濃度，不易調配且反應太快反應熱 不易控制’不餘和單體水溶液pH值不低於5 5，若pH低於Μ 時，聚合後水娜體峨存賴含量辦，導致高吸水性樹脂之 物性不佳。 9 200900441 含酸基單體之賴基，應該部份作以㈣成品之阳值^ 其呈中性或微酸性。中和劑為週期表中驗金族或驗土麵氣氧化 物或是碳酸化合物，如：氫氧化鈉、氫氧化卸、碳酸鈉、唆酸:、 碳酸氫鈉、碳酸驗錢類化合物；中和劑可單獨使用—種或多 種混合使用。含酸基單體之羧酸基部份中和成納鹽或卸鹽或録 鹽’中和濃度莫耳百分比為45md%至85md%，宜為如峨至 75mol%。中和濃度莫耳百分比為4編％以下時成品之阳值會 偏低，中和濃度莫耳百分比為85m〇1%以上時成品之阳值會偏 高，成品pH值非呈中性或微酸性時，若不慎與人_觸時柄 太安全。 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 分子以降域本。轉水雜高分子如：部鮮域完全急化的 聚乙烯醇、聚乙二醇、聚丙烯酸、聚丙_胺、·或殿粉衍生 物如甲基纖維素’㈣酸曱基纖《，乙基_素等聚合物；此 等水溶性㊅分子的分子量並補舰定，其中較佳的水溶性高分 子為H部份4化或完全4化的聚乙騎討單獨或混合使 用问及水f生树脂含此等添加水溶性高分子的適當重量百分比為 0至20wt/〇 ’但以〇至胸％較佳，〇至5加％尤佳，添加超過 20wt%時會影響物性，使物性變差。 在進行自由基聚合反應前應先添加自由基聚合反應交聯劑 於未反應早體溶財’此自由基聚合反應交·可選用具有兩個 200900441 或兩個以上不飽和雙鍵的化合物，如:丙烯基)胺、n，n、 次甲基雙丙烯醯胺、Ν,Ν，-次曱基雙曱基丙烯醯胺、丙烯酸丙烯 酯、乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、乙二醇二甲基丙 稀IS曰、聚乙二醇二曱基丙稀酸醋、甘油三丙稀酸酯、甘油三曱 基丙烯酸酯、甘油附加環氧乙烷之三丙烯酸酯或三曱基丙烯酸 酯、三甲醇丙烷附加環氧乙烷之三丙烯酸酯或三甲基丙烯酸酯、 三甲醇丙烧三曱基丙烯酸酯、三甲醇丙烷三丙烯酸酯、n，n，n_: (2-丙烯基)胺、二丙烯酸乙二醇酯、三丙烯酸聚氧乙烯甘油酯、 二丙烯酸二乙基聚氧乙烯甘油酯、二丙烯三甘醇酯等，亦可選用 具有兩個或兩個以上環氧基的化合物’如山梨醇聚縮水甘油醚、 聚丙二醇聚縮水甘油醚、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、雙丙三醇聚縮水甘油醚等。在 進行自由基反應後就可使高吸水性樹脂具有適當交聯度，而使高 吸水性樹脂膠體有適當的加工性。自由基聚合反應交聯劑可單獨 使用或兩種以上混合使用。自由基聚合反應交聯劑適當的添加劑 量在重量百分比0.001〜〖〇/((至5wt%之間（以反應物總固形份為基 準），更適當的用量重量百分比在〇.〇lwt%至3wt%之間，添加劑 量在重量百分比O.OOlwt%以下聚合後水合體太軟且有黏性不利 機械加工’添加劑量在重量百分比5wt%以上吸水性太低，降低 樹脂性能。 聚合反應由自由基聚合反應起始劑的分解產生自由基開 200900441 始。自由基起㈣可熱分解麵始劑，適合雌分解型起始 劑有過氧化物，如：過氧化氫、二_第三丁基過氧化物、過氧化醉 胺或過硫酸鹽(銨鹽、驗金屬鹽)等，及偶氮化合物如：22,_偶氣 基雙(2_脉基丙烧)二鹽酸鹽、2.2\偶氮基雙_-二伸甲基里丁⑹ 二鹽酸鹽；亦可使用還原劑，使成為氧化還原型起始劑"V如：酸 性亞硫酸鹽、疏代硫酸鹽、抗壞血酸或亞鐵鹽；或將氧化還原型 起始劑和熱縛麵始·併使用，首先氧化還縣始劑先進行 反應產生自祕，當自由⑽移至單體上即引發聚合反應的進The water-soluble unsaturated monomer required for producing the super absorbent resin of the present invention, in addition to acrylic acid, can also be made to have a water-soluble chlorophene of a county-unsaturated double bond, such as 'methylpropionic acid, Marinic acid, fumaric acid, 2-propenylamine, 2-methacrylic acid, maleic acid, cis-dicarboxylic acid, anti-dicarboxylic acid, fumaric anhydride, and the like. Single _ can be used only with a specific restriction, or a combination of a plurality of monomers - if necessary, other monomers having unsaturated Wei, such as acrylamide , 乙_2德", f-based propyl 2, silk 酉 酉 、, acrylic acid 曱 i purpose, acrylic acid vinegar, dimethylamine propyl propyl amine, chlorinated propylene sulphur base 曱 _ add material destruction The physical properties of the high-absorbing and fine-grained design are the original 43⁄4 Ming in the free silk and anti-scale, the concentration of the aqueous monomer solution is not particularly limited, but the concentration of the new concentration __ is called b2Gwt% U5wt%, the appropriate concentration is diligent t% to Between the partial %, when the concentration is below the weight percentage, the water turns too soft and the viscosity is not mechanically added after the polymerization. The added concentration is above 55 wt% by weight, close to the saturated concentration, and it is difficult to mix and react too fast. The heat is not easy to control 'not enough and the pH value of the monomer aqueous solution is not lower than 5 5 . If the pH is lower than Μ, the water content of the water after the polymerization is low, and the physical properties of the super absorbent resin are not good. 9 200900441 Acidic The base of the monomer should be partially used as (4) the positive value of the finished product ^ which is neutral or slightly acidic The neutralizing agent is a gold tester or a soil oxide or a carbonic acid compound in the periodic table, such as sodium hydroxide, hydroxide dehydration, sodium carbonate, citric acid: sodium hydrogencarbonate or carbonic acid test compound; The neutralizing agent may be used alone or in combination of two or more. The carboxylic acid group of the acid group-containing monomer is neutralized to form a sodium salt or a salt or salt, and the concentration of the neutralizing concentration is 45 md% to 85 md%, preferably For example, if the percentage of molar concentration is below 4%, the positive value of the finished product will be low. When the percentage of neutral concentration is 85m〇1% or more, the positive value of the finished product will be higher, and the finished product pH will be higher. When the value is not neutral or slightly acidic, if it is inadvertently safe with the human _ handle, the water-soluble polymer may be added to the aqueous monomer solution to reduce the domain before the radical polymerization. For example, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, or powder derivatives such as methylcellulose '(tetra) sulphate-based fiber, ethyl ketone, etc. The molecular weight of these water-soluble six molecules is supplemented by the ship, of which the preferred water-soluble polymer is H A suitable weight ratio of the water-soluble polymer to be added to the water-soluble polymer is 0 to 20 wt / 〇 ', but preferably from 〇 to chest %, It is especially preferable to add 5% to 5%, and when it is added more than 20% by weight, the physical properties are affected, and the physical properties are deteriorated. Before the radical polymerization reaction, a radical polymerization crosslinking agent should be added to the unreacted early body. Polymerization reaction. Optional compounds with two 200900441 or more than two unsaturated double bonds, such as: acryl) amine, n, n, methine bis acrylamide, hydrazine, hydrazine, - fluorenyl hydrazine Acrylamide, propylene acrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethyl propylene IS oxime, polyethylene glycol dimercapto acrylate vinegar, triglyceride Dilute ester, glyceryl tridecyl acrylate, glycerin plus ethylene oxide triacrylate or tridecyl acrylate, trimethylol propane plus ethylene oxide triacrylate or trimethacrylate, trimethyl methacrylate Burning tridecyl acrylate, trimethylolpropane triacrylate, n, n, N_: (2-propenyl)amine, ethylene glycol diacrylate, polyoxyethylene glyceryl triacrylate, diethyl polyoxyethylene glyceryl diacrylate, dipropylene triethylene glycol ester, etc., or two Or a compound of two or more epoxy groups such as sorbitol polyglycidyl ether, polypropylene glycol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , propylene glycol polyglycidyl ether and the like. 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. The amount of the appropriate amount of the radical polymerization crosslinking agent is 0.001 to 〇 / ((to 5 wt% (based on the total solids of the reactants), more appropriate amount by weight in 〇.〇lwt% to Between 3wt%, the amount of the additive is less than 0.001% by weight, and the hydrate is too soft and viscous after polymerization. Unfavorable mechanical processing 'The amount of the additive is less than 5 wt% by weight. The water absorption is too low, and the resin property is lowered. The polymerization reaction is free. The decomposition of the base polymerization initiator produces free radicals starting at 200900441. The radicals are (4) thermally decomposable surface initiators, suitable for female decomposition initiators with peroxides, such as: hydrogen peroxide, di-t-butyl Peroxide, peroxidic amine or persulfate (ammonium salt, metal salt), and azo compounds such as: 22, _ gas-based bis (2-cyanopropan) dihydrochloride, 2.2\ Azobis-bis-methyldibutyl(6) dihydrochloride; a reducing agent can also be used to make a redox-type initiator "V-acid sulfite, sulfite, ascorbic acid or sub- Iron salt; or use of a redox-type initiator and a heat-binding surface, First, the oxidation of the county first agent is first reacted to produce self-mystery. When the free (10) is moved to the monomer, the polymerization reaction is initiated.

行，由於聚合反應進行時會觀出大制熱量而使溫度升高，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_分解’而使整個聚合反應更臻於完全。—般自由基聚 合反應賴繼當用量為重量百分比為_lwt%至胸％(以中 和丙烯酸鹽重量為基準）’更適當用制在…㈣至5wt%之間， 使用重量百分比_lwt%以下日夺，反應太慢不利經濟效益，使用 重置百分比lOwt0/。以上時，反應太快反應熱不易控制。 尚吸水性樹脂為不溶解之親水性聚合體，樹軸部具有均句 ) 生的术u冓痛又為了改善品質如:提高吸收速率、提高膠體強 度、提南抗結塊性、液體滲透性等，都會在樹脂的表面再作進一 步架橋。此表面交聯處理即利用具有能與酸基反應之多官能基交 如；=|丨在此之兩已有許多專利提出；如分散高吸水性樹脂與交聯 劑於有機溶劑中進行表面交聯處理（JP-A-56-131608、 12 200900441 JP-A_57_44627、JP_A_58_426〇2、Jp_A58_U7222)，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、 醚化&物（JP-A-2-153903)等；這些表面處理的方法雖能提高吸 收速率提高壓力下吸水倍率，但將造成保持力下降過多的不良後 果’降低實際應用之性能。 根據本發明於表面處理時能同時進行反應的交聯劑可為多 兀醇如：丙三醇、乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙 ®子1，4 丁二醇、三脛基曱基丙烷、山梨醇等；或可使用多元 胺如：f G—fe、一乙二、三乙二胺、聚乙二胺；或可使用具有 __個以上環氧基的化合物如··山雜雜水甘細、聚丙 〇 細水甘油醚、乙二醇二縮水甘油醚、二乙二醇二縮水甘油 ^ ' Jr? 7 - I- 醇二縮水甘油醚、雙丙三醇聚縮水甘油醚等；亦可使 用^酸亞烴酯如：乙二醇碳酸酯、4-甲基-1,3-二氧雜環戊烷-2-酮、 4 5-.— ® ’一基-1，3-二氧雜環戊烷_2_酮、4,4-二甲基-i，3-二氧雜環戍烷 酉同、4 ,泣Ί 二氧雜環戊烷！酮、1,3-二氧雜環己烷-2-酮、 4,6-二甲 | 。 A—氧雜環己烧_2-顚)或1,3-二氧雜環庚烧-2-酮等。 彳的用法可單獨使用或兩種以上混合使用。交聯劑的適當添 力口齊丨| _ 田 巧里在重量百分比O.OOlwt%至i〇wt%之間（以反應物總固形份 200900441 為基準），更適當的用量在0.005wt%至5wt%之間，交聯劑添加劑 量在重量百分比O.OOlwt%以下時無法顯出效果，交聯劑添加劑量 在重量百分比l〇wt%以上時’吸水性太低，降低樹脂性能。 聚合反應可於傳統批次反應容器中，或於輪送帶式反應器上 進行反應，反應所得之高吸水性樹脂，先利用絞碎機切成體積 10cm3以下小凝膠體，再進行筛選。 篩選固定粒徑之凝膠體直徑以2.00 cm以下為宜，以〇 〇5 cm 至1.50 cm間較佳，粒徑大於2.00 cm之凝膠體則重新送回絞碎機 進行再次切碎。粒徑〇.〇5Cm以下之凝膠體進行烘乾、粉碎處理 後，易產生成品細粉量提高，粒徑2.〇〇Cm以上之凝膠體進行烘 乾時’容易因為熱料效果不佳，致成品在赫單體偏高，其 他物性表現不佳之缺點。丙烯酸鹽凝膠體的顆粒大小分佈越集 中’不僅可使凝賴在祕後雛表現翻最錄態，而且有利 於控制烘乾的時間及溫度。 本發明所採行之低溫烘乾溫度以50°C至100。(3進行烘乾為 且’供乾溫度50⑽下烘乾時間會太久，不具鑛效益。供乾溫 度1〇〇C以上，將增加能源的消耗，除以低溫供乾外，可以搭配 不高於30%相對濕度低濕度的風，用以節省烘乾時間。 乾秌後進行粉碎、筛選固定粒徑，再進行表面交聯劑塗覆處 里表面又恥釗塗覆處理時，表面交聯劑之添加方式則依據表面 200900441 溶液添 1 懷二，直接添加，或調成表面交聯劑水 性有機二表::=:^ 沒有特殊限制，可形成溶液即可，料；甲西_、甲麵、乙_ 利6_65號)。表面交聯劑添加日 I㈣义佳(吳國專 蹄於太 # 卞同吸水树脂中可添加惰性無機In the line, when the polymerization reaction is carried out, the large amount of heat is observed to increase the temperature. When the temperature reaches the decomposition temperature of the thermal decomposition type initiator, the second stage thermal decomposition type initial decomposition is caused to cause the whole The polymerization is more complete. - The free radical polymerization reaction is used in a weight percentage of _1wt% to chest% (based on the weight of the neutralized acrylate). It is more suitably used between (4) and 5% by weight, using weight percentage _lwt% The following days, the reaction is too slow and unfavorable economic benefits, using the reset percentage lOwt0 /. Above, the reaction is too fast and the heat of reaction is not easy to control. The water-absorbent resin is an insoluble hydrophilic polymer, and the root of the tree has a uniformity. It is also used to improve the quality, such as: increasing the absorption rate, increasing the strength of the colloid, increasing the anti-caking property of the south, and the liquid permeability. Etc., the bridge will be further bridged on the surface of the resin. The surface cross-linking treatment utilizes a polyfunctional group capable of reacting with an acid group; =|丨 has been proposed in many of the two patents; for example, dispersing a superabsorbent resin and a cross-linking agent in an organic solvent for surface cross-linking Joint treatment (JP-A-56-131608, 12 200900441 JP-A_57_44627, JP_A_58_426〇2, Jp_A58_U7222), directly mixing the crosslinking agent and the crosslinking agent solution into the superabsorbent resin using inorganic powder (JP-A60-163956, JP-A-60-255814), after adding a crosslinking agent, steam treatment (JP-A_1-113406) 'surface treatment using an organic solvent, water and polyol (JP-A-1_292004, US Patent No. 6346569)' Organic solution, water, etherification & (JP-A-2-153903), etc.; these surface treatment methods can increase the absorption rate and increase the water absorption rate under pressure, but will cause the adverse effect of excessive retention reduction. Application performance. The crosslinking agent capable of simultaneously performing the reaction in the surface treatment according to the present invention may be a polyterpene alcohol such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, or C-property 1, 4 butanediol, tridecylmercaptopropane, sorbitol, etc.; or polyamines such as: f G-fe, monoethylene, triethylenediamine, polyethylenediamine; or more than __ Epoxy-based compounds such as ··············································· , diglycerol polyglycidyl ether, etc.; may also use alkylene esters such as: ethylene glycol carbonate, 4-methyl-1,3-dioxolane-2-one, 4 5- .— ® '-yl-1,3-dioxol-2-one, 4,4-dimethyl-i,3-dioxacyclononane, 4, weeping dioxane Cyclopentane! Ketone, 1,3-dioxan-2-one, 4,6-dimethyl | A-oxocyclohexane-2-顚) or 1,3-dioxepin-2-one. The usage of hydrazine may be used singly or in combination of two or more. Appropriate addition of the cross-linking agent | _ Tian Qiao Li between the weight percentage of O.OOlwt% to i〇wt% (based on the total solids of the reactants 200900441), a more appropriate amount of 0.005wt% to 5wt% Between the amount of the cross-linking agent additive, the effect is not exhibited when the weight percentage is less than 0.001% by weight, and the amount of the cross-linking agent additive is less than the weight percentage of 〇wt%, and the water absorption is too low to lower the resin property. The polymerization reaction can be carried out in a conventional batch reaction vessel or on a round belt reactor, and the superabsorbent resin obtained by the reaction is first cut into a small gel body having a volume of 10 cm 3 or less by a mincer, and then subjected to screening. . The diameter of the gel with a fixed particle size is preferably 2.00 cm or less, preferably between 5 cm and 1.50 cm, and the gel having a particle diameter of more than 2.00 cm is returned to the mincer for re-shearing. After drying and pulverizing the gel with a particle size of 〇.〇5Cm or less, it is easy to produce a fine powder of the finished product. When the gel of the particle size of 2. 〇〇Cm or more is dried, it is easy because the effect of the hot material is not Good, the shortcomings of the finished product in the high monomer, other physical properties are not good. The more concentrated the particle size distribution of the acrylate gel is, the more the condensate can be turned into the most recorded state, and it is beneficial to control the drying time and temperature. The low temperature drying temperature employed in the present invention is from 50 ° C to 100 ° C. (3) Drying and 'drying time 50 (10) will take too long to dry, no mineral benefit. For dry temperature above 1〇〇C, it will increase energy consumption, divided by low temperature for dry, can not match high The wind with 30% relative humidity and low humidity is used to save the drying time. After drying, the pulverization, screening and fixing the particle size, and then the surface of the surface cross-linking agent coating is treated with shame coating, the surface is treated. The addition method of the joint agent is based on the surface of the 200900441 solution, adding 1 or two, directly added, or adjusted to the surface cross-linking agent aqueous organic two table::=:^ No special restrictions, can form a solution, material; Jiaxi _, A Face, B_Li 6_65). Addition of surface cross-linking agent I (4) Yijia (Wu Guozhan Hoof Yutai # 卞 吸水 吸水 吸水 吸水 吸水 惰性 惰性 惰性 惰性

心㈣嶋㈣躺、或二氧 -化紹，或氧化鎂等或其混合物。其中以碳酸紹、二氧 人匕惰性無機鹽粉末的用法可單獨使用或合併兩種以上混 :用。’嶋機鹽粉末添加範圍在重量百分比_減至 t%之間，其中以_wt%至4.0wt%較佳。 進行表面交·塗覆處輯，再㈣至2靴範圍内進行 4處理’使表面交聯舰均勻而且快速的進行交聯反應，並使 内部_愧行交聯反應而達到本發明之效果。熱處理溫度航 =下父聯反應時間太久，不具經濟效益，熱處理溫度2坑以上 樹:易劣化影響品質，熱處理時間以3G分鐘至15〇分鐘為宜， 依照欲獲得_表面處理效賴減理溫度調整，減理溫度高 則熱處理時間短’熱處理溫度低時，職處理溫度時間長。 使用普通的乾燥器或加熱爐即可完成熱處理的步驟，適用於 本發明的熱處縣置有包括：隧道式混合乾制、轉鼓式乾燥 益、臺式乾燥器、流化床乾燥器、氣流式乾燥器以及紅外線乾燥 器等。 15 16 16200900441 表面又％熱處理後，於高吸水細旨中添加水不溶性微粉，進 行抗結塊處理，目的在增加高吸水樹賴粒之__，使高吸 水祕知在吸收减後仍有高流動性。水不溶性齡添加方式為直 接添加，射_έ著劑將水不溶性微_著於高吸水樹脂表面； 水不岭性彳政粉包括硫酸鋁、硫酸鎂、氧化鋁、氧化鎂、氧化辞、 碳_弓、石粦酸趟、碌酸鋇、石夕藻土、軟土、黏土、滑石粉、彿石、 门袅土恥土、活性灰、二氧化矽、二氧化鈦之無機鹽粉末，及 如纖維素粉末、聚酯、聚乙稀、聚氯乙稀、聚苯乙稀之有機粉末。 上述之水不溶性微粉+，以添加無频粉末·果最好。無機鹽 粉末的用法可單獨使用或合併兩種以上混合使用。添加範圍在重 置百分比o.ooiwt%至I〇.〇wt〇/0之間，其中以〇 〇lwt%至4 〇城％較 ^。水不溶性微粉之粒子大小最好不大於mm，更適當的大小 為0.6 mm以下。黏著劑可為多元醇如：丙三醇、聚乙二醇、山 4醇專，或可使用聚乙稀亞胺。黏著劑的用法可單獨使用或合併 兩種以上混合使用。黏著劑的適當添加劑量在重量百分比 O.OOlwt%至l〇wt%之間(以反應物總固形份為基準），更適當的用 量在0.005wt%至5wt%之間’黏著劑添加劑量在重量百分比 0.001 wt%以下時無法使惰性無機鹽粉末完全黏著於高吸水樹脂 表面’黏著劑添加劑量在重量百分比〗〇wt%以上時，吸水性太低， 降低樹脂性能。 200900441 【實施方式】 '本《明之目的在提供-種粉狀、不溶於水，可吸收水液或尿 液及金液’具有高保持力、低殘存未反應單體，且在較高的壓力 下具有較高吸收倍率特性的高性能高吸水性樹脂。其製造方至 少包括： )中矛比率在45至85莫耳%之範圍内，不飽和單體水溶液的 濃度在20至55重量份之範圍； ⑹中和聚合生成之高吸水性獅水導，先經由絞切成大塊Heart (4) 嶋 (4) lie, or dioxin-salt, or magnesium oxide or the like or a mixture thereof. Among them, the use of the carbonated and dioxin inert inorganic salt powder may be used singly or in combination of two or more. The amount of the turmeric salt powder added is in the range of % by weight to minus t%, with _wt% to 4.0% by weight being preferred. The surface cross-coating and coating were carried out, and the treatment was carried out in the range of (4) to 2, and the cross-linking reaction was carried out uniformly and rapidly, and the internal cross-linking reaction was carried out to achieve the effect of the present invention. Heat treatment temperature hang = lower parent reaction time is too long, no economic benefit, heat treatment temperature 2 pits or more trees: easy to deteriorate affect quality, heat treatment time is 3G minutes to 15 〇 minutes, according to the _ surface treatment effect reduction Temperature adjustment, the heat treatment time is short when the temperature is lowered. When the heat treatment temperature is low, the occupation temperature is long. The heat treatment step can be completed by using an ordinary dryer or a heating furnace, and the heat storage county suitable for the present invention includes: tunnel type mixed dry, drum type drying benefit, bench top dryer, fluidized bed dryer, Airflow dryers, infrared dryers, etc. 15 16 16200900441 After the surface has been heat treated, the water-insoluble fine powder is added to the high-absorption water-repellent material for anti-caking treatment. The purpose is to increase the __ of the high-absorbent tree, so that the high water-absorbing secret is still high after absorption reduction. fluidity. The water insoluble age is added directly, the water-insoluble agent is slightly insoluble on the surface of the superabsorbent resin; the water-insoluble bismuth powder includes aluminum sulfate, magnesium sulfate, aluminum oxide, magnesium oxide, oxidation, carbon _ bow, barium strontium sulphate, sulphuric acid sorghum, shixia, soil, soft clay, clay, talcum powder, buddha, shovel soil, active ash, cerium oxide, titanium dioxide inorganic salt powder, and such as fiber Organic powder of powder, polyester, polyethylene, polyvinyl chloride and polystyrene. The above water-insoluble fine powder + is preferably added with a frequency-free powder and fruit. The inorganic salt powder may be used singly or in combination of two or more. The addition range is between the reset percentage o.ooiwt% to I〇.〇wt〇/0, where 〇 wt lwt% to 4 〇%% is ^. The particle size of the water-insoluble fine powder is preferably not more than mm, and a more appropriate size is 0.6 mm or less. The adhesive may be a polyhydric alcohol such as glycerol, polyethylene glycol, or a diol, or a polyethyleneimine may be used. The adhesive may be used singly or in combination of two or more. The appropriate amount of the additive of the adhesive is between 0.001 wt% and 1 wt% (based on the total solids of the reactants), and more suitably between 0.005 wt% and 5 wt%, the amount of the adhesive additive is When the weight percentage is 0.001 wt% or less, the inert inorganic salt powder cannot be completely adhered to the surface of the superabsorbent resin. When the amount of the adhesive additive is more than 重量% by weight, the water absorption is too low, and the resin property is lowered. 200900441 [Embodiment] 'The purpose of this article is to provide - powdery, insoluble in water, absorbable liquid or urine and gold liquid' with high retention, low residual unreacted monomer, and at higher pressure A high-performance superabsorbent resin with high absorption rate characteristics. The manufacturer comprises at least: a medium spear ratio of 45 to 85 mol%, and an unsaturated monomer aqueous solution concentration of 20 to 55 parts by weight; (6) a highly water-absorbing lion water guide formed by neutralization polymerization, First cut into large pieces by twisting

水凝膠塊； A (c) 將大塊錢膠塊以絞碎方絲成小難凝膠體； (d) 以低/J2L度、低濕度的乾燥風乾燥，再進行粉碎及篩選； (e) 表面交聯劑塗覆；及 ⑴溫度9G°C至23Gt加熱表面改質處理。 生產聚丙_純高吸水性樹瞒，會在粉碎、研磨以及筛 選的_中，產生粒徑不大於·阿（網目為丨條灿）的高吸 水性树知’#之為細粉；細粉成量的多寡與高吸水性樹脂表面乾 的速率、方式有極大賴係，當高吸水性樹脂在高溫中快速乾 燥時’高吸水性樹脂在内部越容易因為水分來不及逸出，而在内 部膨漲形成錢，氣泡㈣越多，在粉碎、研磨過程巾的撥壓與 切削’容易使氣泡空洞周圍的高吸水性樹脂破碎、形成細粉，造 成高吸水性樹脂粉塵量的增加；細粉量的多寡對環境以及生物體 200900441 產生—定程度之辟，尤其是空氣巾㈣浮錄經由呼吸道進入 肺部因而對肺部產生刺激，增加肺部與呼吸道病變的機會，而且 2粉讀多時’代表顆粒之大小適合商業化使用的高吸水性樹 脂量減少，回收的細粉量愈多，將減低生產效率並增加成本。 本發明除上述單純觀低溫乾燥的方式外，尚可搭配低濕度 的方式’來增進焕乾效率。此之低濕度係指不高於1〇%相對濕度。 U δ ’切度不高於1Q(rc時，水份形成水蒸氣的效率較差， 仏升7成水蒸氣與水蒸氣形成水份會形成一動態平衡。藉由控制 在'度私走水条氣來破壞動態平衡，使的環境中的水蒸氣比例降 低知θ大大地k升水份形成水蒸氣的效率，使的高吸水性樹脂 的乾燥時間縮短。 為檢視本發明對細粉之影響，可藉由下述方法檢驗。首先將 單體中和，加入觸媒聚合得高吸水性樹脂水凝膠，再以撕裂方式 ί取數塊適备體積之水凝膠塊，經孔徑為13mm的絞碎機（精浩公 司之產品，型號為CH102型）製粒，或以擠壓機（美利德公司之 產品，型號為MRT-SCN-2S型）製粒，而其孔徑為17mm及Smm， 經乾燥機（千銳儀器公司之產品，型號為〇乂7〇型；或美利德公 司之產品，型號為MRT-SCN-2S型）以7〇t、1%相對濕度，或 其他溫度、相對濕度烘乾，後將上述乾燥後之高吸水性樹脂顆粒 粉碎磨，以標準篩網筛出並計算各粒徑的分佈比例，檢測不同烘 乾溫度，所產生氣泡空洞對細粉生成量的影響，並進行比較，以 200900441 觀察其影響。 =發明係利用JIS標準筛網來檢驗細粉的生成量 平般的^驗觸駕_(_爾岭法；輸叫 孤勺師、，，罔置於震動器中，筛網排列順序為網孔 =其震，一，一段時間後停止震動器，二= 分佈高吸水性樹脂，並利用下列方輕式計算出各板㈣Hydrogel block; A (c) The large block of rubber is made into a small hard gel with a broken square wire; (d) dried with a dry air of low/J2L degree and low humidity, and then pulverized and screened; e) surface cross-linking agent coating; and (1) temperature 9G ° C to 23 Gt heating surface modification treatment. Production of polypropylene - pure super absorbent tree stalks, in the smashing, grinding and screening of _, the production of particles with a particle size not greater than · A (mesh is the 丨 灿 灿) high water absorption tree know '# is fine powder; fine The amount of powder and the rate and manner of drying the superabsorbent resin surface are extremely high. When the superabsorbent resin is rapidly dried at high temperature, the more highly absorbent resin is inside, the easier it is because moisture does not escape, but internally. Inflating to form money, the more bubbles (four), the pressure and cutting of the smashing and grinding process are easy to break up the superabsorbent resin around the bubble cavity, forming fine powder, resulting in an increase in the amount of superabsorbent resin dust; fine powder The amount of the amount of the environment and the organism 200900441 produced a certain degree, especially the air towel (four) floating through the respiratory tract into the lungs and thus stimulate the lungs, increase the chance of lung and respiratory lesions, and 2 powder reading for a long time 'The amount of superabsorbent resin representing the size of the granules suitable for commercial use is reduced, and the more the amount of fine powder recovered, the lower the production efficiency and the higher the cost. In addition to the above-mentioned simple method of low-temperature drying, the present invention can be combined with a low-humidity method to improve the resilience efficiency. The low humidity means no more than 1% relative humidity. U δ 'cut is not higher than 1Q (when rc, water is less efficient in forming water vapor, soaring 70% of water vapor and water vapor form a dynamic balance. By controlling the 'private water strip' Gas to destroy the dynamic balance, so that the proportion of water vapor in the environment is reduced, and the efficiency of forming water vapor by k liter of water is greatly increased, and the drying time of the super absorbent resin is shortened. To examine the effect of the present invention on fine powder, It can be tested by the following method. Firstly, the monomer is neutralized, and the catalyst is polymerized to obtain a superabsorbent resin hydrogel, and then a plurality of hydrogel blocks of suitable volume are obtained by tearing, and the pore diameter is 13 mm. Granulator (fine product, model CH102) granulated, or granulated with an extruder (Melly's product, model MRT-SCN-2S) with a pore size of 17mm and Smm, dried dryer (product of Qianrui Instrument Co., model 〇乂7〇; or Meridian company, model MRT-SCN-2S) with 7〇t, 1% relative humidity, or other Drying at a temperature and a relative humidity, and then pulverizing the above-mentioned dried superabsorbent resin particles, The standard sieve screens out and calculates the distribution ratio of each particle size, detects the different drying temperatures, and the effect of the bubble voids on the amount of fine powder produced, and compares them to observe the impact of 200900441. = The invention uses JIS standard sieve To test the amount of fine powder produced by the flat tester _ (_ er Ling method; lose the so-called spoon teacher,, 罔 placed in the vibrator, the screen order is mesh = its shock, one, a section Stop the vibrator after the time, 2 = distribute the super absorbent resin, and calculate the plates by the following methods (4)

粒徑分佈比率(％) = 旨重量 所有篩網内高吸水性*100% 一本發縣便於使㈣選性能的，係將高吸雜樹脂中， 粒到、於1〇6聰(邶鮮_為14Gmesh)視為細粉，_其所占 比率的增減來判斷乾燥溫度對細粉的影響。Particle size distribution ratio (%) = Weight of all screens High water absorption *100% A county is easy to make (4) Select the performance, the system will be high-absorbing resin, grain to, in 1〇6 Cong _ is 14Gmesh) as a fine powder, _ its proportion of increase or decrease to determine the effect of drying temperature on fine powder.

為彰顯本發明之高吸水性樹脂的壓力下吸水倍率，本發明利 时壓魏_力貞荷·· 2Gg/em2及49g/em2)_定。錢吸收 量係根據歐尋獅A號綱#第七頁_純的方法測 定；將初始重量的高吸水性樹脂放在依據有筛網底部的圓柱體 中’對粉體加以2〇g/cm2及49g/cm2的勤，接著將此圓柱體置 於吸收性需求測試壯’讓此高吸水性樹脂吸㈣9%的氯化納水 溶液-小時，再制吸水重量將所得數值除以高吸水性樹脂的重 罝’即得受屋吸收重數值。 19 20 200900441 本發明之保持力（CRC)係利用茶袋試驗 法測定，並以五次 1測結果，去除最高值以及最低值後，取平均值；將的高吸 水性樹脂裝在茶袋裡，並浸泡於0.9%的NaCl水溶液20分鐘，然 後將此次泡後的茶袋置於離心機中離心(直徑23cm、轉速14〇〇rpm) 二分鐘後科重。所得之數值先減去未充填高吸水性樹脂的空白組 命袋重(以相同步驟操作)再除以聚合物重即得保持力數值。 【實施例】 f - '實施例一： 1) 取48%氫氧化鈉水溶液802g及1〇69 2g的水置入於4〇〇〇c c圓 錐瓶中’緩慢加入330g丙烯酸並保持瓶内中和反應系統的溫度 在40°C以下，中和後之水溶性不飽和單體pH值為12.6。靜置 5分鐘後’再將660g丙烯酸加入部份中和完成的水溶性不飽和 單體中，其完全中和後之水溶性不飽和單體{)^1值為5 6，此時 I 得水溶性不飽和單體濃度42wt%水溶液，其中7〇mol%(莫耳比) 丙烯酸部份中和為丙烯酸鈉。 2) 再加入1.518 g的Ν,Ν，-次T基雙丙烯醯胺於水溶性不飽和單體 溶液，並維持溫度於2(TC左右。 3) 加入〇.528g雙氧水，6.62 g亞硫酸氫鈉及6·62 g過硫酸銨以起 始反應。 4) 利用切式粉碎機將反應後生成的凝膠體切碎，並篩選出粒徑直 20 200900441 、 21 徑大小為0.5〜2〇mm的凝膠體。 5) 以溫度7叱、相對濕度之風絲μ小時。 6) 經研磨後，利用JIS標準筛網，（網目為U0粒徑為10_)， 震動器震糊為1Q分鐘_選，其細粉量所佔之比例及保持力 (CRC) 2〇g/cm墨力下吸水倍率㈣A?) 壓 倍雜MAP)之爾結取崎―咐。 實施例二： e ' 1) 重覆實施例一步驟 ~ W ’但切碎後的凝膠體，改以7〇t、 28%相對濕度之風乾燥2.5小時。 2) 重覆實施例一步驟6)。 實施例三 υ重覆實施例—步驟㈣，但切碎後的凝膠體，改以啊、 1%相對濕度之風乾燥ι.5小時。 / κ ' 2)重覆實施例一步驟6)。 實施例四 υ重覆實施例-步驟υ〜5)，但切碎後的凝膠體，改以7叱、 28%相對濕度之風乾燥丨.$小時。 2)重覆實施例一步驟6)。 22 22200900441 實施例五 1) 重覆實施例一步驟1)〜5)，但切碎後的凝膠體，改以90°c、 1%相對濕度之風乾燥2.5小時。 2) 重覆實施例一步驟6)。 實施例六 1) 重覆實施例一步驟1)〜5)，但切碎後的凝膠體，改以90°c、 28%相對濕度之風乾燥2.5小時。 2) 重覆實施例一步驟6)。 實施例七 1) 重覆實施例一步驟1)〜5)，但切碎後的凝膠體，改以90°C、 1%相對濕度之風乾燥1.5小時。 2) 重覆實施例一步驟6)。 實施例八 3) 重覆實施例一步驟1)〜5)，但切碎後的凝膠體，改以90°C、 28%相對濕度之風乾燥1.5小時。 4) 重覆實施例一步驟6)。 比較例一： 1)重覆實施例一步驟1)〜5)，但切碎後的凝膠體，改以150°c、 28°/。相對濕度之風乾燥2.5小時。 22 23 200900441 2)重覆實施例一步驟6)。 比較例二： 1) 重覆實施例一步驟1)〜5)，但切碎後的凝膠體，改以150°C、 40%相對濕度之風乾燥2.5小時。 2) 重覆實施例一步驟6)。 表一 CRC 0.3AAP 0.TAAP 細粉量 實施例一 28. 3g/g 27. 5g/g 17. 6g/g 2. 34% 實施例二 29. ls/g 27. 16. 1. 83% 實施例三 27. 26. 15. 9g/g 3. 46% 實施例四 28. lg/ff 27. lg/g 17. 4g/g 3. 25% 實施例五 29. 6g/g 27. 8g/g 17. 2s/g 3. 86% 實施例六 28.6g/g 25. lg/g 17. 8g/g 4. 55°/〇 實施例七 30.2g/g 26. 7g/g 17. 2g/g 3. 42% 實施例八 29.Tg/g 28. 7r/s 18. lg/g 4 52% 比較例一 27. _ 23. 5g/g 14. 15. 25°/〇 比較例二 27. 23. 13. 7^/2 19. 86% 23 24 200900441 【圖式簡單說明】 【主要元件符號說明】 ./ 24In order to demonstrate the water absorption ratio under pressure of the superabsorbent resin of the present invention, the present invention has a pressure of _力_力··2Gg/em2 and 49g/em2). The amount of money absorbed is determined according to the method of pure escaping lion A No. 7 _ pure method; the initial weight of super absorbent resin is placed in a cylinder according to the bottom of the screen '2 〇g/cm 2 of the powder And 49g/cm2 of the diligent, then put the cylinder in the absorption requirement test to make the superabsorbent resin absorb (four) 9% of the sodium chloride aqueous solution - hour, and then make the water absorption weight and divide the obtained value by the super absorbent resin The heavy weight of the house is subject to the weight of the house. 19 20 200900441 The retention force (CRC) of the present invention is determined by the tea bag test method, and after removing the highest value and the lowest value by five times, the average value is taken; the super absorbent resin is placed in the tea bag, and The solution was immersed in a 0.9% NaCl aqueous solution for 20 minutes, and then the bubbled tea bag was centrifuged in a centrifuge (diameter 23 cm, rotation speed 14 rpm) for two minutes. The value obtained is first obtained by subtracting the blank group weight of the unfilled superabsorbent resin (operating in the same step) and dividing by the weight of the polymer to obtain the retention value. [Examples] f - 'Example 1: 1) 48g of 48% sodium hydroxide solution and 1〇69 2g of water were placed in a 4〇〇〇cc conical flask. Slowly add 330g of acrylic acid and keep the bottle neutralized. The temperature of the reaction system was below 40 ° C, and the pH of the water-soluble unsaturated monomer after neutralization was 12.6. After standing for 5 minutes, 660 g of acrylic acid was added to the partially neutralized water-soluble unsaturated monomer, and the water-soluble unsaturated monomer after complete neutralization was 5, 6, which was obtained. The water-soluble unsaturated monomer concentration is a 42 wt% aqueous solution in which 7 mol% (mole ratio) of the acrylic acid is partially neutralized to sodium acrylate. 2) Add 1.518 g of hydrazine, hydrazine, -T-based bis acrylamide to the water-soluble unsaturated monomer solution, and maintain the temperature at 2 (TC or so. 3) Add 528.528g hydrogen peroxide, 6.62 g hydrogen sulfite Sodium and 6.62 g of ammonium persulfate were used to initiate the reaction. 4) The gel formed after the reaction was chopped by a cutter mill, and a gel having a particle diameter of 20 200900441 and a diameter of 0.5 to 2 mm was selected. 5) Winds with a temperature of 7 叱 and relative humidity for μ hours. 6) After grinding, use JIS standard sieve, (the mesh size is U0 particle size is 10_), the vibrator is 2Q minutes, the proportion of fine powder and the retention capacity (CRC) 2〇g/ The suction capacity under cm ink force (4) A?) The pressure is mixed with MAP). Example 2: e ' 1) Repeat the procedure of Example 1 ~ W ' but the chopped gel was dried by air at 7 〇t, 28% relative humidity for 2.5 hours. 2) Repeat step 1) of Example 1. Example 3 υ Repeated Example - Step (4), but the chopped gel was dried by air at 1% relative humidity for 5 hours. / κ ' 2) Repeat step 1) of Example 1. Example 4 υRepeat Example - Step υ~5), but the chopped gel was dried in a wind of 7 叱, 28% relative humidity for $. 2) Repeat step 6) of Example 1. 22 22200900441 Example 5 1) The steps 1) to 5) of Example 1 were repeated, but the chopped gel was dried by air at 90 ° C and 1% relative humidity for 2.5 hours. 2) Repeat step 1) of Example 1. Example 6 1) The steps 1) to 5) of Example 1 were repeated, but the chopped gel was dried by air at 90 ° C and 28% relative humidity for 2.5 hours. 2) Repeat step 1) of Example 1. Example 7 1) The steps 1) to 5) of Example 1 were repeated, but the chopped gel was dried by air at 90 ° C and 1% relative humidity for 1.5 hours. 2) Repeat step 1) of Example 1. Example 8 3) The steps 1) to 5) of Example 1 were repeated, but the chopped gel was dried by air at 90 ° C and 28% relative humidity for 1.5 hours. 4) Repeat step 1) of Example 1. Comparative Example 1: 1) Repeat steps 1) to 5) of Example 1, but the chopped gel was changed to 150 ° C, 28 ° /. The air of relative humidity was dried for 2.5 hours. 22 23 200900441 2) Repeat step 6) of Example 1. Comparative Example 2: 1) The steps 1) to 5) of Example 1 were repeated, but the chopped gel was dried by air at 150 ° C and 40% relative humidity for 2.5 hours. 2) Repeat step 1) of Example 1. Table 1 CRC 0.3AAP 0. TAAP Fine powder amount Example 1 28. 3g / g 27. 5g / g 17. 6g / g 2. 34% Example 2 29. ls / g 27. 16. 1. 83% implementation Example 3 27. 26. 15. 9g/g 3. 46% Example 4 28. lg/ff 27. lg/g 17. 4g/g 3. 25% Example 5 29. 6g/g 27. 8g/g 17. 2s/g 3. 86% Example 6 28.6g/g 25. lg/g 17. 8g/g 4. 55°/〇 Example 7 30.2g/g 26. 7g/g 17. 2g/g 3 42% Example VIII 29.Tg/g 28. 7r/s 18. lg/g 4 52% Comparative Example 1 27. _ 23. 5g/g 14. 15. 25°/〇 Comparative Example 2 27. 13. 7^/2 19. 86% 23 24 200900441 [Simple description of the diagram] [Explanation of main component symbols] ./ 24

Claims (1)

25 200900441 十、申請專利範圍： 該方法 1. 一種以不飽和單體溶液製備高吸水性樹脂的製造方法 之特徵在於： ' (=和比率在45至85細之範_，稍和.水溶液的 浪度在20至55重量份之範圍； 中孝♦ &生成之尚吸水性樹脂水凝膠，絞碎成體積小於1此出3 以下之小顆粒凝膠體； (c)以低舰度、低濕度的風乾燥，再行粉碎及篩選。 2·:申請專利範圍第丨項所述之高吸水财f脂之製造方法，其低 μ度乾燥風之溫度範圍為7〇。〇至9〇。〇之間者。 一 3.如申請專利範圍第丨項所述之高吸水性樹脂之製造方法，其低 濕度乾燥風之相對濕度範圍為不高於30%RH者。 … 的製造方法，該方法 4. -種以不飽和單體溶液製備高吸水性樹脂 包括：25 200900441 X. Patent application scope: The method 1. A method for producing a super absorbent resin by using an unsaturated monomer solution is characterized by: '(= and the ratio is in the range of 45 to 85 fine, slightly and aqueous. Waves in the range of 20 to 55 parts by weight; Zhongxiao ♦ & generated water-absorbent resin hydrogel, minced into a small particle gel with a volume less than 1 and less than 3; (c) with low ship Drying with low humidity, re-pulverizing and screening. 2: The manufacturing method of the high-absorbency fat fat described in the scope of the patent application, the temperature range of the low-degree dry wind is 7〇. 1. The method for producing a super absorbent resin according to the invention of claim 2, wherein the relative humidity of the low-humidity dry wind is not higher than 30% RH. , the method 4. The preparation of the superabsorbent resin with an unsaturated monomer solution comprises: (a)==45至85糾之細内，鄕單體水溶液的 /辰度在20至55重量份之範圍； 合生狀高脂水凝膠，絞碎成體積小於 10cm以下之小顆粒凝膠體； ⑹以低溫度、脑度，再行粉碎及賢 ⑷再以溫度听至2耽進行表面交聯劑塗覆. ⑷添加水不溶性微粉及黏著劑，進行抗結塊處理。 25 26 26200900441 5.如申請專利範圍第4項所述之高吸水性樹脂之製造方法’其表 面交聯劑為二元以上多元醇或乙二醇二縮水甘油醚或乙二醇碳 酸酯或其混合物。 6·如申請專利範圍第4及5項所述之高吸水性樹脂之製造方法， 其表面交聯劑添加範圍在重量百分比0.005wt%至5.0wt°/〇之間。 7. 如申請專利範圍第4項所述之高吸水性樹脂之製造方法，其水 不溶性微粉可為硫酸鋁、碳酸鈣、氧化鎂、沸石、高嶺土、二 氧化鈦或二氧化矽之無機鹽粉末；水不溶性微粉的用法可單獨 使用或合併兩種以上混合使用，添加範圍在重量百分比 O.Olwt%至 4.0wt%之間。 8. 如申請專利範圍第6項所述之高吸水性樹脂之製造方法，其水 不’谷性彳政粉之粒子大小為不大於〇·6 mm者。 9·如申》月專利範圍第4項所述之高吸水性樹脂之製造方法，其黏 著別可為丙二醇、聚乙二醇、山梁糖醇、聚乙稀亞胺或其衍生 物’黏著劑_法可單獨使贼合併兩種以上混合使用。 10.如申明專利範圍第4及$項所述之高吸水性樹脂之製造方法， 』著』添加範圍在重量百分比G·⑻Swt%至5.〇wt%之間。 26(a) == 45 to 85 to correct the fineness, the monomer / aqueous solution in the range of 20 to 55 parts by weight; confluent high-fat hydrogel, minced into a small particle gel less than 10cm in volume (6) with low temperature, brain degree, re-pulverization and sage (4) and then temperature to 2 耽 for surface crosslinking agent coating. (4) Add water-insoluble micro-powder and adhesive, anti-caking treatment. 25 26 26200900441 5. The method for producing a super absorbent resin according to claim 4, wherein the surface crosslinking agent is a dihydric or higher polyhydric alcohol or ethylene glycol diglycidyl ether or ethylene glycol carbonate or mixture. 6. The method for producing a super absorbent resin according to any of claims 4 and 5, wherein the surface crosslinking agent is added in a range of from 0.005 wt% to 5.0 wt% per hydr. 7. The method for producing a super absorbent resin according to claim 4, wherein the water-insoluble fine powder is an inorganic salt powder of aluminum sulfate, calcium carbonate, magnesium oxide, zeolite, kaolin, titanium dioxide or cerium oxide; The use of the insoluble fine powder may be used singly or in combination of two or more kinds, and the addition is in the range of from 0.01% by weight to 4.0% by weight. 8. The method for producing a super absorbent resin according to claim 6, wherein the particle size of the water is not more than 〇·6 mm. 9. The method for producing a super absorbent resin according to item 4 of the patent application of the Japanese Patent Application, the adhesive of which may be propylene glycol, polyethylene glycol, sorbitol, polyethyleneimine or a derivative thereof The _ method can be used to combine thieves and two or more. 10. The method for producing a super absorbent resin according to claims 4 and 3, wherein the addition range is between a weight percentage of G·(8)Swt% and 5.〇wt%. 26