200900438 九、發明說明： （ 【發明所屬之技術領域】 高吸水性樹脂是廣泛地被運用於農業或園藝方面的水保持 劑、建築材料中的抗露珠凝結劑以及移除石油中水份的材料，戋 作為電纜線中的外層防水包覆劑以及用之於衛生用品如尿布、婦 女衛生用品、抛棄式的擦巾等。 【先前技術】 r 技蟄界已知高吸水性樹脂的成分材料，有遇水分解型的澱 鈿丙烯腈(hydrolyzed starchacrylonitrile)接枝聚合物（日本公開 特許公報昭49(1974M3,395)，中和之殿粉-丙烯酸接枝聚糾 :日本專利公開公報昭51 (1976)_125,468)，皂化乙稀醋酸—丙 _共聚物（日本專利公開公報昭52(1977H4,689)，水解丙烤 腈共聚物或丙烯醯胺共聚物（日本專利公報昭％ (1978M5,959) ’及部份中和聚丙烯酸（曰本專利公開公報昭 1 5509叫84,3〇4)等。其中殿粉-丙烯腈接枝聚合物的原料中， 因為含有天然的高分子—驗，會引起腐難的分解，所以無法 長時間的保存；再者，其製造方法十分_，所以現今高吸水性 樹脂之製備方式以使用丙稀酸及丙稀酸鹽進行交聯聚合所得之 高吸水性氣録大部份也料轉，制、因躺烯輕共聚物 的㈣-_酸可迅速域場上購得，且製得的高吸水性樹脂具 有很回的吸水i力，及具有製造成本低廉以及不會服腐爛性的 分解且最競濟效益，故成為最料化的高吸水性樹脂。 6 7 200900438 聚合丙稀酸及丙稀酸鹽形成高吸水性樹脂的方法可由數種 已知的方法製得，如水溶液聚合反應、逆相懸浮液聚合反應、乳 化聚合反應或將單體喷灑或塗覆於纖維基質上進行聚合反應等方 法。在這些方法中，逆相懸浮液聚合反應以及乳化聚合反應必須 使用到有機溶劑，但是若無法有效的控制聚合反應時的溫度，有 機溶劑將造成反應系統溫度以及壓力的增加，會產生起火現象甚 至引發爆炸，進而威脅到操作現場人員的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。 θ高吸水性樹脂顆粒會因為其高吸濕的特性時，無論在儲存或 ^用於製造衛生用品的過程t，會因為吸收空氣中的水氣而導致 樹脂彼此黏著，因而無法順利的從連續定量的供量設備中進料， 使得製造^來的衛生用品中之高吸水性樹月旨的含量分布不均，因 進ΠΪ吸水叫&吸濕結塊之問題已成為—項新的研究趨勢。 至今財衫科學家-直為減少高吸水性觸的吸渴後合 ::努力，技藝界已有許多降低高吸水性： =::::如:使用具有氨基或環氧基的變性㈣與 積_以上1___33558)，添加比表面 性樹财（日本特 =.I以下之疏水性二氧化石夕於吸水 細外亦有平使用二 /、有至V 12烷基的陽離子型界面活性劑喷 200900438 =水性樹脂表面（日本_ 61德4)進行表面處理後， ㈣溶點的有機化合物粉末(如：硬脂輔等，而達到降低 吸水性樹脂吸驗結塊啊的目的。 - 上述使用具有氨基或環氧基的變性石夕油，由於勒度偏々 易造成清理時的困難外，使用疏水性二氧化雜吸水性樹脂中各 ==水性樹脂的吸收速度。使用二氧化術物、氧化紹水 口或德鈦水合物添加於吸水性樹脂的絲，賴不會降低吸 收f度’但是’由於此類無機鹽粉末是微粉狀，容易產生粉塵的 問題，利賜離子型界面活性㈣吸水性雛表面的方法， 則會降低吸水性樹脂的吸收倍率。 【發明内容】 本發明所製成之高吸水性樹脂，係以引發自由基進行聚合反 應，其所需的含酸基單體除丙稀酸外，尚可使用其它且有不飽人 雙鍵的水雜單體，如：甲絲烯酸、馬林酸、富馬酸、2-丙i 私-2-甲基丙垸續酸等。單體之選用不特定限制只可使用一種， 亦可合併多種單體—起制，亦可視情況需要添加具有不飽和雙 鍵之其他親水性的單體’如：丙騎胺、甲基丙觸胺、丙稀酸 2一烴基乙酯、曱基丙烯酸2_烴基乙酯、丙烯酸曱酯、丙烯酸乙酯、 一甲胺丙烯丙烯醯胺、氯化丙烯醯胺基三曱銨等（美國專利 4, 〇57, 521 號、4, 062, 817 號、4, 525, 527 號、4, 286, 082 號及 8 200900438 4, 295, 9δ7號）’但添加量以不破壞高吸水性樹脂之物性為原則。9 在進行自由基聚合反應前，單體水溶液濃度宜控制在重量百 分比20wt%至55wt%間，適當濃度為施伐至心敗間，濃度在 重里百77比2Gwt似Τ'日〗’聚合後水合膠體太軟且有黏性不利機 械加工添加展度在重量百分比55wtto上，過於接稍和濃度 時有不易概_且反應讀反軸形不緒制。 又 工t风ΠΠ之pH值會偏 若不慎與人體接觸時均不 含酸基單體之魏基應部份巾和以控織品之阳值，使呈 中性或微雜。作_週練愤麵顿土麵氫氧化物2 是碳酸化合物，如：氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸奸、碳 賴鋼、碳酸氫_氨類化合物；中和劑可單敏用-種或多^ 此合使用。含酸基單體之獄基部份中和成納鹽物鹽或錢鹽， 中和濃度料百分比為45md%至85福％，較宜為編_ 75m〇U ’中和濃度莫耳百分比為45則1%以下時成品之阳值合 偏低，t和濃度莫耳百分比為8加。1%以上時成品 :200900438 IX. Description of the invention: (Technical field to which the invention pertains) Superabsorbent resins are water retaining agents widely used in agriculture or horticulture, anti-dew beads coagulants in building materials, and materials for removing moisture from petroleum. , as an outer layer waterproofing agent in cable, and used in sanitary articles such as diapers, feminine hygiene products, disposable wipes, etc. [Prior Art] r The composition materials of superabsorbent resins are known in the art, There is a water-decomposable type of hydrolyzed starch acrylonitrile graft polymer (Japanese Laid-open Patent Publication No. 49 (1974M3, 395), Zhonghe Temple Powder-Acrylic Graft Copolymerization: Japanese Patent Publication No. 51 ( 1976) _125, 468), saponified ethylene acetate-propylene copolymer (Japanese Patent Publication No. Sho 52 (1977 H4, 689), hydrolyzed acrylonitrile copolymer or acrylamide copolymer (Japanese Patent Publication No. 1978M5, 959) 'and part of neutralizing polyacrylic acid (Japanese Patent Publication No. 1 5509 is called 84,3〇4), etc. Among the raw materials of the temple powder-acrylonitrile graft polymer, because it contains natural polymer-test , It causes decomposition of the rot, so it cannot be stored for a long time. Moreover, the manufacturing method is very _, so the high water absorbing resin is prepared by cross-linking polymerization using acrylic acid and acrylate. Most of the gas recordings are also expected to be converted, and the (tetra)-acids of the light-based copolymers are commercially available in a rapid field, and the obtained super absorbent resin has a very good water absorption force and has a manufacturing cost. It is the most advanced superabsorbent resin because it is inexpensive and does not take down decomposition and is the most competitive. 6 7 200900438 Polymerization of acrylic acid and acrylate to form superabsorbent resin can be known by several methods. a method such as aqueous solution polymerization, reverse phase suspension polymerization, emulsion polymerization or spraying or coating a monomer onto a fibrous substrate for polymerization. In these methods, reverse phase suspension polymerization is carried out. And the emulsion polymerization must use an organic solvent, but if the temperature at the time of the polymerization reaction cannot be effectively controlled, the organic solvent will cause an increase in the temperature and pressure of the reaction system, and a fire will occur. It even causes an explosion, which threatens the safety of the personnel on the operating site and causes environmental pollution problems. The finished product also has the doubt of organic solvent residue. θ Superabsorbent resin particles will be used for storage or use because of their high hygroscopic properties. The process of manufacturing sanitary products t causes the resins to adhere to each other by absorbing moisture in the air, and thus cannot be smoothly fed from a continuous quantitative supply device, so that the high water absorption in the sanitary products manufactured by the company is high. The content of the purpose is unevenly distributed, and the problem of moisture absorption and agglomeration has become a new research trend. Up to now, the financial shirt scientists have been trying to reduce the hyperabsorbent contact. There have been many reductions in high water absorption in the art world: =:::: such as: use of amino acid or epoxy group denaturation (four) and product _ above 1___33558), adding specific surface wealth (Japan special =. I below the hydrophobicity The dioxide is also used in the outer layer of the water-absorbing fine, and the cationic surfactant is sprayed to the V 12 alkyl group. 200900438 = surface of the aqueous resin (Japan _ 61 de 4) for surface treatment, (4) melting point The organic compound powder (eg: secondary stearyl, etc., but the water-absorbent resin to reduce absorption test object blocking of ah. - The above-mentioned denatured tartar oil having an amino group or an epoxy group is used, and the absorption rate of each == aqueous resin in the hydrophobic anaerobic water-absorbent resin is used because of the difficulty in cleaning during the degree of eccentricity. The use of a dioxide, a oxidized water or a titanium hydrate to add a silk to a water-absorbent resin does not reduce the absorption of f-degree but 'because the inorganic salt powder is micro-powder, which is prone to dust generation. The method of imparting ionic interfacial activity (IV) to the water-absorbent surface will reduce the absorption ratio of the water-absorbent resin. SUMMARY OF THE INVENTION The superabsorbent resin produced by the present invention is a polymerization reaction initiated by initiating a radical, and the required acid group-containing monomer may be used in addition to acrylic acid, and other unsaturated double bonds may be used. The water-containing monomer, such as: methic acid, marinic acid, fumaric acid, 2-propidin-2-methyl propyl hydrazine, and the like. The selection of the monomers is not limited to one type, and a plurality of monomers may be combined, and other hydrophilic monomers having unsaturated double bonds may be added as needed, such as: acrylamide, methyl propylene Amine, 2-hydrocarbyl ethyl acrylate, 2-hydrocarbyl ethyl acrylate, decyl acrylate, ethyl acrylate, monomethyl propylene acrylamide, chlorinated acrylamide ruthenium amide, etc. (US Patent 4 , 〇57, 521, 4, 062, 817, 4, 525, 527, 4, 286, 082 and 8 200900438 4, 295, 9δ7) 'but added in order not to damage the physical properties of the superabsorbent resin For the principle. 9 Before the free radical polymerization, the concentration of the aqueous monomer solution should be controlled between 20% and 55% by weight, and the appropriate concentration is between the application and the failure. The concentration is in the weight of 77% to 2Gwt. The hydrated colloid is too soft and sticky. The mechanical processing addition is on the weight percentage of 55wtto. When it is too close to the concentration, it is not easy to be _ and the reaction is reversed. The pH value of the worker's wind will be partial or slight. If it is inadvertently in contact with the human body, the Weiji should not contain the acid-based monomer and the positive value of the fabric should be neutral or slightly mixed. _ Weekly practice indigo surface soil hydroxide 2 is a carbonic acid compound, such as: sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid, carbon Lai steel, hydrogen carbonate _ ammonia compound; neutralizer can be single sensitive Use one or more of them. The base of the acid-containing monomer is neutralized to form a salt or a salt of a salt, and the percentage of the neutralizing concentration is 45 md% to 85 bf%, preferably _75 m〇U 'the concentration of the neutralizing concentration is When 45 is less than 1%, the positive value of the finished product is low, and the percentage of t and concentration of mole is 8 plus. Finished product at 1% or more:
聚乙烯醇、聚乙二醇、聚丙烯酸、聚丙烯醯胺、 物如曱基纖維素，丙烯酸曱基纖維素，乙 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 分子叫低成本’此等水雜高分子如：部份故妓全息化= 哗贴妝、歟粉或澱粉衍生 乙基纖維素等聚合物； 200900438 λ*々、一 10 寺水溶性高分子的分子量跡制限定，財紐的水溶性高分 子為殿粉、部份皂化或完全4化的聚乙_等翔或混合使用。 高吸水性樹脂含此等添加水溶性高分子的適當重量百分比為〇至 20wt%，但以〇至編。/輕，〇至嬉尤佳，添加超過勤故 時會影響物性，使物性變差。 在進㈣由基聚合反應前應先添加自由基聚合反應交聯劑 於未反液中’此自由絲合反應交聯劑可選用具有兩個 或兩個以上不飽和雙鍵的化合物，如:耶，_雙(2•丙稀基)胺侧， =甲基雙丙烯_、N,N，_次甲基雙甲基丙稀醯胺、丙烯酸丙婦 -曰乙酉子一丙稀酸酯、聚乙二醇二丙缔酸酉旨、乙二醇二甲基丙 稀@_、聚乙m基丙稀酸酯、甘油三_酸自旨、甘油三甲 土丙稀酉夂!曰甘油附加環氧乙烧之三丙稀酸醋或三甲基丙婦酸 酷、三甲醇丙烧附加環氧乙烧之三丙稀酸醋或三甲基丙烯_旨、 三甲醇丙燒三甲基丙稀_旨、三曱醇丙烧三丙稀酸醋、n難三 (一2-丙烯基)胺、二丙稀酸乙二醇酯、三丙烯酸聚氧乙烤甘油酿' 烯-夂乙基水氧乙婦甘油酯、二丙稀三甘醇酯等，亦可選用 f有兩個或兩個以上環氧基的化合物，如山梨醇》水甘_、 來丙4聚縮水甘油韆、乙二醇二縮水甘_、二乙二醇二縮水 甘摘、聚乙二醇二縮水甘_、雙丙三醇聚縮水甘簡等。在 進行自域反顧財使高财性樹脂具有適當交聯度，而㈣ 吸水性樹轉體有她^性。自域聚合反歧聯劑可單獨 200900438 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 置在重量百分比〇.〇〇lwt%至5wt%之間（以反應物總固形份為基 準），更適當的用量重量百分比在001wt%至3wt%之間。添加劑 i在重量百分比0.001wt%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。 - 眾合反應由自由基聚合反應起始劑的分解產生自由基開 始。自由基起㈣可選賴分解型起關，適合的熱分解型起始 劑有過氧化物’如··過氧化氫、二_第三丁基過氧化物、過氧化酿 胺或過硫酸鹽(纏、驗金屬鹽)#，及減化合物如：比偶氮 基雙(2-脒基丙烧)二鹽酸鹽、2.2，_基雙(取_二伸甲基異丁喲 二鹽酸鹽；亦可使闕原劑，使縣氧化還起始劑，如：酸 性亞硫_、硫代硫_、抗壞血酸或賴鹽；或職化還原型 起始劑和齡㈣触劑合併制。首絲化·起始劑先進行 反應產生自由基’當自由基轉移至單體上即引發聚合反應的進 行，由於聚合反驗行時铸料大㈣歸崎溫度升高，當 溫度到達齡麵触_麵溫料，又料料二段数分解 型起始劑的分解，峨㈣聚合反應更臻於完全。—般自由基聚 合反應起始批適當為重量百分比咖讓至_(以中 和丙稀酸鹽重量為基準），更適當用制在G.lwt%至5wi%之間。 使用重量百分比咖购下時，反應太慢不利經濟效益，使用 200900438 重夏百分比l〇wt%以上時，反應太快反應熱不易控制。 生產聚丙烯酸系的高吸水性樹脂其聚合反應，—般係於傳統 批次反應容n巾，或於輪送帶式反應器上進行反應，反應所得之 问吸水性樹脂，先利用絞碎機切成直徑20mm以下小凝膠體，直 徑10mm以下更佳，再進行篩選。 篩選固定粒徑之凝膠體直徑以2.〇〇 mm以下為宜，以〇 〇5 mm至1.50 mm間較佳，粒徑大於2.〇〇 mm之凝膠體則重新送回 Ί石τ钱進行再次切碎。粒徑〇 以下之凝膠體進行烘乾、粉 砰處理後，易產生成品細粉量提高，粒徑2 〇〇mm以上之凝膠體 進打烘乾時，容易因為熱傳導效果不佳，導致成品殘存單體偏高 及其他物性表現不佳之缺點。 依據本發明，丙烯酸鹽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最佳狀態，而且有利於控制烘乾 的時間及溫度，篩選完成後再進行烘乾。 烘乾溫度以溫度1〇〇它至180°c進行烘乾為宜。烘乾溫度 ioo°c以下烘乾，時間會太久不具經濟效益，烘乾溫度18〇t以上 烘乾，會使交聯劑提早進行交聯反應，使得後續的乾燥過程中， 因交聯度過高而無法有效的去除殘存單體而達到降低殘存單體 之效果。 . 乾燥後進行粉碎、篩選固定粒徑，再進行表面交聯劑塗覆處 200900438 〇獅_佳’減_mm 下之細粉使成品粉 徑].〇〇mm以上之粒子使成品吸水 才 酸鹽聚合物的.大小分佈越窄越好。U依據本發明，丙歸 表面交聯劑塗覆處理時，表面交聯劑之添加方式則是 ^龜類，讎面交亀齡，_絲劑 =加’或調成表面交聯劑親水性有機溶劑水溶液添加。親 ==劑如曱醇、乙醇、丙醇、異丁醇，、甲一 寻>又料_，可形成溶液即可，其中以㈣、乙醇較 加時高吸水樹脂中可添加惰性無機鹽粉末，以幫助溶 刀月，J4無機麵末可為硫_、或二氧切，或氧化無， 或其混合物，其中以_、二氧切較佳。惰性- 的物糊賴合她似恤。惰性無機 ㈣添加關在重量百分比_5w· 1()細％之間，里中以 O.Olwt%至 4.0wt%較佳。 ’、 進行表岐聯齡覆處理後，_听至23{)1;範_ -------Polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polypropylene decylamine, such as fluorenyl cellulose, fluorenyl acrylate cellulose, B can also be added to the aqueous solution of the monomer before the radical polymerization reaction Called low-cost 'such water-like polymers such as: some 妓 holographic = 哗 makeup, 欤 powder or starch-derived ethyl cellulose and other polymers; 200900438 λ * 々, a 10 temple water-soluble polymer molecular weight The trace system is limited, and the water-soluble polymer of Caixin is used as a powder, partially saponified or completely condensed or mixed. The superabsorbent resin contains 适当 to 20% by weight of the water-soluble polymer, and is preferably 〇 to 20% by weight. / Light, 〇 嬉 嬉 嬉 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the case of the (4) radical polymerization reaction, the radical polymerization crosslinking agent should be added to the unreacted liquid. This free silking reaction crosslinking agent can be selected from compounds having two or more unsaturated double bonds, such as: Ye, _ bis (2 propyl) amine side, = methyl bis propylene _, N, N, _ methine dimethyl propyl amide, acrylic acrylate - 曰 酉 一 丙 acrylate, Polyethylene glycol dipropionate 酉, ethylene glycol dimethyl propylene @ _, polyethyl propyl acrylate, glycerol ternary acid, glycerol trimethyl propylene 酉夂 曰 glycerol additional ring Oxygen triacetate or trimethyl acetoacetate, trimethyl methacrylate, propylene oxide or trimethyl propylene, trimethyl propylene trimethyl propylene _, tridecyl alcohol propylene triacetate, n difficult three (mono-2-propenyl) amine, ethylene glycol diacrylate, triacetin polyoxyethylene roast glycerol brewing 'ene-夂 ethyl water Oxygen glyceryl glyceride, dipropylene triethylene glycol ester, etc., may also be selected from compounds having two or more epoxy groups, such as sorbitol, water, glycerol, propylene glycol, polyglycidol, ethylene Alcohol condensed water _, two ethylene two Diglycidyl off, polyethylene glycol diglycidyl _, bis glycerol polyglycidyl Jane like. In the self-regulation of wealth, the high-yield resin has a proper degree of cross-linking, and (4) the water-absorbing tree has her sex. Self-domain polymerization anti-aggregation agents can be used alone or in combination of two or more. The free radical polymerization crosslinker suitable additive is placed between 重量% by weight and 5% by weight based on the total solids of the reactants, more suitably in a weight percentage between 001% and 3% by weight. . The additive hydrate is too soft and viscous after polymerization at a weight percentage of 0.001% by weight or less. Mechanical processing, the amount of the additive is too low at a weight percentage of 5 wt% or more, and the resin property is lowered. - The crowd reaction begins with the decomposition of the radical polymerization initiator to generate free radicals. Free radicals (4) can be selected according to the decomposition type, suitable thermal decomposition type initiators are peroxides such as hydrogen peroxide, di-tert-butyl peroxide, peroxylated amine or persulfate (wound, test metal salt) #, and subtractive compounds such as: azo bis(2-mercaptopropenyl) dihydrochloride, 2.2, _ bis (take _ diexet methyl isobutyl hydrazine dihydrochloride Salt; can also make the bismuth agent, the county oxidation also starter, such as: acid sulfite, thiosulfur _, ascorbic acid or lysine; or occupational reduction initiator and age (four) contact agent. The first filamentization and the initiator start the reaction to generate a radical. When the radical is transferred to the monomer, the polymerization reaction is initiated. Due to the polymerization, the casting material is large (4), and the temperature rises when the temperature reaches the age. Touching the surface temperature material, and decomposing the second-stage decomposition type initiator, the 峨(4) polymerization reaction is more complete than the complete. The general free radical polymerization starting batch is appropriate to the weight percentage of coffee to _ (to neutralize C Based on the weight of the dilute acid salt, it is more suitably used between G.1wt% and 5wi%. When using the weight percentage coffee, the reaction is too slow and uneconomical. Benefit, when using 200900438 heavy summer percentage l〇wt% or more, the reaction is too fast, the reaction heat is not easy to control. The polymerization reaction of producing polyacrylic superabsorbent resin is generally based on the traditional batch reaction capacity, or in the round The reaction is carried out on a belt-feeding reactor, and the water-absorbent resin obtained by the reaction is first cut into a small gel having a diameter of 20 mm or less by a mincer, and the diameter is preferably 10 mm or less, and then subjected to screening. The diameter is preferably less than 2. 〇〇mm, preferably between 〇〇5 mm and 1.50 mm, and the gel having a particle size greater than 2. 〇〇mm is re-sent back to the scorpion τ money for re-crushing.烘干The following gels are dried and powdered, which tends to increase the amount of finished fine powder. When the gel with a particle size of 2 〇〇mm or more is pressed and dried, it is easy to survive due to poor heat transfer. According to the invention, the narrower particle size distribution of the acrylate gel body not only enables the gel body to perform optimally after drying, but also facilitates controlled baking. Dry time and temperature Drying is carried out after the screening is completed. The drying temperature is preferably dried at a temperature of 1 〇〇 to 180 ° C. The drying temperature is below ioo °c, the time will be too long, and the drying temperature is 18〇. Drying above t will cause the cross-linking agent to cross-link early, so that the effect of reducing the residual monomer can not be effectively removed due to the high degree of cross-linking during the subsequent drying process. Crushing and screening the fixed particle size, and then applying the surface cross-linking agent coating at 200900438 〇 _ _ _ _ _ mm under the fine powder to make the finished powder diameter]. 〇〇 mm or more of the particles to make the product absorb the acid polymer The narrower the size distribution, the better. U According to the invention, when the surface crosslinking agent is coated, the surface crosslinking agent is added in the form of turtles, 雠面交亀, _丝剂=加' or The surface crosslinking agent is added to a hydrophilic organic solvent aqueous solution. A pro-== agent such as decyl alcohol, ethanol, propanol, isobutanol, and A _ _ _ _ _ can be formed into a solution, wherein (4), ethanol can be added to the super absorbent resin can add inert inorganic salts The powder may be used to help dissolve the knife. The J4 inorganic surface may be sulfur- or dioxin, or oxidized, or a mixture thereof, wherein _ and dioxotomy are preferred. The inertia - the paste of the matter depends on her. The inert inorganic (iv) addition is preferably between 5% by weight and 5% by weight, preferably from 0.001% by weight to 4.0% by weight. ', after the performance of the joint age, _ heard to 23{) 1; Fan _ -------
丄 又P反應而達到本發明之效果。熱處理溫度8(TC 料^聯反應時間太久，不具經濟效^，熱處理溫度23叱以上 品質’熱處理時間以2分鐘至18。分鐘為宜，依 于、表面處理效果做熱處理溫度調整，熱處理溫度高則 200900438 熱處理時間短’滅理溫度溫度低時，則減理溫度時間長。 本發明所指謂之無機鹽水溶液是指硫酸鋁、硫酸鎂、氧化 鋁、氧化鎂、氧化鋅、碳酸鈣、磷酸鈣、磷酸鋇、矽藻土、軟土、 黏土、滑石粉、沸石、高嶺土、膨土、活性碳、二氧化石夕、二氧 化鈦之I機鹽粉末與水混合所產生的水溶液。混合過程中所利用 的置須具能夠產生大的混合力，使混合能充分均勻；無機 鹽粉末的用法可單獨使用或合併兩種以上混合使用。其無機鹽粉 末之比表面積50m2/g以上為宜，15〇m2/g以上較佳。 上述本發明之無機鹽水溶液的黏度範圍在1〇至l4〇〇rf)s 之間。無機鹽水溶液之添加範圍在重量百分比〇 〇丨械％至2〇 〇wt〇/。 之間，其中以O.Olwt%至10wt%較佳。無機鹽粉末之粒子大小最 好不大於l〇mm ’更適當的大小為〇.6mm以下。 【貫施方式】 為充分彰顯本發明，本發明吸水性樹脂以及無機鹽水溶液 在混合裝置中能充分混合均勻，混合過程中所利用的混合裝置必 需能夠產生大的混合力，使混合能夠充分均勻。用之於本發明的 混合裝置可以V-型混合器、柱式混合器、高速攪拌混合器、螺旋 式混合器、氣流混合器、雙臂捏合機、雙臂錐形混合器、螺條混 合益、密壁式混合器、粉碎捏合機、旋轉混合器以或螺桿擠出機。 200900438 ⑻使用-種含有丙烯酸(鹽)與/或丙烯_(鹽)的水溶性不5 飽和單體，其中和比率在45至85莫耳％之範圍内，不 餘和單體水騎的濃度在μ至％餘份之範 反應； ⑼反應後生成的凝膠體，利用溫度·t至⑽。〇範_ 4風乾無、粉碎、篩選； ⑷以表面交聯劑及無機鹽水溶液塗覆後，於_至靴 域表面處理；或如表面交聯舰覆於高吸水性樹 月曰表面後’於8〇 c至230°C加熱表面處理，再使用無 機鹽水溶液塗覆。 ’' 一上这本I明之特徵，係湘表面交聯航無频水溶液塗覆 方、门吸表面’㈣加熱表面處理的過程，使得無機鹽粉 末能完全_著在純水性翻旨表面，或是將無频水溶液塗覆 於完成表祕質的高财_脂表面。上述龄法，均能使無機 鹽粉末充分的轉於與高吸水性樹脂表面，降低生產廠區以及高 吸水性樹脂成品t的發塵量，並且減少高吸水性概吸濕後之結 塊問題’及減少對環境以及生物體的影響。 ?尤本七月而D，僅利用無機鹽水溶液噴麗於吸水性樹脂表 面^可成侧將錢餘末黏棘與高吸水性義表面，進而 降低高吸水性樹脂成品與生產·的發塵量及減少高吸水性樹 200900438 脂吸濕後結塊問題。而用來製備合於此敘述的水溶性不飽和單體 的步驟並無特殊之限制。 經由本發明所製造的高吸水性難，由於具有低發塵量的特 性，所以可降倾生物體與環境的影響，並且具備減少高吸水性 樹脂吸濕後結塊的躲’ m而大幅減低了衛生用品中之高吸水性 樹脂的含f不均㈣題。經由上述本發明之方法所得之高吸水性 樹脂’職更_於各翻式的衛线品、農t肢食品保鮮用 的吸水劑。 為註示本發明之高吸水性樹脂的壓力下吸水倍率，本發明利 用受壓吸收麵力負荷：2Gg/em2)來般，受壓吸收量係根據歐 洲糊咖61 A號說明書第七頁情描述的方法測定；將初始 重1的高吸水性旨放在有篩網底部的圓柱體巾，對粉體加以 2〇g/cm2的壓力’接著將此圓柱體置於吸收性需求測試器上，讓 —吸水性樹脂·α9%的氯化鈉水溶液—辦，再將測吸水重 量將所得數值除以高吸水性樹_重量，即得受壓吸收量數值。 ^月之保持力係利用茶袋試驗法測定，並以五次量測結 2嶋值以及最低值後，取平均值；將叫的㈣性樹 衣土才、衣裡，亚次泡於〇·9%的氯化納水溶液分鐘，然後將 此浸泡後的茶袋置於離心機中離心(直徑⑽、轉速剛啊)三 16 200900438 分鐘後秤重。所得之數值 17 代番⑻日门a 值无減去未充填兩吸水性樹脂的空白組革 衣(烟㈣㈣)驗《聚合㈣即得轉力數值。' 二結塊效果的判定，係利用3.°克高吸水性樹 月曰置入直彳工β公分的培養皿中丄 P reacts to achieve the effects of the present invention. Heat treatment temperature 8 (TC material reaction time is too long, no economic effect ^, heat treatment temperature 23 叱 or more quality 'heat treatment time is 2 minutes to 18 minutes, depending on the surface treatment effect of heat treatment temperature adjustment, heat treatment temperature High is 200900438 Short heat treatment time 'When the temperature is low, the temperature is reduced. The inorganic salt solution referred to in the present invention refers to aluminum sulfate, magnesium sulfate, aluminum oxide, magnesium oxide, zinc oxide, calcium carbonate, An aqueous solution produced by mixing calcium phosphate, strontium phosphate, diatomaceous earth, soft soil, clay, talc, zeolite, kaolin, bentonite, activated carbon, cerium oxide, titanium dioxide, and a salt of a titanium salt with water. The used whisker can generate a large mixing force to make the mixing energy sufficiently uniform; the inorganic salt powder can be used alone or in combination of two or more. The inorganic salt powder has a specific surface area of 50 m 2 /g or more, 15 Preferably, 〇m2/g or more. The above-mentioned inorganic salt aqueous solution of the present invention has a viscosity ranging from 1 Torr to 14 〇〇rf)s. The addition of the aqueous inorganic salt solution ranges from 5% by weight to 〇 〇wt〇/. Preferably, it is O.Olwt% to 10wt%. The particle size of the inorganic salt powder is preferably not more than 10 mm. The more appropriate size is 〇.6 mm or less. [Complex application method] In order to fully demonstrate the present invention, the water-absorbent resin and the inorganic salt aqueous solution of the present invention can be sufficiently mixed and uniformly in a mixing device, and the mixing device used in the mixing process must be capable of generating a large mixing force, so that the mixing can be sufficiently uniform. . The mixing device used in the present invention can be a V-type mixer, a column mixer, a high-speed agitating mixer, a spiral mixer, a gas stream mixer, a two-arm kneader, a two-arm conical mixer, and a ribbon mixing benefit. , a dense wall mixer, a pulverization kneader, a rotary mixer or a screw extruder. 200900438 (8) Use of a water-soluble non-saturated monomer containing acrylic acid (salt) and/or propylene (salt), the ratio of which is in the range of 45 to 85 mol%, and the concentration of monomer water riding In the range of μ to % remainder; (9) The gel formed after the reaction, using temperature · t to (10). 〇范_ 4 air drying, smashing, screening; (4) after surface coating with a cross-linking agent and an aqueous solution of inorganic salt, on the surface of the _ to the shoe field; or after the surface cross-linking ship is overlaid on the surface of the highly water-absorbent tree The surface treatment was heated at 8 ° C to 230 ° C and then coated with an aqueous solution of an inorganic salt. ''The characteristics of this I, the surface of the surface of the cross-linking water-free aqueous solution coating, door suction surface' (four) heating surface treatment process, so that the inorganic salt powder can be completely on the surface of pure water, Or apply a non-frequency aqueous solution to the high-fat surface of the finished table. The above-mentioned ageing method can fully transfer the inorganic salt powder to the surface of the superabsorbent resin, reduce the amount of dust generated in the production plant area and the superabsorbent resin product t, and reduce the agglomeration problem after the high water absorption is absorbed. And reduce the impact on the environment and organisms.尤本July and D, only use the inorganic salt aqueous solution sprayed on the surface of the water-absorbent resin to form a side of the sticky end of the sticky spine and the highly water-absorbing surface, thereby reducing the dusting of the superabsorbent resin product and production. Amount and reduce the high water absorption tree 200900438 The problem of caking after moisture absorption. The procedure for preparing the water-soluble unsaturated monomer described herein is not particularly limited. The high water absorption property produced by the present invention is difficult, and has the characteristics of low dust generation, so that the influence of the living organism and the environment can be lowered, and the reduction of the agglomeration of the superabsorbent resin after moisture absorption can be greatly reduced. The unevenness of the superabsorbent resin in sanitary products (4). The superabsorbent resin obtained by the method of the present invention described above is a water absorbing agent for fresh-keeping of the reticle and the food for fresh-keeping of the agricultural products. In order to indicate the water absorption ratio under pressure of the super absorbent resin of the present invention, the present invention utilizes a pressure absorption surface load of 2 Gg/em 2 ), and the pressure absorption amount is based on the seventh page of the European Food and Cosmetics No. 61 A specification. The method described is determined; the high water absorption of the initial weight of 1 is applied to the cylindrical towel having the bottom of the sieve, and the powder is subjected to a pressure of 2 〇g/cm 2 '. Then the cylinder is placed on the absorbent demand tester. Let the water-absorbent resin · α 9% aqueous sodium chloride solution - and then measure the water absorption weight and divide the obtained value by the superabsorbent tree _ weight, that is, the pressure absorption amount value. ^The retention of the month is determined by the tea bag test method, and the average value of the knot is measured in five times and the lowest value is taken; the average value is called (four) sex tree clothing soil, clothing, sub-bubble in the 〇· After 9% of the sodium chloride aqueous solution, the soaked tea bag was placed in a centrifuge for centrifugation (diameter (10), speed just after) three 16 200900438 minutes and weighed. The value obtained 17 Daifan (8) The value of the day a value is not subtracted from the blank group of leather that is not filled with two water-absorbent resins (smoke (4) (4)). 'The determination of the effect of the two agglomerates is carried out in a Petri dish with a high hygienic tree of 3.°g.
淨水的抽氣梦^ 將机養孤放入底部含有300mL 六Μ 9⑽ 刪deSlCCat〇r)内，並利用抽氣幫浦將墨 %抽氣1分鐘’關閉抽氣幫浦，7分鐘後取出培参 皿並緩慢旋轉⑽度後，以分析天平秤取殘留在培養皿中的高吸 水! 生樹MW)。當w值小於G.4克，絲吸難抗結塊效果良好， W值界於1騎4克之間，表示吸濕後抗結塊效果尚可，當則直 大於1.0克，表示賴後抗結塊效果不良。 本心月之^塵f ’係在密閉空财距離底部高度為術爪處 置篇斗ϋ利用隔板盍住漏斗底部，將1〇〇运吸水性樹脂放 置於漏相’㈣卩帛板，使吸水性樹n下，糊粉塵計腿_廳了 HD 1100型儀為’以雷射光掃猫方法測定粉塵濃度，並以五次量 測結果，去除最高值以及最低值後，取平均值。 以下以貫施例說明本發明；但本發明之專利範圍不受這些實 例所限制。 實例一： 1)取48%氫氧化鈉水溶液2丨8 7g緩慢加入放27〇g丙烯酸及29丨6g 的水之50〇c.c圓錐瓶中，氫氧化鈉/丙烯酸的滴加比率在〇·85 18 18200900438 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42wt%水溶液， 其中70mol°/〇(莫耳比)丙烯酸部份中和為丙稀酸鈉。 2) 再加入G.414 g的N，N’·次T基雙丙湘驗於水溶性不飽和單體 溶液，並維持溫度於20°C左右。 3) 加入0.144g雙氧水’ 1.8 g亞硫酸氫納及18 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，並篩選出粒徑大 小為2mm直徑以下的凝膠體。 5) 以130°C溫度乾燥2小時；利用篩網篩選〇 lmm〜〇 85mm固定 粒徑，得粉狀高吸水性樹脂。 6) 秤取此高吸水性樹脂l〇〇g，加入二氧化矽/水=1/9(重量比)溶液 4.0g(黏度=40cPs)，待混合均勻後再加入乙二醇碳酸酯/水/曱醇 = 1/1/1(重量比)溶液3.9g，以2〇〇°C溫度加熱處理15分鐘，冷 卻後’即得高性能高吸水性樹脂之測定保持力為3l 2g/g， 20g/cm2壓力下吸水倍率29.6g/g，w值=0.20g(吸濕後抗結塊效 果良好），發塵量0.72mg/m3。 實例二: 18 19 19200900438 秤取100g咼吸水性樹脂（品名：台速保BC286LE)，加入二氧化 矽/水-1/9(重量比）溶液4〇g(黏度=4〇cPs)，其測定保持力為 3〇.4g/g ’ 20g/cm壓力下吸水倍率29 2g/g，w值=〇11以吸濕後 抗結塊效果良好）’發塵量0.53 mg/m3。 實例三： 重覆貫例二，但高吸水性樹脂改用（品名：台速保BC283)，其 測疋保持力為3〇.5g/g ’ 2〇g/em2壓力下吸水鲜29勉，％值 -0.〇7g(吸>驗抗結塊效果&好），發塵量⑽爪咖3。 實例四： -重覆貫例二’加入二氧化石夕/水，重量比)溶液2娜度 ，CPS)。其測定保持力為3〇 lg/g，2〇gW壓力下吸水倍率 29.1g/g ’ W值=0.〇9g(吸濕後抗結塊效果良好），發塵量 mg/m3 〇 實例五： —重覆實例二’加人高嶺土 /水,重量比）溶液2.5g(黏度 -158cPs)。其測定保持力為29 8g/g，2〇§/咖2壓力下吸水倍率 28.9g/g ’ W值=〇.；[#(吸濕後抗結塊效果良好），發塵量or mg/m3 ° 實例六: 20 200900438 重覆實例二’加入碳酸詞/水，重量比）溶液2.娜度 。其測定保持力為29勉，2〇加2壓力下吸水倍率 28.7g/g ’ W㈣.llg(料後抗結塊效果良好），發塵量㈣ mg/m3 ° 實例七： 重後κ例® ;&入—氧切水溶液的添加量提高至恤(黏度 V 9〇CPS)其測疋保持力為28勉，2〇gW屢力下吸水倍率 28.7g/g，W值=0.09g(吸濕後抗結塊效果良好），發塵量〇 ιι mg/m3。 比較例一： 重覆實例二，但先加入二氧化石夕粉末〇也，待混合均勾後，再 添加山梨糖醇^ 1/9(重量比）溶液3%。其測定保持力為 29输2〇g/Cm，下吸水倍率28场，W值⑽]g(吸濕後抗 結塊效果尚可），發塵量6.71mg/m3。 比較例二： / Q加人焉嶺土粉末〇.4g，待混合均勻後，再 ===醇/水，重量比）溶液叫定 刀下从倍率加g/g，Wta96g(吸濕後抗 、，，。塊政果㈣），發塵量Μ、#。 20 21 21200900438 比較例三： 重覆比較例―，但改用聚乙二醇(PEG-8000)/水==1/9(重量比) 溶液。其測定保持力為26.3g/g，20g/cm2壓力下吸水倍率24.〗g/g， W值〇.92g(及傲後抗^結塊效果尚可），發塵量9.i6mg/m3。 比較例四： 重覆實例一 ’但加入純水l.〇g，並充分攪拌均勻。其測定保 持力為25.6g/g，20g/cm2壓力下吸水倍率23.7g/g，49g/cm2壓力 下吸水倍率13.9g/g，W值=2.79g(吸濕後抗結塊效果不良），發塵 置 8.54mg/m3。 【圖式簡單說明】 【主要元件符號說明】 21The pumping dream of clean water ^ Put the machine in the bottom containing 300mL six Μ 9 (10) delete deSlCCat〇r), and use the pumping pump to pump the ink for 1 minute to turn off the pumping pump, take out after 7 minutes After incubating the dish and slowly rotating it (10) degrees, the analytical balance is used to weigh the high water absorption remaining in the culture dish! When the w value is less than G.4 grams, the silk sucking resistance is good, and the W value is between 1 and 4 grams, indicating that the anti-caking effect is acceptable after moisture absorption, and when it is directly greater than 1.0 gram, it means Poor caking effect. The dust of the heart of the month is based on the height of the bottom of the closed empty space. For the claw treatment, the baffle is used to cover the bottom of the funnel, and the water-absorbing resin is placed in the leaky phase (4). Under the water-absorbent tree n, the paste dust meter legs _ hall HD 1100 type instrument for 'measuring the dust concentration by the laser light sweeping cat method, and taking five measurements, after removing the highest value and the lowest value, take the average. The invention is illustrated by the following examples; however, the scope of the invention is not limited by these examples. Example 1: 1) Take 48% sodium hydroxide aqueous solution 2丨8 7g slowly into a 50〇cc conical flask containing 27〇g acrylic acid and 29丨6g water. The dropping ratio of sodium hydroxide/acrylic acid is 〇·85 18 18200900438 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, a monomer concentration of 42 wt% aqueous solution is obtained, wherein 70 mol / 〇 (mo The ear ratio is partially neutralized with sodium acrylate. 2) Further add G.414 g of N,N'·sub-T-based dipropene to the water-soluble unsaturated monomer solution and maintain the temperature at about 20 °C. 3) The reaction was initiated by adding 0.144 g of hydrogen peroxide '1.8 g of sodium hydrogensulfite and 18 g of ammonium persulfate. 4) The gel formed after the reaction was chopped by a cutter mill, and a gel having a particle diameter of 2 mm or less was selected. 5) Drying at 130 ° C for 2 hours; screening the 〇 lmm~〇 85 mm fixed particle size by a sieve to obtain a powdery superabsorbent resin. 6) Weigh this superabsorbent resin l〇〇g, add 4.0g (viscosity = 40cPs) of cerium oxide / water = 1 / 9 (weight ratio) solution, add ethylene glycol carbonate / water after mixing / sterol = 1 / 1 / 1 (weight ratio) solution 3.9g, heat treatment at 2 ° ° C temperature for 15 minutes, after cooling, the high performance superabsorbent resin measured retention of 3l 2g / g, The water absorption ratio under the pressure of 20 g/cm 2 was 29.6 g/g, the w value was 0.20 g (the anti-caking effect was good after moisture absorption), and the dust generation amount was 0.72 mg/m 3 . Example 2: 18 19 19200900438 Weigh 100g of water-absorbing resin (product name: Taiwan speed BC286LE), add cerium oxide / water -1 / 9 (weight ratio) solution 4 〇 g (viscosity = 4 〇 cPs), the determination The holding force is 3 〇.4g/g '20 g/g under water pressure, the pressure is 29 2g/g, the w value = 〇11 is good for anti-caking after moisture absorption) 'dusting amount 0.53 mg/m3. Example 3: Repeated example 2, but the super absorbent resin was changed to use (product name: Taiwan speed BC283), and its measuring retention was 3〇.5g/g '2〇g/em2 under pressure, 29吸水% value - 0. 〇 7g (suck > test anti-caking effect & good), dusting amount (10) claw coffee 3. Example 4: - Repeated example 2 'added to the dioxide dioxide / water, weight ratio) solution 2 Nat, CPS). The measured retention is 3〇lg/g, and the water absorption ratio under 2〇gW pressure is 29.1g/g 'W value=0.〇9g (good anti-caking effect after moisture absorption), dust emission mg/m3 〇Example 5 : - Repeat example 2 'addition of kaolin / water, weight ratio) solution 2.5g (viscosity -158cPs). The measured retention is 29 8g/g, and the water absorption ratio under pressure of 2〇§/咖2 is 28.9g/g 'W value=〇.;[#(good anti-caking effect after moisture absorption), dust amount or mg/ M3 ° Example 6: 20 200900438 Repeat example 2 'Add carbonate word / water, weight ratio) solution 2. Nadu. The measured retention is 29 勉, 2 〇 plus 2 pressure, water absorption ratio 28.7g / g 'W (four). llg (good anti-caking effect after the material), dust amount (four) mg / m3 ° Example seven: heavy κ case ;&----------------- Good anti-caking effect after wet), dusting amount 〇ιι mg/m3. Comparative Example 1: Repeat Example 2, but first add the dioxide to the powder, and then add sorbitol ^ 1 / 9 (by weight) solution 3%. The measured retention is 29 〇 2 g/cm, the lower water absorption ratio is 28 fields, the W value is (10)] g (the anti-caking effect is good after moisture absorption), and the dust generation amount is 6.71 mg/m3. Comparative Example 2: / Q plus human glutinous earth powder 〇. 4g, after mixing evenly, then === alcohol / water, weight ratio) solution called the knife from the magnification plus g / g, Wta96g (anti-moisture resistance ,,,,,,,,,,,,,,,,,,,,,,,,,,,, 20 21 21200900438 Comparative Example 3: Repeat the comparison example, but use a solution of polyethylene glycol (PEG-8000) / water = = 1 / 9 (weight ratio). The measured retention force is 26.3 g/g, and the water absorption ratio under the pressure of 20 g/cm 2 is 24. g/g, the W value is 92.92 g (and the aggravation effect is still acceptable), and the dust generation amount is 9.i6 mg/m3. . Comparative Example 4: Repeat Example 1 'but add pure water l.〇g and stir well. The measurement retention was 25.6 g/g, the water absorption ratio under pressure of 20 g/cm 2 was 23.7 g/g, the water absorption ratio under pressure of 49 g/cm 2 was 13.9 g/g, and the W value was 2.79 g (poor anti-caking effect after moisture absorption). The dust is set at 8.54 mg/m3. [Simple description of the diagram] [Explanation of main component symbols] 21