l338〇l6 九、發明說明： 【發明所屬之技術領域】 本發明係提供一種減少高吸水性樹脂細粉產生的方法。經此 製造方法可以在相同的情況下，減少細粉所占的比例，提升高吸 水性樹脂的製程能的穩定性，又能增加高吸水性樹脂的生產效 〇 【先前技術】 高吸水性樹脂廣泛地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，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。 在本技藝界已知的高吸水性樹脂的成分材料有遇水分解型 的又粕丙稀腈(hydrolyzed starchacrylonitri le)接枝聚合物 (日本公開特許公報昭49(1974)-43, 395)，中和之殿粉-丙稀 酸接枝聚合物（日本公開特許公報昭51 (1976)_125,468)，息 化乙婦醋酸_丙烯酯共聚物（日本公開特許公報昭 52(1977)~14’ 689)，水解丙烯腈共聚物或丙烯醯胺共聚物（曰本 公報昭53 (1978)_15, 959)，及部份中和聚丙稀酸（曰 本特4公報昭55(198G)'84,3G4)等。其中·_丙烯腈接 聚°物的原料中’因為含有天然的高分子一澱粉，會引起腐爛 5 1338016 性的分解，所以無法長時間的保存；再者，其製造方法十分複雜， J 所以現今高吸水性樹脂之製備方式以使用丙烯酸及丙烯酸鹽進 • 行交聯聚合所得之高吸水性樹脂佔最大部份也最為經濟，其原因 為丙烯酸鹽共聚物的原料-丙烯酸可迅速由商場上購得，且製得 的高吸水性樹脂具有高的吸水能力，及具有製造成本低廉且最具 經濟效益以及不會引起腐爛性的分解，故成為最普遍化的高吸水 性樹脂。 # 聚合丙稀酸及丙烯酸鹽形成高吸水性樹脂的方法可由數種 已知的方法製得’如水溶絲合反應、逆姆雜聚合反應、乳 • 化+合反應或將單體噴濃或塗覆於纖維基質上進行聚合反應等 方法。在14些方法巾’逆娜浮液聚合反細及乳化聚合反應必 :· 碰用到«溶劑，但是若無法有⑽控娜合反應時的溫度， 有機溶劑將造献應系統溫度以及壓力的增加，引發起火現象甚 # 雜炸’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。 【發明内容】 - 【擬解決之問題】 在本技藝界已開發出料_增加表面積方式，來改善高吸 水性樹脂的物理性質或是提高生產效率的方法，例如:添加發泡劑 的方法’包括在線性水雜聚合物愤用碳酸鮮發泡劑，一邊 中和、一邊加入交聯劑交聯結構的方法（美國專利第4529739 6 ^38〇16 號、第4,529,739號），將碳酸鹽加入到單體中的方法（特公昭 62-34042號公報、特公平2-60681號公報、美國專利第5，154 714 唬、第5,314,420號），以微波聚合含有碳酸鹽的單體溶液的方法 (美國專利第4,808,637號）’將彿點4〇 C-150°C的有機溶劑，添 加到單體中進行聚合的方法（美國專利第4,703,067號），添加疏 水性有機溶劑於特定壓力下進行聚合的方法（美國專利第 ’328,935號、第5,338,766號）等’這些提高高吸水性樹脂物理 性質的方法中，都利用發泡劑或低沸點有機溶劑於聚合、受熱的 過程中分解產生氣體或汽化來產生氣泡孔洞，用以增加吸水時的 表面積，但氣泡孔洞過多的高吸水性樹脂，於研磨過程中易造成 細粉量的增加’使的成品於吸水時容易造成gel-blocking，若沒有 適當減少細粉量的生成，都會大大降低實際應用之效能。 【解決問題之技術手段】 本發明所製造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了丙烯酸外，尚可使用其它具有不飽 合雙鍵的水溶性單體，如：甲基丙烯酸、馬林酸、富馬酸、2-丙 稀胺-2-曱基丙烷磺酸等。單體選用不特定限制只可使用一種， 亦可合併多種單體一起使用，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：丙烯醯胺、曱基丙烯醯胺、丙烯酸2-煙基乙醋、曱基丙烯酸2-烴基乙酯、丙烯酸甲酯、丙烯酸乙酯、 二曱胺丙烯丙烯醯胺、氣化丙烯醯胺基三甲銨等（美國專利 13380*16 4, 057, 521 號、4, 062, 817 號、4, 525, 527 號、4, 286, 082 號及 4’ 295’ 987號），但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前，單體水溶液濃度宜控制在重量百 分比20wt%至55wt°/〇間，適當濃度為30wt%至45wt°/。之間，濃度在 重量百分比20wt%以下時，聚合後水合膠體太軟且有黏性不利機 械加工，添加濃度在重量百分比55wt%以上，過於接近飽和濃度 時有不易調配問題且反應太快反應熱過多不易控制。 含酸基單體之羧酸基應部份中和以控制成品之pH值，使呈 中性或微酸性’中和劑為氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸卸、 碳酸氫納、碳酸氫鉀及氨。錢基單體之舰基部份巾和成納鹽 或鉀鹽或銨鹽，中和濃度莫耳百分比為45船1%至85祕，宜為 50mol%至75_%，巾和敍莫耳百分比為杨版下時成品之 PH值會偏低，中和滚度莫耳百分比為85祕以上時成品之邱值 會偏高，成品pH值非呈中性或微酸性時，若不慎與人體接觸時 均不太適合也較不安全。 在進行自由絲合反麵，單體水溶射村添加水溶性高 分子以降域核制特殊祕，鱗水雜高分子如：部份矣 化或完全皂化的聚乙_、聚乙二醇、聚丙騎、聚丙_胺、 殿粉或殿粉衍生物如素，⑽酸甲基纖料，乙其纖维 素等聚合物’·料水紐高分子的分子量並獨職定，対較 8 1338016 佳的水溶性高分子為澱粉、部份皂化或完全皂化的聚乙烯醇等單 獨或混合使用。高吸水性樹脂含此等水溶性高分子的適當重量百 分比為0至20wt%，但以0至I0wt%較佳，〇至5wt%尤佳，添加 超過20wt%時高吸水性樹脂有效吸水成分偏低，會影響物性使吸 水能力變差。 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 於未反應單體溶液中，此自由基聚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：Ν,Ν-雙（2-丙稀基）胺、 Ν’Ν -次曱基雙丙烯醯胺、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 曱基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、甘油三丙烯酸酯、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 烯酸醋、三曱醇丙烷附加環氧乙烷之三丙烯酸酯或三曱基丙烯酸 醋、三甲醇丙烷三f基丙烯酸酯、三曱醇丙烷三丙烯酸酯、Ν，Ν，Ν一 三（2-丙烯基）胺、二丙烯酸乙二醇酯、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、聚丙三醇聚縮水甘油醚、乙二醇二縮水甘油醚、二乙二醇二 縮水甘油醚、聚乙二醇二縮水甘油醚、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 9 1338016 添加劑量在重量百分比0. OOlwt%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〇. 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。若為了增加高吸水性樹脂的吸水量，亦可選用較長 鍵的架橋劑’如：美國專利第5,506,324號所示添加長鏈的2— 乙基丙二醇二聚乙二醇丙稀酸酯，此長鏈交聯劑的特性將有效的 •提升高吸水性樹脂的保持力。 ♦合反應由自由基聚合反應起始劑的分解產生自由基開 始。自由基起始劑可選用熱分解型起始劑，適合的熱分解型起始 : 劑有過氧化物，如：過氧化氫、二-第三丁基過氧化物、過氧化 ； 醯胺或過硫酸鹽（銨鹽、鹼金屬鹽）等，及偶氮化合物如：2, 2, ~ 偶氤基雙（2-脒基丙烷）二鹽酸鹽、2, 2，_偶氮基雙⑺，^二伸甲 籲基異丁脉）二鹽酸鹽：亦可使用還原劑，使成為氧化還原型起始 劑，如：酸性亞硫酸鹽、硫代硫酸鹽、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，首先氧化還原起 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，由於聚合反應進行時會釋放出大量的熱量而使溫度 升兩，當溫制賴分解型起始泰分解溫度時，又會引發第二 段熱分卿起始綱分解，而使整個聚合反應更胁完全。一般 自由基聚合反應起始劑適當用量為重量百分比為請_至 10 1338016 10wt%(以中和丙烯酸鹽重量為基準），更適當用量則在〇. lwt%至 ； 5wt%之間，使用重量百分比〇. OOlwt%以下時，反應太慢不利經濟 效盈’使用重量百分比l〇wt%以上時，反應太快反應熱不易控制。 【實施方式】 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，反應所得之水凝膠聚合物即為本發明之高吸水性 • 樹脂。本發明所定義之水凝膠聚合物泛指未經烘乾前之高吸水性 樹脂，將此聚合反應後所得之水凝膠體切割成大小一致，體積為 200cm3以下之凝膠體，再經絞碎機粉碎成體積1〇cm3以下小凝膠 體，進行烘乾。 ； 純溫度以溫度丨啊至進行烘乾為宜，烘乾溫度溫 度100 C以下烘乾’其時間太久不具經濟效益，烘乾溫度18〇。匸 卩上綠’紐高吸水性職自身進行交聯反應，影響後續的乾 燥過程中’因交聯度過高而無法有效的去除殘存單體，達到降低 殘存單體之效果。 生產聚丙烯酸系的高吸水性樹脂時，會在粉碎、研磨以及篩 選的過程中’產生粒徑不大於1G6m的高吸水性樹脂，稱之為 :細粉；細粉成量的多寡與高吸水性樹财所形成喊泡空洞有絕 對的_ ’當高吸水性樹脂氣·泡空洞愈多，在粉碎、研磨過程中 所造成的擠壓與_ ’使氣泡空關_高吸水性_破碎、形 成細粉’造成高吸水性樹脂粉塵量增加；細粉量的多賴環境以 及生物體產生—定裎度之縛，尤其是空氣中_浮微粒經由呼 吸道進入肺部因而對肺部產生繼，增加肺部與呼吸道的病變機 會’而且當細粉量❹時，代表驗大小適合她刚的高吸 水性樹脂倾少’抓的轉Η，將魏生纽率並增加成 本；高吸水性樹脂水凝膠大小的分佈（均—性）良好與否，直接 影響了成品的細粉量，當膠體離大小的均—性越高，生產過程 中所產生細粉的_就越低，成品中的細粉量就越低，越能符合 成品品質的要求，如何降低單位時間内細粉生成量，即為一項重 要的研究課題。 為降低吸水性樹脂單位時間内細粉生成量，增加生產效率， 並保持穩疋生產，本發明利用一種高效率的絞切，此種絞切方法 特徵在於： (1) 聚合後之高吸水性樹脂水凝膠，經絞碎製粒過程前， 其體積應控制為200cm3以下之水凝膠體。 (2) 水凝耀·體於切割後，其體積大小應一致，即均一性。 當水凝膠經絞切後，若體積為200cm3以上，將之剪切、製粒 成小顆粒水凝膠的過程中，其小顆粒（不大於5cm”水凝膠製粒 性不佳，本發明中所謂製粒性係指水凝膠於製粒的過程中，通過 一固定大小的孔洞或篩網，得到所需大小的顆粒，而此小塊膠體 顆粒大小受限於孔洞或篩網孔徑，當顆粒大小愈接近，其製粒性 12 I33S016 愈佳。 絞切後之小輸水凝膠，經驗、烘乾會成為鶴的高吸水 性樹脂顆粒’乾燥触中，若加熱速度太快，易造成小顆粒水凝 膠表面先行乾燥部未乾，造錢體紐逸出1在其中形 成氣泡孔洞，大雛高吸水性難尤其顯著，當高吸水性樹脂氣 泡孔洞過多’研錢所產生的細粉亦隨之增加。L338〇l6 IX. Description of the Invention: [Technical Field of the Invention] The present invention provides a method for reducing the generation of fine powder of superabsorbent resin. According to this manufacturing method, the proportion of the fine powder can be reduced under the same conditions, the process performance of the superabsorbent resin can be improved, and the production efficiency of the super absorbent resin can be increased. [Prior Art] Superabsorbent resin Widely used in water conservation agents for agriculture or horticulture, anti-dew beads coagulants in building materials, and materials for removing moisture from petroleum, or outer layer waterproofing agents in cable and sanitary articles such as diapers, feminine hygiene Supplies, disposable wipes, etc. The component material of the superabsorbent resin known in the art is a hydrolyzed starch acrylonitrile graft polymer (Japanese Laid-open Patent Publication No. Sho 49 (1974)-43, 395). Neutralization Hall powder-acrylic acid graft polymer (Japanese Laid-open Patent Publication No. Sho 51 (1976) _125, 468), acetylated acetic acid _ propylene ester copolymer (Japanese Open Patent Gazette Sho 52 (1977) ~ 14 '689), hydrolyzed acrylonitrile copolymer or acrylamide copolymer (曰本公告昭 53 (1978) _15, 959), and partially neutralized polyacrylic acid (曰本特4告昭55(198G)'84 , 3G4) and so on. Among them, the raw material of _acrylonitrile is in the form of a natural polymer-starch, which causes the decomposition of rot 5 1338016, so it cannot be preserved for a long time. Moreover, the manufacturing method is very complicated, so J is nowadays The preparation method of the super absorbent resin is the most economical by using the superabsorbent resin obtained by cross-linking polymerization of acrylic acid and acrylate. The reason is that the raw material of the acrylate copolymer - acrylic acid can be quickly purchased from the market. In addition, the highly water-absorbent resin obtained has a high water absorption capacity, and has the advantages of low production cost, most economical efficiency, and decomposition without causing rot, so that it is the most general superabsorbent resin. # Polymeric acrylic acid and acrylate to form a superabsorbent resin can be obtained by several known methods such as water-soluble silk-spinning reaction, reverse-molecular polymerization, milking + reaction or monomer spray or A method of performing polymerization or the like by coating on a fibrous substrate. In 14 method towels, the reverse liquid suspension polymerization and emulsion polymerization must: use the solvent, but if there is no (10) control temperature, the organic solvent will contribute to the system temperature and pressure. The increase, causing the phenomenon of fire, even the miscellaneous bombings, threatens the safety of the personnel at the operating site and causes environmental pollution problems, and the finished product also has doubts about the residual organic solvent. SUMMARY OF THE INVENTION - [Problems to be Solved] In the art, methods have been developed to increase the surface area to improve the physical properties of the superabsorbent resin or to increase the production efficiency, for example, a method of adding a foaming agent. The method comprises the steps of: adding a crosslinked structure of a cross-linking agent to a linear water-hybrid polymer inversion with a fresh carbon foaming agent, while neutralizing and adding a cross-linking agent (U.S. Patent No. 4,529, 739, 6 to 38, No. 4, No. 4, 529, 739), adding a carbonate A method of polymerizing a monomer solution containing a carbonate by microwave (a method of superimposing a monomer solution of a carbonate (Japanese Patent No. 5,154,714, No. 5,314,420) U.S. Patent No. 4,808,637, the entire disclosure of which is incorporated herein by reference to U.S. Pat. No. 4, s. The method (U.S. Patent No. '328,935, No. 5,338,766), etc., wherein these methods for improving the physical properties of the superabsorbent resin utilize a blowing agent or a low boiling organic solvent for polymerization and heating. During the process, gas is decomposed to generate gas or vaporize to create pores for increasing the surface area when water is absorbed. However, the superabsorbent resin with too many pores in the pores tends to cause an increase in the amount of fine powder during the grinding process, which makes the finished product easy to cause when it absorbs water. Gel-blocking, if the amount of fine powder is not properly reduced, will greatly reduce the effectiveness of the actual application. [Technical means for solving the problem] The superabsorbent resin produced by the present invention is subjected to a polymerization reaction by initiating a radical. The acid-containing monomer required for the acid-containing monomer can be used in addition to acrylic acid, and other water-soluble solvents having unsaturated double bonds can be used. A monomer such as methacrylic acid, marinic acid, fumaric acid, 2-acrylamide-2-mercaptopropane sulfonic acid or the like. The monomers may be used without any particular limitation, and may be used in combination with a plurality of monomers. Optionally, other hydrophilic monomers having unsaturated double bonds may be added, such as acrylamide, mercapto acrylamide, acrylic acid. 2-yanyl ethyl vinegar, 2-hydrocarbyl ethyl methacrylate, methyl acrylate, ethyl acrylate, diamine propylene acrylamide, gasified acrylamide trimethyl ammonium, etc. (US Patent 13380*16 4, 057 , Nos. 521, 4, 062, 817, 4, 525, 527, 4, 286, 082 and 4' 295' 987), but the addition amount is based on the principle of not impairing the physical properties of the superabsorbent resin. The concentration of the aqueous monomer solution is preferably controlled to be in the range of from 20% by weight to about 55% by weight, based on the weight of the monomer, and the appropriate concentration is from 30% by weight to 45% by weight. Between the concentration below 20wt% by weight, the hydrated colloid is too soft and sticky after polymerization, which is unfavorable mechanical processing. The added concentration is above 55wt% by weight. When it is too close to the saturation concentration, it is difficult to prepare and the reaction is too fast. Too much to control. The carboxylic acid group of the acid group-containing monomer should be partially neutralized to control the pH of the finished product so that the neutral or slightly acidic 'neutralizer' is sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid unloading, sodium bicarbonate. , potassium bicarbonate and ammonia. The base of the money base monomer and the sodium or potassium salt or ammonium salt, the concentration of the molar concentration of the molar is 45 ships 1% to 85 secret, preferably 50mol% to 75_%, the percentage of towels and Symol For the Yang version, the PH value of the finished product will be low. When the percentage of the neutralization rolling molar is 85 or more, the value of the finished product will be high. If the pH value of the finished product is not neutral or slightly acidic, if it is inadvertently connected with the human body. It is neither suitable nor safe to contact. In the process of free silk-bonding, the water-soluble polymer is added to the water-soluble polymer to reduce the special secret of the core, such as: partially or completely saponified polyethylene, polyethylene glycol, polypropylene Riding, polyacrylamide, temple powder or temple powder derivatives such as vegetarian, (10) acid methyl fiber, B, cellulose and other polymers '· material water polymer molecular weight and sole responsibility, 対 better than 8 1338016 The water-soluble polymer is used alone or in combination of starch, partially saponified or fully saponified polyvinyl alcohol. The water-absorbent resin preferably has a suitable weight percentage of the water-soluble polymer of from 0 to 20% by weight, preferably from 0 to 110% by weight, particularly preferably from 5% to 5% by weight, and the water-absorbent component of the superabsorbent resin is more than 20% by weight. Low, will affect the physical properties to make the water absorption capacity worse. Before the radical polymerization reaction, a radical polymerization crosslinking agent should be added to the unreacted monomer solution, and the radical polymerization crosslinking agent may be a compound having two or more unsaturated double bonds. Such as: Ν, Ν-bis(2-propenyl)amine, Ν'Ν-decyl bis acrylamide, ν, ν' _ decyl bis decyl acrylamide, propylene acrylate, ethylene glycol Diacrylate, polyethylene glycol diacrylate, ethylene glycol dimercapto acrylate, polyethylene glycol dimethacrylate, glycerin triacrylate, glyceryl tridecyl acrylate, glycerin plus ethylene oxide Triacrylate or tridecyl acrylate vinegar, triterpene propane plus ethylene oxide triacrylate or tridecyl acrylate vinegar, trimethylolpropane trifyl acrylate, triterpene propane triacrylate, hydrazine, hydrazine , tris(2-propenyl)amine, ethylene glycol diacrylate, dipropylene triethylene glycol ester, etc., and compounds having two or more epoxy groups, such as sorbitol polyglycidyl ether, may also be used. , polyglycerol polyglycidyl ether, ethylene glycol dihydrate Oleic ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycerin polyglycidyl ether, and the like. After the radical reaction is carried out, 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 free radical polymerization crosslinker is suitably 9 1338016. The added dose is between 0.001% by weight and 5% by weight (based on the total solids of the reactants). More suitable amounts by weight in 〇.〇lwt% to 3wt Between 5% by weight, the amount of the additive is 0.001 wt% or less. The hydrated body is too soft and viscous after polymerization, and the amount of the additive is too low in water absorption of 5 wt% or more to lower the resin property. In order to increase the water absorption capacity of the superabsorbent resin, a long-chain bridging agent may be used, such as: long-chain 2-ethylpropanediol diethylene glycol acrylate, as shown in U.S. Patent No. 5,506,324. The properties of the long-chain cross-linking agent will effectively increase the retention of the superabsorbent resin. The reaction is initiated by the decomposition of the radical polymerization initiator to generate free radicals. The free radical initiator may be selected from a thermal decomposition type initiator, and a suitable thermal decomposition type starting agent: a peroxide such as hydrogen peroxide, di-tert-butyl peroxide, peroxidation; Persulfate (ammonium salt, alkali metal salt), etc., and azo compounds such as: 2, 2, ~ decyl bis(2-amidinopropane) dihydrochloride, 2, 2, azobis(7) , ^二伸甲甲基丁丁脉) Dihydrochloride: a reducing agent can also be used to make a redox initiator, such as: acidic sulfite, thiosulfate, ascorbic acid or ferrous salt; or The redox type initiator and the thermal decomposition type initiator are used in combination. First, the redox initiator starts to react to generate a radical, and when the radical is transferred to the monomer, the polymerization reaction is initiated, because the polymerization reaction proceeds. It will release a large amount of heat and raise the temperature by two. When the temperature is lowered, the decomposition temperature of the initial decomposition will trigger the decomposition of the second stage of the heat division, and the whole polymerization reaction will be more complete. Generally, the free radical polymerization initiator is used in an amount of _ to 10 1338016 10wt% (based on the weight of the neutralized acrylate), and more suitably in the range of 〇. lwt% to; 5wt%, using the weight Percentage 〇. OOlwt% or less, the reaction is too slow, unfavorable economic efficiency. When using the weight percentage above l〇wt%, the reaction is too fast and the reaction heat is not easy to control. [Embodiment] The polymerization reaction of the present invention can be carried out in a conventional batch reaction vessel or on a conveyor belt reactor, and the hydrogel polymer obtained by the reaction is the superabsorbent resin of the present invention. The hydrogel polymer as defined in the present invention generally refers to a super absorbent resin before drying, and the hydrogel obtained by the polymerization reaction is cut into a gel having a uniform size and a volume of 200 cm 3 or less, and then The mincer is pulverized into a small gel having a volume of 1 cm 3 or less and dried. The pure temperature is suitable for drying at a temperature of 丨, and drying at a temperature of 100 C or less. The time is too long to be economical, and the drying temperature is 18 〇.匸 绿 绿 绿 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 自身 自身 自身 自身 自身 ’ ’ ’ ’ ’ ’ ’ ’ ’ 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身 自身When producing polyacrylic superabsorbent resin, it will produce a superabsorbent resin with a particle size of not more than 1G6m during the process of pulverization, grinding and screening, which is called: fine powder; the amount of fine powder and high water absorption Sexual tree finances form a shouting bubble, there is absolute _ 'When superabsorbent resin gas · more bubble holes, the squeezing caused by smashing and grinding process _ 'to make bubbles empty _ high water absorption _ broken, The formation of fine powder' causes an increase in the amount of superabsorbent resin dust; the amount of fine powder depends on the environment and the production of the organism - the binding of the degree of enthalpy, especially in the air, the floating particles enter the lungs through the respiratory tract and thus produce the lungs. Increase the chance of lung and respiratory lesions' and when the amount of fine powder is sputum, the representative size is suitable for her fresh superabsorbent resin to reduce the 'catch of the turn, the Weisheng New rate and increase the cost; super absorbent resin water The distribution of gel size (homogeneity) is good or not, which directly affects the fine powder content of the finished product. When the uniformity of the size of the colloid is higher, the lower the fine powder produced in the production process, the lower the finished product. The lower the amount of fine powder, the more In line with the quality of the finished product requirements, how to reduce the amount of fines generated per unit time, that is a heavy research want. In order to reduce the amount of fine powder generated per unit time of the water-absorbent resin, increase production efficiency, and maintain stable production, the present invention utilizes a high-efficiency twisting method, which is characterized by: (1) high water absorption after polymerization The resin hydrogel should be controlled to a hydrogel of less than 200 cm3 before the granulation process. (2) Water condensate · After the body is cut, its volume should be the same, that is, uniformity. When the hydrogel is twisted and cut, if the volume is above 200 cm3, it is sheared and granulated into a small particle hydrogel. The small particles (not more than 5 cm) have poor granulation properties. In the context of the invention, granulating means that the hydrogel is granulated by a fixed-size hole or sieve to obtain particles of a desired size, and the size of the small colloidal particles is limited by the pore or mesh aperture. When the particle size is closer, the granulating property of 12 I33S016 is better. After the twisting, the small water-transfer gel, experience and drying will become the super absorbent resin particles of the crane's dry touch, if the heating speed is too fast, It is easy to cause the surface of the small particle hydrogel to dry before the drying part, and the money body is escaping 1 to form a bubble hole therein, and the high water absorption of the large chick is difficult to be particularly remarkable, when the super absorbent resin has too many pores of the bubble. Fine powder also increased.
时為檢驗本發明對細粉之料，可藉由下财法檢驗。首先將 早體中和，加入觸媒聚合得高吸水性樹脂水凝膠，取^水凝膠， 秤其重’得到其密度’再輯財式取數塊適當體積之水凝膠 塊’經孔徑為13刪的絞肉機（精浩公司之產品，型號為咖2 型）製粒，或以纏機（美利德公司之產品，型號為聽-SCN-2SIn order to test the fine powder material of the present invention, it can be inspected by the following financial method. Firstly, neutralize the early body, add the catalyst to polymerize the superabsorbent resin hydrogel, take the hydrogel, weigh the weight to get its density, and then collect the appropriate volume of the hydrogel block. A meat grinder with a pore size of 13 (a product of Jinghao Company, model No. 2) granulation, or a winding machine (Meleide's product, model is listening - SCN-2S
型）製粒，而其孔徑為17咖及8mm，隨機取樣1〇〇克高吸水性樹 脂顆粒，先秤得每-轉體難之質量，水凝_度之轉 換’換算出體積’以取得其顆粒體積之分佈。於此試驗中，大顆 粒水凝敎義減射掃^心錢膠，經贈c烘乾4〇 分鐘，後將上述細㈣吸___細粒，以標 準筛網網目為議，筛出並計算各粒徑的分佈比例，檢測不同大 小的水凝馳，所產錢泡㈣對細粉生成韻辟’並進行比 較，觀察水凝膠體積大小對造粒均一性的影響。Type) granulation, and its pore diameter is 17 coffee and 8mm, randomly sample 1 gram of superabsorbent resin particles, first weigh the quality of each turn, the conversion of water _ degree 'converted volume' to obtain Its particle volume distribution. In this test, the large particles of water condensed 敎 减 减 ^ 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心 心And calculate the distribution ratio of each particle size, detect the water condensation of different sizes, produce the bubble (four) on the fine powder to generate rhyme and compare, observe the effect of the size of the hydrogel on the uniformity of granulation.
，根據EDANA 本發明利JIS標準筛網來檢驗細粉的生成量 1338016 k驗方法第WSP 220· 2(05)號所描述的方法；將底部具有平盤白勺 篩網置於震動器中，篩網排列順序為網孔小者在下，啟動震動 器，其震幅為1.0刪，一段時間後停止震動器，篩選並分類出不 同粒徑的高吸水性樹脂，並利用下列方程式計算出各粒徑的分佈 比率。 粒徑分佈比率(%) = ,-一 脂[量―*100% 所有師網内南吸水性樹脂重量之總和 本發明為便於使用師選性能的評估，係將高吸水性樹脂中’ 粒徑小於l〇6um(JIS標準篩網為140mesh)視為細粉，利用其户斤占 比率的增減來判斷均一性對細粉的影響。 以下以實施例說明本發明；但本發明之專利及技術範圍則不 受這些實施例所限制。實施例中製粒機之孔徑為13mm，乾燥前高 吸水性樹脂顆粒膠體體積大於0.45cm3，視為製粒性較差者。 【實施例】 貫施例一： 1)將聚合後所得之高吸水性樹脂水凝膠（取lcm3水凝膠，科其 重為1.49克’密度為1.49 g/άτι3)，以撕裂方式取5塊體積 約為200cm3水凝膠’經孔徑13mm的絞肉機，絞碎製粒，隨機 取樣100克高吸水性樹脂顆粒’秤得每一個膠體顆粒之重量， 利用水凝膠密度為1.49 g/cm3，換算出體積，體積不小於 133^016 〇· 45cm3之大顆粒高吸水性樹脂水凝膠質量百分比’如表一所According to the EDANA invention, the JIS standard sieve is used to inspect the amount of fine powder produced by 1338016 k. The method described in the method of WSP 220· 2 (05); the sieve having the flat disk at the bottom is placed in the vibrator. The screen is arranged in the order of the smaller mesh, and the vibrator is activated. The amplitude of the screen is 1.0. After a period of time, the vibrator is stopped, the superabsorbent resin of different particle size is selected and classified, and each particle is calculated by the following equation. The distribution ratio of the diameter. Particle size distribution ratio (%) = , - one fat [quantity - * 100% The sum of the weights of the south water absorbent resin in the division network. The present invention is an evaluation of the performance of the candidate for the use of the water absorbent resin. Less than l〇6um (JIS standard screen is 140mesh) is regarded as fine powder, and the influence of uniformity on fine powder is judged by the increase or decrease of the proportion of the household. The invention is illustrated by the following examples; however, the patents and technical scope of the invention are not limited by these examples. In the examples, the pore size of the granulator was 13 mm, and the colloidal volume of the superabsorbent resin particles before drying was more than 0.45 cm3, which was considered to be poor in granulation. EXAMPLES Example 1: 1) A highly water-absorbent resin hydrogel obtained after polymerization (take a lcm3 hydrogel having a density of 1.49 g and a density of 1.49 g/άτι3), and take it in a tearing manner. 5 pieces of a volume of about 200cm3 hydrogel 'a meat grinder with a pore size of 13mm, ground granulation, random sampling of 100 grams of superabsorbent resin particles' to weigh the weight of each colloidal particle, using a hydrogel density of 1.49 g /cm3, the volume is converted, the volume is not less than 133^016 〇· 45cm3 of the large particle superabsorbent resin hydrogel mass percentage' as shown in Table 1
Tfx ° 2)將上述絞碎後之大、小水凝膠顆粒，以180°C乾燥40分鐘， 研磨後，利用JIS標準篩網篩選細粉量，網目為140，震動器 震盈時間為10分鐘，細粉之質量比如表一所示。 實施例二： 1) 重覆實施例一步驟1)，取得其體積之質量分佈比，如表二所 示0 2) 重覆實施例-步驟2)，將上述隨機取樣1〇〇 {高吸水性樹脂 膠體顆粒’乾燥、研磨、筛選後，細粉之質量比如表二所示。 實施例三： 重覆實施例二，改取長議刪、寬m :=:_水凝膠進行試驗，其膠體顆粒與細粉之質: 實施例四： 重覆實施例二，改取長50 umm良50細1、厚4〇 高吸水性雛錢膠，赫 100cm3 ^ 細粉之質量比如表二所示。 比較例一： I33S016 重覆實施例一，改取體積約500cm3高吸水性樹脂水凝膠聚合 物，其乾燥、研磨、篩選後，細粉之比例如表一。 比較例二： 重覆實施例一，改取體積約100、150、200、250及300 cm3 高吸水性樹脂水凝膠各一，其乾燥、研磨、篩選後，細粉之比例 如表一0 水凝膠體積（cm3) 大顆粒水凝 大顆粒水凝膠 小顆粒水凝膠研 ·， X塊數 膠比 研磨後細粉量 磨後細粉量 ，· 實例一 200x5 6. 35% 8. 60% 3. 23% • 比較例一 500x5 12. 11% 25. 64% 3. 06% 100x1 、 150x1 * 比較例二 200x1 、 250x1 9. 21% 16. 24% 3. 62% • 300x1 16 1338016Tfx ° 2) The above-mentioned ground large and small hydrogel particles were dried at 180 ° C for 40 minutes. After grinding, the fine powder amount was screened by JIS standard sieve, the mesh was 140, and the vibrator shock time was 10 Minutes, the quality of the fine powder is shown in Table 1. Example 2: 1) Repeat step 1) of Example 1 to obtain the mass distribution ratio of the volume, as shown in Table 2, 2) Repetitive Example - Step 2), and randomly sample 1 〇〇{high water absorption After the resin colloidal particles are dried, ground and screened, the quality of the fine powder is shown in Table 2. Example 3: Repeat the second embodiment, and change the long-term deletion and width m:=:_ hydrogel test, the quality of the colloidal particles and the fine powder: Example 4: Repeat the second embodiment, change the length 50 umm good 50 fine 1, thick 4 〇 high water absorption chick money, He 100cm3 ^ fine powder quality as shown in Table 2. Comparative Example 1: I33S016 By repeating Example 1, a superabsorbent resin hydrogel polymer having a volume of about 500 cm 3 was changed, and after drying, grinding, and screening, the ratio of fine powder was as shown in Table 1. Comparative Example 2: Repeating Example 1, the volume of each of the superabsorbent resin hydrogels having a volume of about 100, 150, 200, 250 and 300 cm3 was changed, and after drying, grinding and screening, the ratio of the fine powder was as shown in Table 1. Hydrogel volume (cm3) Large particle hydrogel large particle hydrogel small particle hydrogel research · X block number of rubber than fine powder after grinding, fine powder amount, · Example one 200x5 6. 35% 8. 60% 3. 23% • Comparative Example 1 500x5 12. 11% 25. 64% 3. 06% 100x1, 150x1 * Comparative Example 2 200x1, 250x1 9. 21% 16. 24% 3. 62% • 300x1 16 1338016
表二 水凝膠 塊體積 不同水凝膠顆粒體積之質量分佈比 細粉量 >0.45 0.45 〜0.3 0.3 〜0.15 <0.15 實例二 200 cmJ 5. 62% 27. 85% 45.12% 21.42% 3. 91% 實例三 100 cm3 (長 10cm 寬 10cm 高 1cm) 3. 28% 28. 59% 49. 33% 18. 8% 1,44% 實例四 100 cm3 (長 5cm 寬5cm 高 4cm) 3.81% 27. 31°/〇 48. 25°/〇 20.63% 1.62%Table 2: The volume distribution of hydrogel block volume is smaller than that of fine powder volume > 0.45 0.45 ~ 0.3 0.3 ~ 0.15 < 0.15 Example 2 200 cmJ 5. 62% 27. 85% 45.12% 21.42% 3. 91% Example 3 100 cm3 (length 10cm width 10cm height 1cm) 3. 28% 28. 59% 49. 33% 18. 8% 1,44% Example 4 100 cm3 (length 5cm width 5cm height 4cm) 3.81% 27. 31°/〇48. 25°/〇20.63% 1.62%