201100472 六、發明說明： 【發明所屬之技術領域】 本發明是有關於高吸水性樹脂的製造方法，特別是一種細粉回收方 法。本發明所述的方法相當簡便，除了可以提高生產效率外，更能夠使製 造過程趨於穩定。 【先前技術】 尚吸水性樹脂的成分材料有遇水分解型的澱粉丙烯腈(hydr〇丨 starch-acrylonitrile)接枝聚合物（日本專利公開公報昭49^974)43 395)， 中和之澱粉丙烯酸接枝聚合物（日本專利公開公報昭51 (1976)-125,468)，4化乙觸酸丙㈣共聚物（日本專利公開公報昭 52(1977)-14,689) ’水解丙烯腈共聚物或丙烯醯胺共聚物（日本專利公報 昭53 (1978)-15,959)，及部份十和聚丙烯酸（日本專利公開公報昭 55(1980)-84,304)等。其中以使用丙稀酸及丙婦酸鹽進行交聯聚入所得之 高吸水性樹脂佔最大部份也最為經濟，其為㈣酸可迅速:市隹取 得:且製㈣高吸水性齡具有高的吸水能力，及具有製造成本低廉且最 具經濟效益’故成為最普遍化的高吸水性樹脂。 用於進行丙烯酸鹽聚合的反應記被衫開發成功201100472 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a super absorbent resin, and more particularly to a method for recovering fine powder. The method of the present invention is relatively simple, and in addition to improving production efficiency, the manufacturing process can be stabilized. [Prior Art] The component material of the water-absorbent resin is a water-decomposable starch acrylonitrile-acrylonitrile graft polymer (Japanese Patent Laid-Open Publication No. SHO 49-974) 43 395), neutralized starch Acrylic graft polymer (Japanese Patent Laid-Open Publication No. Sho 51 (1976)-125, 468), 4-B-Acetylpropane (tetra) copolymer (Japanese Patent Publication No. Sho 52 (1977)-14, 689) 'Hydrolyzed Acrylonitrile Copolymer or Acrylonitrile An amine copolymer (Japanese Patent Publication No. Sho 53 (1978)-15, 959), and a part of the tenth and polyacrylic acid (Japanese Patent Laid-Open Publication No. Sho 55 (1980)-84,304) and the like. Among them, the superabsorbent resin obtained by cross-linking and using acrylic acid and proacetate is the most economical, and it is (4) acid can be quickly: market-achieved: and (4) high water-absorbent age is high Its water absorption capacity, and its low cost of manufacture and the most economical benefits, it has become the most popular superabsorbent resin. The reaction quilt used for acrylate polymerization was successfully developed.
48(1973) 4)，捏拌 ^2,46^ ’皮τ式帶反應器（曰本專利公開昭和58(1983Μ9,7Ί4)， 機反應器（日本專利公開昭和57(1982W他、站松 ’48 (1973) 4), kneading the ^2,46^' skin t-belt reactor (曰本专利专利昭和58(1983Μ9,7Ί4), machine reactor (Japanese Patent Publication Showa 57 (1982W He, Station Song ’
201100472 低實際應用之性能 【發明内容】 高吸水性麵具錢大_水力，可做秘甚錄千條 的水’且吸水後可賴具有簡錢__，即使施祕力也不會渗漏， 且被吸收的水可緩緩地在大氣巾㈣。由於具有上述之·，所以最早使 用於農森林業的土壌保水劑，近年因高吸水性樹脂社產技術有相當大的 ，步，所以也廣泛地於衛錢品如尿布、成人失翻品及婦女衛生用 πσ的吸水劑及保存食物用的保鮮應用等。 Ο201100472 Low practical application performance [Invention content] High water absorption mask money big _ water power, can do secrets even record thousands of water 'and water absorption can rely on simple money __, even if the secret force will not leak, And the absorbed water can be slowly in the air towel (4). Because of the above, the earliest water-retaining agent used in the agricultural forestry industry has been widely used in the past few years because of the high-absorbency resin production technology, so it is also widely used in money-saving products such as diapers and adult products. Women's hygiene uses πσ water-absorbing agent and preservation application for preserving food. Ο
本發明之製造吸水性樹财法巾的含雜單體，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_酸、或馬林酸、或富馬 酸、或2-丙烯胺-2-f基丙貌猶等。單體選用不特定限制只可使用一種， 亦可合併多鮮體-齊制，亦可視情況需要添加具林飽和雙鍵其他親 水性的單體，如:丙_胺、甲基丙烯_、丙稀酸2_烴基乙醋、甲基丙稀 酸2-煙基乙醋、丙烯酸甲醋、丙稀酸乙醋、二甲胺丙稀丙稀酿胺、氣化丙 稀丙稀醯胺基三愤但添加量以不破壞高吸水性樹脂之物性為原則。 在進行自由絲合反應前，單體水溶液濃度宜㈣在重量百分比 20wt%至55wt%@’適當濃度為3Qwt%^45wt%：^，敍在重量百分比 =wt%以下時’聚合後水合體錄且有雜私織械加工，添加濃度在重 畺百刀比55wt/〇ixji ’接近飽和濃度，不胃調配且反應太快反應熱不易控 含酸基單體之紐基應部份令和以控制成品之pH值，使呈中性或微酸 f生中和劑為氫氧化鐘、氫氧化鈉、氫氧化鉀、碳酸裡、碳酸鈉、碳酸鉀、 碳酸氫H、碳酸氫鋼、碳酸氫舒及氨。含酸基單體之竣酸基將部份中和成 經鹽或鈉鹽物贱紐或兩種以上混合魏，中和濃度莫耳百分比為 5mol/S至85m〇l%，適當濃度為5〇mol%至75mol%，中和漢度莫耳百分 比為45=1%以下時成品之pH值會偏低，中和濃度莫耳百分比為85_% 以上時成品之pH值會偏高，成品pH值若非呈條或微酸性時，不慎與人 體接觸時均不太適合也較不安全。 5 201100472 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’此自由絲合反應交·可選用具有兩個或兩個社不飽和雙 鍵的化合物，例如，N，N-雙(2-丙烯基)胺、N，N‘-次甲基雙丙稀酿胺、N N‘_ 次甲基雙甲基丙烯醯胺、丙烯酸丙烯酯、乙二醇二丙烯酸酯、聚乙二醇二 丙烯酸酯、乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、甘油三丙 烯酸酯、甘油二甲基丙烯酸酯、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 甲醇丙烷三甲基丙烯酸酯、三甲醇丙烷三丙烯酸酯、n n，n_三(2_丙烯基） 胺、二丙烯酸乙二醇S旨、二丙烯三甘_旨等’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_001wt%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0.01wt%至3wt%之間，添加劑量在重量百分比〇 〇〇1wt%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。 聚合反應由起始劑的產生自由基開始，而起始劑可選用熱分解型起始 劑，例如過氧化氫、二-第三丁基過氧化物、過氧化醯胺或過硫酸鹽(銨鹽、 驗金屬鹽)等’及偶氣化合物如，2,2，-偶氮基雙(2-脒基丙烷)二鹽酸鹽、2,2，-偶氮基雙(N，N-二伸曱基異丁脎)二鹽酸鹽；亦可使用還原劑，使成為氧化還 原型起始劑，例如酸性亞硫酸鹽、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高，當溫度到達熱分解型 起始劑的分解溫度時，又會引發第二段熱分解型起始劑的分解，而使整個 聚合反應更臻於完全。一般自由基聚合反應起始劑適當用量為重量百分比 為0_001wt%至10wt%(以中和丙烯酸鹽重量為基準），更適當用量則在 201100472 〇.1wt%至5wt%之間，使用重量百分比O.OOlwt%以下時，反應太慢不利經 濟效益，使用重量百分比10wt%以上時’反應太快反應熱不易控制。 本發明係將聚合反應所得成品之塊狀膠體，先利用絞碎機切成直徑 20mm以下小凝膠體(直徑i〇mm以下更佳），而後進行烘乾。 烘乾溫度可於100°C至250°C下進行乾燥，乾燥溫度則以12CTC至180 °C進行烘乾為宜，當烘乾溫度溫度120。(：以下則烘乾時間太久不具經濟效 益，烘乾溫度18CTC以上烘乾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，達到降低低殘存單 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理。薛選 〇 固定粒徑以6〇pm至ΊΟΟΟμηι間為宜，以ΐΟΟμηι至85c^m間較佳，粒徑 以下細粉使成品粉塵提高，粒徑1〇〇〇pm以上粒子使成品吸水= 變慢。 ， 、^ 乾燥後進行粉碎、篩選固定粒徑，再進行表面交聯劑塗覆處理。篩選 固定粒彳坐以60μιτι至ΊΟΟΟμπι間為宜，以ΐΟΟμηη至85〇μηη間較佳。粒徑 大於850μηι的吸水性樹脂會使後來成品吸水速率變慢，需再一次進行研 磨；粒徑小於1〇〇pm的吸水性樹脂則會造成成品粉塵量偏高，故需要進行 回收的步驟以節省成本舆提高生產效率。一般來說，回收的方式有二：第 一 ^將粒徑在1〇〇μηΊ至850pm的吸水性樹脂與粒徑小於1〇〇邮的吸水性 〇 樹脂以適當的比例作混合；第二，以增濕的方式，使粒徑小於的吸 水&細3黏附於粒彳纟在至8_m的吸水性細旨表面，以達到回 與降低粉塵的侧。上述兩種方式均有不適當的地方，第―種回收方式六 易=響品質穩定性，而第二種方式則需要增設細粉造粒的設備，且日= 有堍備清理與維修的問題(細粉增濕易產生結塊) 。鐘於此，本發明提供了 _ 種回收細粉的方法，其主要步驟為： ’、— 1.於縣槽内，將欲回收之粒徑小於1〇_、細粉與驗性中和劑依1 : 1〜1 : 13重量比例混合攪拌； 2·將含酸基單體水溶液中和度5〇^%以上與上述液體混合； 3.添加父聯劑至2所述之單體水溶液中後； 再添加起始劑於3.進行聚合反應，並於反應器_滯留25分； 201100472 5.使單體水溶液逐漸轉變為膠體。 與中和劑混二=Γ理並不會造成生產上的另-個負擔，因為細粉 摻二中=;粉增濕的結塊現象。最重要的是，細粉不混 成β中對於ασ質的穩定性也不會造成影響。 本發明之枝於轉㈣減後，於表面處 聯劑可為多元醇如：丙三醇、乙二醇、 bn W了反應的父 5 三煙基曱基碰、山梨醇等；或可使眼胺如：乙 氣、二H紅二胺；或可使㈣有兩個或兩個以上環 Γ= 梨醇聚縮水甘油醚、聚丙三醇聚縮水甘_、己二醇 、二乙二醇二縮水甘_、聚乙二醇二聚縮水甘油醚、雙丙 二，聚縮水甘油鱗；亦可使祕酸亞触旨如：乙二醇碳_ H 3_ -二雜環戊烷-2-酮、4,5-二曱基-1,3-二氧雜it戊烷_2嗍、4 I 3_ 二氧雜環戊务2嗍、4-乙基-1,3-二氧雜軸烧_2__、j 3_二 ^ ’ ^你二甲基-以二氧雜環己极酮或以二氧雜環魏抑等。-法可單獨使用或兩種以上混合使用。表聽交聯_適當添 加劑1在重1百纽議^%至_%之間(以反應物總_份為基 更適當_量在Q.⑽wt%至5wt%之間，表面處交聯獅㈣量^量百 分比_1wt%以下時無法顯出效果，絲處交鶴添加·在重量百分比 1〇wt%以上時，吸水性太低，降低樹脂性能。 表面交聯劑塗覆處理時’纟面交聯劑之添加可絲面交聯劑直接添 加’或調絲面交_水溶液添加’或調絲面交聯舰水性^溶劑水 溶液添加，親水性有機溶劑如曱醇、乙醇、丙醇、異丁醇、丙酮、甲醚、 乙醚等没有特殊限制，可形成溶液即可，其中以曱醇、乙醇較佳。表面交 聯劑添加時高吸水樹脂中可添加惰性無機鹽粉末，以幫助溶液^散^隋性 無機鹽粉末可為硫酸鋁、或二氧化矽，或氧化鋁，或氧化鎂等或其混合^。 其中以硫酸鋁、二氡化矽較佳。惰性無機鹽粉末添加範圍在重量^分比 0.005wt%至i〇.〇wt%之間，其中以0.01 wt%至4.0wt%較佳。 刀 進行表面交聯劑塗覆處理後，再以8CTC至23CTC加熱處理，使表面交 聯劑能進行交聯反應，並使内部交聯劑進行交聯反應而達到本發明之$ 201100472 〇 廉度80C以下父聯反應時間太久，不具經濟效益，處理溫度2230 3周Γ易劣化影響品質。至於處理時間則以2〜150分鐘為宜，依處理 &度凋整，溫度高則時間短，溫度低則時間長。The hetero-containing monomer for producing the water-absorbing tree of the present invention can use other water-soluble monomers having unsaturated double bonds, such as methyl-acid, or marlinic acid, or fuma, in addition to acrylic acid. Acid, or 2-propenylamine-2-f-based propylene. Monomers can be used without any specific limitation. They can also be combined with multi-fresh-synthesizing. It is also necessary to add other hydrophilic monomers with saturated double bonds, such as: propylamine, methacrylic _, and C. Dilute acid 2_hydrocarbyl ethyl vinegar, 2-methyl ketone methacrylate, methyl acetonate, acetoacetate, dimethylamine propylene amide, gasified propylene amide Indignant, but the amount added is based on the principle of not destroying the physical properties of the superabsorbent resin. Before the free silking reaction, the concentration of the aqueous monomer solution is preferably (4) at a weight percentage of 20% by weight to 55wt%@'the appropriate concentration is 3Qwt%^45wt%: ^, when the weight percentage = wt% or less, 'the hydrated body after polymerization And there is a heterogeneous woven machine processing, adding concentration in the weight of a hundred knives ratio 55wt / 〇 ixji 'close to saturation concentration, no stomach compounding and reaction too fast reaction heat is not easy to control the acid-based monomer of the new base should be Control the pH value of the finished product so that the neutralizing agent is neutral or slightly acidic. The hydroxide, sodium hydroxide, potassium hydroxide, carbonic acid, sodium carbonate, potassium carbonate, hydrogen carbonate H, hydrogen carbonate steel, hydrogen carbonate Shu and ammonia. The decanoic acid group containing an acid group monomer is partially neutralized to a salt or a sodium salt lanthanum or a mixture of two or more kinds, and the concentration of the neutralizing concentration is from 5 mol/s to 85 m 〇l%, and the appropriate concentration is 5 〇mol% to 75mol%, the neutralization of the molar percentage of 45 = 1% or less will lower the pH of the finished product, the neutralization concentration of the molar percentage of 85% or more will be higher, the finished product pH will be higher, the finished product pH If it is not stripped or slightly acidic, it is not suitable or safe to contact with the human body. 5 201100472 Before the free radical polymerization, the free radical polymerization crosslinker should be added to the unreacted monomer solution. 'This free silky reaction can be mixed. ·A compound with two or two unsaturated double bonds can be selected. For example, N,N-bis(2-propenyl)amine, N,N'-methine diacrylamide, NN'_ methine dimethyl methacrylate, propylene acrylate, ethylene glycol II Acrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, glycerin triacrylate, glycerin dimethacrylate, glycerin plus ethylene oxide Acrylate or tridecyl acrylate, trimethylolpropane plus ethylene oxide triacrylate or trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, nn, n_three ( 2—propenyl)amine, ethylene glycol diacrylate, dipropylene triethylene, etc. may also be selected from compounds having two or more epoxy groups, such as sorbitol polyglycidyl ether, polyglycerol Polyglycidyl ether, ethylene glycol diglycidyl ether, diethyl Glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether and the like bis. After the radical reaction, the superabsorbent resin can have a proper degree of crosslinking, and the highly water-absorbent resin colloid has 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 present in an amount of from 0 to 001% by weight to 5% by weight based on the total solids of the reactants, more suitably in an amount of from 0.01% by weight to 3% by weight, based on the amount of the additive. The hydrate is too soft and viscous after polymerization at a weight percentage of 〇〇〇 1 wt% or less. Mechanical processing 'The amount of the additive is too low at a weight percentage of 5 wt% or more to lower the resin property. The polymerization starts with the free radicals of the initiator, and the initiator can be selected from thermal decomposition initiators such as hydrogen peroxide, di-tert-butyl peroxide, guanidinium peroxide or persulphate (ammonium). Salt, metal salt, etc. and oxy compounds such as 2,2,-azobis(2-amidinopropane) dihydrochloride, 2,2,-azobis(N,N-di Dihydrochloride; dihydrochloride; may also be used as a redox initiator, such as acidic sulfite, thiosulfate, ascorbic acid or ferrous salt; or redox The initiator and the thermal decomposition initiator are used in combination. First, the redox initiator first reacts to generate a radical, and when the radical is transferred to the monomer, the polymerization reaction is initiated, and a large amount is released due to the polymerization reaction. The heat increases the temperature, and when the temperature reaches the decomposition temperature of the thermal decomposition type initiator, decomposition of the second stage thermal decomposition type initiator is caused, and the entire polymerization reaction is more complete. Generally, the radical polymerization initiator is suitably used in an amount of from 0 to 001% by weight to 10% by weight based on the weight of the neutralized acrylate, and more suitably in the amount of from 201,100,472 to 1% by weight to 5% by weight, using the weight percentage O. When the pressure is below OOlwt%, the reaction is too slow and the economic benefit is unfavorable. When the weight percentage is 10% by weight or more, the reaction is too fast and the heat of reaction is not easily controlled. In the present invention, the finished block-like colloid obtained by the polymerization reaction is first cut into a small gel body having a diameter of 20 mm or less (better than the diameter i〇mm or less) by a mincer, and then dried. The drying temperature can be dried at 100 ° C to 250 ° C, and the drying temperature is preferably dried at 12 CTC to 180 ° C, and the drying temperature is 120. (: The following drying time is too long and has no economic benefit. The drying temperature is above 18CTC to make the cross-linking agent cross-link early, so that the residual drying process is too high and the residual residue cannot be effectively removed. Body, to reduce the effect of low residual monomer. - After drying, pulverize, screen fixed particle size, and then apply surface crosslinker coating. Xuexun 〇 fixed particle size from 6〇pm to ΊΟΟΟμηι is appropriate, ΐΟΟμηι It is better to 85c^m, the fine powder below the particle size is used to improve the finished dust, and the particles above 1 pm are used to make the finished product absorb water = slow down. , , ^ After drying, pulverize, screen the fixed particle size, and then carry out the surface. Cross-linking agent coating treatment. Screening of fixed granules is preferably between 60μmτι and ΊΟΟΟμπι, preferably between ΐΟΟμηη and 85〇μηη. The water-absorbent resin with a particle diameter of more than 850μηι will slow down the water absorption rate of the finished product. Grinding; water-absorbent resin with a particle size of less than 1 pm will result in a high amount of finished dust, so a recycling step is required to save costs and improve production efficiency. There are two ways of recycling: first, the water-absorbent resin having a particle diameter of 1 〇〇μηΊ to 850 pm and the water-absorbing cerium resin having a particle diameter of less than 1 Å are mixed in an appropriate ratio; second, to humidify In a manner, the water absorption & fine 3 having a particle diameter of less than 5 mm is adhered to the surface of the water-repellent fine-grained surface of the granules to reach the side of the dust-reducing dust. The above two methods have inappropriate places, the first species The recycling method is easy to sound = the quality is stable, while the second method requires the addition of fine powder granulation equipment, and the day = there is a problem of cleaning and maintenance (fine powder humidification is easy to produce agglomeration). The present invention provides a method for recovering fine powder, the main steps of which are: ', - 1. In the county tank, the particle size to be recovered is less than 1 〇 _, fine powder and the neutralizing agent according to 1: 1~1 : 13 by weight mixing and stirring; 2. Mixing the acid group-containing monomer aqueous solution with a degree of neutralization of 5 〇^% or more with the above liquid; 3. Adding the parent crosslinking agent to the aqueous monomer solution described in 2; Adding the initiator to 3. Carry out the polymerization and retain 25 minutes in the reactor; 201100472 5. Let the aqueous monomer solution gradually It is converted into a colloid. Mixing with the neutralizing agent = does not cause another burden on the production, because the fine powder is mixed with the second; the powder is humidified and agglomerated. The most important thing is that the fine powder is not mixed. β does not affect the stability of ασ. After the branch of the present invention is reduced, the crosslinking agent at the surface may be a polyol such as glycerol, ethylene glycol or bn W. Trisodium thiol thiophene, sorbitol, etc.; or ophthalmic amines such as: Ethylene, diH red diamine; or (4) having two or more ring Γ = sorbitol polyglycidyl ether, polypropylene Alcohol polycondensation _, hexanediol, diethylene glycol diglycidyl _, polyethylene glycol dimerglycidyl ether, double propylene di, polyglycidol scale; can also make the secret acid sub-touch as: Alcohol carbon_H 3_ -bicyclopentan-2-one, 4,5-dimercapto-1,3-dioxa itpentane 2嗍, 4 I 3_dioxolane 2嗍, 4-Ethyl-1,3-dioxolexostat_2__, j 3_二^ ' ^ You dimethyl-dioxane hexanone or dioxane oxime. The method may be used singly or in combination of two or more. Table Listening Crosslinking_Appropriate Additive 1 is between 1% and _% by weight (more suitably based on the total amount of reactants). The amount is between Q. (10) wt% and 5 wt%. (4) When the amount is less than or equal to _1wt%, the effect cannot be exhibited. When the weight is above 1% by weight, the water absorption is too low to lower the performance of the resin. The addition of the surface crosslinking agent can be directly added to the silk-face crosslinking agent, or the addition of the surface of the wire to the surface of the water-soluble solvent, and the hydrophilic organic solvent such as decyl alcohol, ethanol, propanol, Isobutanol, acetone, methyl ether, diethyl ether, etc. are not particularly limited, and a solution may be formed, wherein decyl alcohol and ethanol are preferred. When a surface crosslinking agent is added, an inert inorganic salt powder may be added to the superabsorbent resin to help the solution. The powder of the inorganic salt may be aluminum sulfate or cerium oxide, or aluminum oxide, magnesium oxide or the like or a mixture thereof. Among them, aluminum sulfate and cerium oxide are preferred. The inert inorganic salt powder is added in the range of The weight ratio is between 0.005 wt% and i〇.〇wt%, wherein 0.01 wt% to 4.0 wt% is preferred. After the knife is subjected to surface crosslinking agent coating treatment, heat treatment is performed at 8 CTC to 23 CTC to enable the surface crosslinking agent to carry out a crosslinking reaction, and the internal crosslinking agent is subjected to a crosslinking reaction to reach the invention of $201100472. The degree of parental reaction time below 80C is too long, and it has no economic benefit. The treatment temperature is 2230, 3 weeks, and it is easy to degrade and affect the quality. The treatment time is 2~150 minutes, depending on the treatment & degree, the temperature is high and the time is short. The temperature is low and the time is long.
=吸水性樹脂具有賴後結塊的現象，域免在絲度地區使用高吸 =:=結塊導致加工不順，一般會在高吸水性樹脂表面塗附 青:、機皿如末或界面活性劑，使表面略具親油性而使高吸水性樹脂保有 吸濕後不躲_雜，此雜錢藉末可選驗義、或二氧化石夕、 f氧化銘，、或氧化鎖、或氧化約、或高嶺土、或碳酸辦、或碳酸鎂等或其 此口，，if巾此惰性無機鹽粉末的添加量與無機鹽粉末顆粒粒徑大小有 關^顆粒粒HJ、其無機鹽粉末比表面積較大，所以有效惰性無機鹽粉 末用量可較小’其.紐無機鹽粉末添加範圍為重量比百分比q 至 mowt%之間，射以0.01福至4 〇wt%較佳，惰性無機鹽粉末其粒徑為 0_001μΜ至1〇〇μΜ ’若選用顆粒小於〇 〇〇1|jM的無機鹽粉末則成本過高 不利^工業化生產’若選用顆粒大於1〇_的無機鹽粉末則有添加量過高 衫響同吸雜樹脂吸收力賴題。惰性無_粉末可單獨添加或可伴隨界 面活性劑或具減錢化合物加人，其界面雜臟具減有機化合物可 選用HLB值12以上非離子性界面活性劑、或水溶性陰離子型界面活性劑、 或陽離子型界面活_、或陰陽兩性型界面活性劑、或其混合物，通常界 面活性劑或獅度錢化合物可使用甘油、乙二醇、己六醇、聚氧乙稀醇、 或聚乙二醇、或硬月旨酸聚乙二醇醋、或硬脂酸聚乙二醇己六醋 '或聚氧 化乙稀壬苯醚、或聚氧化乙烯辛_、或聚氧化乙烯十二苯醚、或聚氧化 乙烯院基_、絲輸乙婦月細等此界研性贼純度錢化合物可 調配成水雜養、;6〇人或糊加人’適當的界面活性贼具紐有機化合 物添加劑量在重量百分比0.001wt%S 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0.01wt%至3wt%之間。 本發明係提供-種高吸水性樹脂的製造方法，此方法包括以下步驟： (1)將粒徑小於100pm回收細粉與鹼性中和劑依彳：彳〜彳：13重量比 混合攪拌； (2) 再將含酸基爭體水溶液與含細粉之中和劑混合； (3) 添加交聯劑至中和度5〇m〇|e%以上之含酸基單體水溶液； 201100472 (4) 添加起始劑於含酸基單體水溶液單體溶液中進行聚合反應生成水凝 膠體，並於反應器中滯留25分； (5) 以恤度iq〇c至250。〇熱風進行乾燥、粉碎、篩選； (6) 表面交聯劑塗覆處理； ⑺溫度8CTC至230°C加熱表面處理； (8)添加惰性無機鹽粉末。 其中’其篩選後粒徑為15〇μηι至850μηι。 其中，其表面交聯劑添加之重量百分比為〇 〇〇5wt%〜5 〇wt%。 其中’其惰性無機鹽粉末添加之重量百分比為〇 〇倾％〜4 0M%。 本發明提供之方法除可以簡化細粉回收的操作性與提高生產效率之 外，對於品質的穩定性也不會造成影響。 以下詳細地列出工作實例以便說明本發明，但本發明範圍不受這些實 例所限制® _ 【實施方式】 【實例一】 本發明之咼吸水性樹脂的製造方法，此方法包括以下步驟： 1·先於100L反應槽中加入49°/。液鹼15_26kg，並在攪拌下(轉速為 50-75rpm)加入粒徑小於ΙΟΟμητι的高吸水性樹脂〇.6lkg。 2. 之後於冰浴下將丙烯酸水溶液45.74kg(丙烯酸:水=3:4)緩慢加入上 述溶液中進行中和。 3. 加入19_52g的丙三醇聚乙二醇三縮水甘油醚(n=7)於部分中和的丙 烯酸水溶液，並維持溫度於5-8°C左右。 4. 分別控制部分中和的丙烯酸鈉水溶液、抗壞血酸、過硫酸鈉及二_ 第三丁基過氧化氫的流量為61.00kg/hr、249.55g/hr、554.55g/hr 與554.55g/hr，並利用流動的方式使其混合並連續地排入反應皮帶 上。此外’出料後並未發現有細粉於槽内結塊或殘留於槽壁上的現 象。 5. 控制4.所述溶液於皮帶上的滯留時間為25min。 6. 將反應完成的大塊膠體以切刀與擠壓機製成2mm直徑以下的小凝 膠體。 10 201100472 7_以150°C溫度乾燥90分鐘後，將乾燥的凝膠體進行研磨。 8·利用篩網篩選Ι50μηη〜850μηι固定粒徑，得至丨丨古 Α Q t ^ 耻仅仔到叼吸水性樹脂粉體。 9.秤取尚吸水性树脂1〇〇g，加入乙二醇碳酸酯/水/甲醇= (重量比） 溶液4g，以215°C溫度加熱處理1〇分鐘。 10.冷卻後，加入1g碳酸約(台塑公司生產；品名：机2〇〇〇)及2〇%甘 油水溶液2g，均勻混合後即得高性能高吸水性樹月旨。 11_分析所得之高吸水性樹脂的物性表現為：保持力=327g/g、 AAP(0_3psi)=32.1、AAP(0.7psi)=16.8g/g、’殘、留單體含量 =300ppm、可溶份(16hr)=17.1%。 〇 【實例二】 1. 重覆實例一’但將步驟1·所述之粒徑小於ΙΟΟμιτι高吸水性樹脂的添 加量調整為1_83kg。此外’步驟4.所述之L-抗壞血酸的流量也需調 整為 221.82g/hr。 2. 與實例一情形相似’混合槽排空後並未發現有細粉於槽内結塊或殘 留於槽壁上的現象。 3. 分析所得之高吸水性樹脂的物性表現為：保持力=33.0g/g、 AAP(0.3psi)=31.6、MP(0_7psi)=17.3g/g、殘留單體含量=280ppm、 可溶份(16h「)= 18.0%。 〇 【實例三】 ^ 重覆實例一，但將步驟1.所述之粒徑小於1〇〇μηι高吸水性樹脂的添加量調 整為3.05kg。此外，步驟4.所述之L-抗壞血酸的流量也需調整為 194.09g/hr。 1. 與實例一情形相似’混合槽排空後並未發現有細粉於槽内結塊或殘 留於槽壁上的現象。 2. 分析所得之高吸水性樹脂的物性表現為：保持力=32.〇g/g、 AAP(0.3psi)=32.5、MP(〇_7psi)=17.1g/g、殘留單體含量=305ppm、 可溶份(16h「)= 17.5%。 【實例四】 1.重覆實例一’但將步驟1 ·所述之粒徑小於1 ooi·1 m高吸水性樹脂的添 11 201100472 加量調整為4.27kg。此外’步驟4.所述之匕抗壞血酸的流量也需調 整為 166.37g/hr。 2. 與實例一情形相似，混合槽排空後並未發現有細粉於槽内結塊或殘 留於槽壁上的現象。 3. 分析所得之高吸水性樹脂的物性表現為：保持力=33.〇g/g、 AAP(0.3psi)=32.6、AAP(0.7psi)=18_8g/g、殘留單體含量=294ppm、 可溶份(16hr)=16.9%。 【實例五】 1重覆實例一’但將步驟1.所述之粒徑小於ΙΟΟμΓη高吸水性樹脂的添 加量調整為6.10kg。此外，步驟4.所述之L-抗壞血酸的流量也需調 整為 138.64g/hr。 2_與實例一情形相似，混合槽排空後並未發現有細粉於槽内結塊或殘 留於槽壁上的現象。 3_分析所得之高吸水性樹脂的物性表現為：保持力=31 8g/g、 AAP(0·3psi)-32·7、AAP(07psi)=18.1g/g、殘留單體含量=311ppm、 可溶份(16h「)=16.3°/〇。 【實例六】 本發明之南吸水性樹脂的製造方法，此方法包括以下步驟： 1. 先於100L反應槽中加入49%液鹼i5j6kg，並在攪拌下(轉速為 50-75rpm)加入粒徑小於1 〇〇μηη的高吸水性樹脂〇 61 kg。 2. 之後於冰洛下將丙烯酸水溶液45.74kg(丙烯酸:水=3:4)缓慢加入上 述溶液中進行中和。 3. 再加入58.56g的丙三醇聚乙二醇三縮水甘油醚(n=2〇)於部分中和的 丙烯酸水溶液，並維持溫度於5-8°C左右。 4. 分別控制部分中和的丙烯酸鈉水溶液、卜抗壞血酸、過硫酸納及二_ 第二丁基過氧化氫的流量為 61.〇〇kg/hr、249.55g/hf、55455g/hr· 與554.55g/hr，並利用流動的方式使其混合並連續地排入反應皮帶 上。此外，出料後並未發現有細粉於槽内結塊或殘留於槽壁上的現 象。 5. 控制4.所述溶液於皮帶上的滯留時間為25mjn。 12 201100472 6_將反應元成的大塊膠體以切刀與擠壓機製成2mm直徑以下的小凝 膠體。 7·以150 C溫度乾燥90分鐘後，將乾燥的凝膠體進行研磨。 8_利用篩網篩選150μητι〜850μητι固定粒徑，得到高吸水性樹脂粉體。 9_秤取高吸水性樹脂100g，加入乙二醇碳酸酯/水/甲醇=彳/1/1(重量比） 溶液4g，以198°C溫度加熱處理30分鐘。 10_冷卻後’加入1g碳酸鈣(台塑公司生產；品名：NS_2〇〇〇)及2〇〇/0甘 油水溶液2g ’均勻混合後即得南性能高吸水性樹脂。 11.分析所得之高吸水性樹脂的物性表現為：保持力=34.5g/g、 AAP(0.3psi)=32.1、AAP(0_7psi)=16.8g/g、殘留單體含量 〇 =263ppm、可溶份(16hr)=19.1%。 【實例七】 1-重覆實例六，但將步驟1·所述之粒徑小於1〇〇μητι高吸水性樹脂的添 加量調整為1.83kg。此外，步驟4.所述之L-抗壞血酸的流量也需調 整為 221.82g/hr。 2. 與實例一情形相似，混合槽排空後並未發現有細粉於槽内結塊或殘 留於槽壁上的現象。 3. 分析所得之高吸水性樹脂的物性表現為：保持力=33.9g/g、 MP(0.3psi)=32_4、AAP(0.7psi)=17.3g/g、殘留單體含量=282ppm、 可溶份(16hr)=18.7%。 ◎【實例八】 1. 重覆實例六，但將步驟1·所述之粒徑小於100μηη高吸水性樹脂的添 加量調整為3.05kg。此外，步驟4·所述之卜抗壞血酸的流量也需調 整為 194.09g/hr。 2. 與實例一情形相似，混合槽排空後並未發現有細粉於槽内結塊或殘 留於槽壁上的現象。 3. 分析所得之高吸水性樹脂的物性表現為：保持力=34.1g/g、 AAP(0.3psi)=32.4、AAP(〇_7psi)=16.1g/g、殘留單體含量 =2985ppm、可溶份(16hr)= 19.3%。 【實例九】 13 201100472 1.重覆實例六，但將步驟1.所述之粒徑小於1〇〇μηι高吸水性樹脂的添 加量調整為4.27kg。此外，步驟4.所述之L-抗壞血酸的流量也需調 整為 166.37g/hr。 2·與實例一情形相似，混合槽排空後並未發現有細粉於槽内結塊或殘 留於槽壁上的現象。 3·分析所得之高吸水性樹脂的物性表現為：保持力=34.5g/g、 AAP(0.3psi)=32.6、AAP(0.7psi)=17.8g/g、殘留單體含量=254ppm、 可溶份(16hr)=17.9%。 【實例十】 1. 重覆實例六，但將步驟1.所述之粒徑小於100μηη高吸水性樹脂的添 加量調整為6.10kg。此外，步驟4.所述之L-抗壞血酸的流量也需調 整為 138.64g/hr。 2·與實例一情形相似，混合槽排空後並未發現有細粉於槽内結塊或殘 留於槽壁上的現象。 3·分析所得之高吸水性樹脂的物性表現為：保持力=33.8g/g、 AAP(0_3psi)=31.9、AAP(0.7psi)=18.0g/g、殘留單體含量=268ppm、 可溶份(16h「)=19.3%。 【比較例一】 1·重複實例一，但步驟1.中不添加粒徑小於1〇〇pm高吸水性樹脂。 2. 分析所得之高吸水性樹脂的物性表現為：保持力=32.5g/g、 MP(0.3psi)=32.4、MP(0.7psi)=17.5g/g、殘留單體含量=31〇ppm、 可溶份(16hr)=18.0°/。，與回收細粉時相當接近，這點顯示使用本發 明所述方法不會影響成品品質。 【比較例二】 1_重複實例一，但步驟1.中粒徑小於1〇〇μηι高吸水性樹脂的添加量提 高為 7.93kg。 2.分析所得之高吸水性樹脂的物性表現為：保持力=32.1g/g、 AAP(0.3psi)=32.3g/g、AAP(0.7psi)=15.9g/g、殘留單體含量 =306PPm、可溶份(16hr)=18.〇〇/。。與實例一不同的是，混合槽中液 體排空後發現有部分細粉結塊並殘留於槽壁上的現象，而且成品 14 201100472 AAP(0.7psi)下降了 2克左右。 【圖式簡單說明】 【主要元件符號說明】= water-absorbent resin has the phenomenon of agglomeration after the aging, the domain is free from the use of high absorption in the silky area =: = agglomeration leads to poor processing, generally coated on the surface of the superabsorbent resin: the end of the machine or the interface activity The agent makes the surface slightly lipophilic so that the superabsorbent resin retains moisture and does not hide. This miscellaneous money can be optionally tested, or the dioxide is oxidized, or oxidized, or oxidized. About, or kaolin, or carbonate, or magnesium carbonate, or the like, the amount of the inert inorganic salt powder added to the inorganic salt powder particle size is related to the particle size of the inorganic particle powder HJ, its inorganic salt powder specific surface area Large, so the effective inert inorganic salt powder can be used in a small amount. The neo-inorganic salt powder is added in a range of weight ratio q to mowt%, preferably from 0.01 to 4% by weight, and the inert inorganic salt powder is preferably The diameter is 0_001μΜ to 1〇〇μΜ 'If the inorganic salt powder with a particle size smaller than 〇〇〇1|jM is used, the cost is too high. Unstable industrial production. If the inorganic salt powder with a particle larger than 1〇_ is used, the added amount is too high. It is the same as the absorption of the resin. Inert non-powder can be added alone or with surfactants or with money-reducing compounds. The interface is dirty and organic compounds can be selected. HLB value of 12 or more nonionic surfactant or water-soluble anionic surfactant can be used. Or a cationic interface active _, or a cation-yang-type surfactant, or a mixture thereof, usually a surfactant or a lion's money compound may use glycerin, ethylene glycol, hexahexaol, polyoxyethylene alcohol, or polyethylene Glycol, or hard acid acid polyethylene glycol vinegar, or stearic acid polyethylene glycol hexaacetate or polyethylene oxide phthalic acid ether, or polyethylene oxide octane, or polyoxyethylene dodecyl ether , or polyoxyethylene yard base _, silk loses women's monthly fine, etc. This research thief purity money compound can be formulated into water, nourishment; 6 〇 people or paste plus people 'appropriate interface thief with New Organic Compound Additives The amount is between 0.001 wt% S 5 wt% (based on the total solids of the reactants), and a more appropriate amount by weight is between 0.01 wt% and 3 wt%. The present invention provides a method for producing a superabsorbent resin, which comprises the following steps: (1) mixing and recovering the fine powder having a particle diameter of less than 100 pm and an alkaline neutralizing agent according to a weight ratio of 彳:彳: 13; (2) mixing the acid-containing aqueous solution with the fine powder neutralizing agent; (3) adding a crosslinking agent to an aqueous solution containing an acid group-containing monomer having a degree of neutralization of 5〇m〇|e%; 201100472 ( 4) adding a starter to the aqueous solution of the aqueous solution containing the acid-based monomer to form a hydrogel, and retaining 25 minutes in the reactor; (5) to iq〇c to 250. Drying, pulverizing, and screening by hot air; (6) Surface cross-linking agent coating treatment; (7) Heating surface treatment at a temperature of 8 CTC to 230 ° C; (8) Adding an inert inorganic salt powder. Wherein the particle size after screening is from 15 μηηι to 850 μηι. Wherein, the weight percentage of the surface crosslinking agent added is 〇 5 wt% 〜 5 〇 wt%. Wherein the weight percentage of the inert inorganic salt powder added is 〇 〇% to 40% by mole. The method provided by the present invention not only affects the operability of fine powder recovery and improves production efficiency, but also does not affect the stability of quality. The working examples are listed in detail below to illustrate the present invention, but the scope of the present invention is not limited by the examples. _ [Embodiment] [Example 1] A method for producing a water-absorbent resin of the present invention, the method comprising the following steps: • Add 49°/ to the 100L reaction tank. The liquid base was 15_26 kg, and a superabsorbent resin having a particle diameter of less than ΙΟΟμητι was added to 6 kgg under stirring (rotation speed of 50-75 rpm). 2. Thereafter, 45.74 kg of an aqueous acrylic acid solution (acrylic acid: water = 3:4) was slowly added to the above solution for neutralization under an ice bath. 3. Add 19-52 g of glycerol polyethylene glycol triglycidyl ether (n = 7) to the partially neutralized aqueous solution of acrylic acid and maintain the temperature at around 5-8 °C. 4. The flow rates of partially neutralized sodium acrylate aqueous solution, ascorbic acid, sodium persulfate and di-tert-butyl hydroperoxide were respectively controlled to be 61.00 kg/hr, 249.55 g/hr, 554.55 g/hr and 554.55 g/hr. It is mixed by flow and continuously discharged into the reaction belt. In addition, after the discharge, no fine powder was found to agglomerate in the tank or remain on the wall of the tank. 5. Control 4. The residence time of the solution on the belt was 25 min. 6. The reaction-completed bulk colloid is made into a small gel of 2 mm or less with a cutter and an extruder. 10 201100472 7_ After drying at a temperature of 150 ° C for 90 minutes, the dried gel was ground. 8. Use a sieve to screen the 粒径50μηη~850μηι fixed particle size, and obtain the 叼古Α Q t ^ shame only to the 叼 water-absorbent resin powder. 9. Weigh 1 〇〇g of water-absorbing resin, add 4 g of ethylene carbonate/water/methanol = (weight ratio) solution, and heat-treat at 215 ° C for 1 〇. 10. After cooling, add 1 g of carbonic acid (produced by Formosa Plastics Co., Ltd.; product name: machine 2) and 2 g of 2% glycerin aqueous solution, and mix uniformly to obtain a high-performance and high-absorbency tree. The physical properties of the superabsorbent resin obtained by the analysis were as follows: retention force = 327 g/g, AAP (0_3 psi) = 32.1, AAP (0.7 psi) = 16.8 g/g, 'residual, residual monomer content = 300 ppm, The fraction (16 hr) = 17.1%. 〇 [Example 2] 1. Repeat Example 1 but adjust the addition amount of the water-absorbent resin having a particle diameter smaller than that of ΙΟΟμιτι in the step 1· to 1 to 83 kg. Further, the flow rate of L-ascorbic acid described in the step 4. is also adjusted to 221.82 g/hr. 2. Similar to the case of Example 1 After the mixing tank was emptied, no fine powder was found to agglomerate in the tank or remain on the tank wall. 3. The physical properties of the superabsorbent resin obtained were analyzed as follows: retention force = 33.0 g/g, AAP (0.3 psi) = 31.6, MP (0-7 psi) = 17.3 g/g, residual monomer content = 280 ppm, soluble fraction (16h ") = 18.0%. 〇 [Example 3] ^ Repeat example 1, but adjust the addition amount of the superabsorbent resin having a particle diameter of less than 1 〇〇μηι described in step 1. to 3.05 kg. The flow rate of the L-ascorbic acid also needs to be adjusted to 194.09 g / hr. 1. Similar to the case of the case 1 'The phenomenon that the fine powder is agglomerated or remains on the groove wall after the mixing tank is emptied 2. The physical properties of the superabsorbent resin obtained by the analysis are: retention force = 32. 〇g / g, AAP (0.3 psi) = 32.5, MP (〇 _7 psi) = 17.1 g / g, residual monomer content = 305ppm, soluble fraction (16h ") = 17.5%. [Example 4] 1. Repeat example 1 'but the step 1 · The particle size is less than 1 ooi · 1 m super absorbent resin Add 11 201100472 Adjusted to 4.27kg. In addition, the flow rate of ascorbic acid described in step 4. also needs to be adjusted to 166.37g / hr. 2. Similar to the case of case 1, after the mixing tank is empty, no fine powder is found in the tank. The phenomenon of residue on the wall of the tank 3. The physical properties of the superabsorbent resin obtained by the analysis are: retention force = 33. g/g, AAP (0.3 psi) = 32.6, AAP (0.7 psi) = 18_8 g/g, Residual monomer content = 294 ppm, soluble fraction (16 hr) = 16.9%. [Example 5] 1 Repeat Example 1', but the addition amount of the particle size smaller than the ΙΟΟμΓη superabsorbent resin described in the step 1. was adjusted to 6.10 kg. In addition, the flow rate of L-ascorbic acid described in step 4. also needs to be adjusted to 138.64 g / hr. 2_ Similar to the case of Example 1, after the mixing tank is emptied, no fine powder is found in the tank to agglomerate or remain in the tank. Phenomenon on the wall of the tank. The physical properties of the superabsorbent resin obtained by the analysis were: retention force = 31 8 g / g, AAP (0.3 psi) - 32 · 7, AAP (07 psi) = 18.1 g / g, residual Monomer content = 311 ppm, soluble fraction (16h ") = 16.3 ° / 〇. [Example 6] The method for producing a south water-absorbent resin of the present invention, the method comprising the following steps: 1. Adding 49 in a 100 L reaction tank % liquid alkali i5j6kg, and add a super absorbent resin 〇61 kg with a particle size of less than 1 〇〇μηη under stirring (rotation speed 50-75 rpm). 2. Then add acrylic water under ice. 45.74 kg of liquid (acrylic acid: water = 3:4) was slowly added to the above solution for neutralization. 3. Add 58.56 g of glycerol polyethylene glycol triglycidyl ether (n=2〇) to the partially neutralized An aqueous solution of acrylic acid is maintained at a temperature of about 5-8 °C. 4. The flow rates of partially neutralized sodium acrylate aqueous solution, ascorbic acid, sodium persulfate and di-tert-butyl hydroperoxide are respectively controlled to be 61.〇〇kg/hr, 249.55g/hf, 55455g/hr· and 554.55. g/hr, and mixed by flow and continuously discharged into the reaction belt. In addition, no fine powder was found to agglomerate in the tank or remain on the wall of the tank after discharge. 5. Control 4. The residence time of the solution on the belt is 25 mjn. 12 201100472 6_ The large colloid of the reaction element was made into a small gel of 2 mm or less with a cutter and an extruder. 7. After drying at 150 C for 90 minutes, the dried gel was ground. 8_ The particle size was fixed by screening a sieve of 150 μητι to 850 μητι to obtain a superabsorbent resin powder. 9_ A 100 g of superabsorbent resin was weighed, and 4 g of a solution of ethylene glycol carbonate/water/methanol=彳/1/1 (weight ratio) was added, and heat treatment was performed at 198 ° C for 30 minutes. After 10_cooling, 1 g of calcium carbonate (produced by Formosa Plastics Co., Ltd.; product name: NS_2〇〇〇) and 2 g/0 glycerol aqueous solution 2 g' were uniformly mixed to obtain a south-performance superabsorbent resin. 11. The physical properties of the obtained superabsorbent resin were as follows: retention force = 34.5 g/g, AAP (0.3 psi) = 32.1, AAP (0-7 psi) = 16.8 g/g, residual monomer content 〇 = 263 ppm, soluble Parts (16 hr) = 19.1%. [Example 7] 1-Example 6 was repeated, but the amount of addition of the water-absorbent resin having a particle diameter of less than 1 〇〇μητι in the step 1· was adjusted to 1.83 kg. In addition, the flow rate of L-ascorbic acid described in step 4. also needs to be adjusted to 221.82 g/hr. 2. Similar to the case of Example 1, after the mixing tank was emptied, no fine powder was found to agglomerate in the tank or remain on the tank wall. 3. The physical properties of the superabsorbent resin obtained were analyzed as follows: retention force = 33.9 g/g, MP (0.3 psi) = 32_4, AAP (0.7 psi) = 17.3 g/g, residual monomer content = 282 ppm, soluble Serving (16hr) = 18.7%. ◎ [Example 8] 1. Example 6 was repeated, but the addition amount of the superabsorbent resin having a particle diameter of less than 100 μηη described in the step 1· was adjusted to 3.05 kg. In addition, the flow rate of ascorbic acid described in step 4· needs to be adjusted to 194.09 g/hr. 2. Similar to the case of Example 1, after the mixing tank was emptied, no fine powder was found to agglomerate in the tank or remain on the tank wall. 3. The physical properties of the superabsorbent resin obtained were analyzed as follows: retention force = 34.1 g/g, AAP (0.3 psi) = 32.4, AAP (〇_7 psi) = 16.1 g/g, residual monomer content = 2985 ppm, Solute (16 hr) = 19.3%. [Example 9] 13 201100472 1. Example 6 was repeated, but the addition amount of the superabsorbent resin having a particle diameter of less than 1 〇〇μηι described in the step 1. was adjusted to 4.27 kg. In addition, the flow rate of L-ascorbic acid described in step 4. also needs to be adjusted to 166.37 g/hr. 2. Similar to the case of Example 1, after the mixing tank was emptied, no fine powder was found to agglomerate in the tank or remain on the tank wall. 3. The physical properties of the superabsorbent resin obtained by the analysis were as follows: retention force = 34.5 g/g, AAP (0.3 psi) = 32.6, AAP (0.7 psi) = 17.8 g/g, residual monomer content = 254 ppm, soluble Serving (16 hr) = 17.9%. [Example 10] 1. Example 6 was repeated, but the addition amount of the superabsorbent resin having a particle diameter of less than 100 μηη as described in the step 1. was adjusted to 6.10 kg. In addition, the flow rate of L-ascorbic acid described in step 4. also needs to be adjusted to 138.64 g/hr. 2. Similar to the case of Example 1, after the mixing tank was emptied, no fine powder was found to agglomerate in the tank or remain on the tank wall. 3. The physical properties of the superabsorbent resin obtained by the analysis were as follows: retention force = 33.8 g/g, AAP (0_3 psi) = 31.9, AAP (0.7 psi) = 18.0 g/g, residual monomer content = 268 ppm, soluble fraction (16h ") = 19.3% [Comparative Example 1] 1. Repeat Example 1, but do not add a superabsorbent resin with a particle size of less than 1 μm in step 1. 2. Analysis of the physical properties of the superabsorbent resin obtained To be: retention force = 32.5 g/g, MP (0.3 psi) = 32.4, MP (0.7 psi) = 17.5 g/g, residual monomer content = 31 〇 ppm, soluble fraction (16 hr) = 18.0 ° /. It is quite close to the recovery of fine powder, which shows that the method of the present invention does not affect the quality of the finished product. [Comparative Example 2] 1_ Repeat Example 1, but in step 1. The particle size is less than 1〇〇μηι superabsorbent resin The addition amount was increased to 7.93 kg. 2. The physical properties of the obtained superabsorbent resin were as follows: retention force = 32.1 g/g, AAP (0.3 psi) = 32.3 g/g, AAP (0.7 psi) = 15.9 g/ g, residual monomer content = 306PPm, soluble fraction (16hr) = 18. 〇〇 /. Different from the first example, after the liquid in the mixing tank is emptied, some fine powder is found and remains on the tank wall. Phenomenon, and finished product 14 201100472 AAP (0.7psi) dropped by about 2 grams. [Simple diagram] [Main component symbol description]
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