4228 6 6 五 發明説明（ A7 B74228 6 6 5 Description of the invention (A7 B7
本發明係有闞於一種高吸水性樹脂的製造方法， 是有闞於協助反應後樹脂絞碎及分教，而利於乾燥製^其 製造方法。 9 因高吸水性樹脂具有強大的保水力，可吸收百供I 於千倍於本身重量的水，吸水後可膨潤且具有保持^ 至 的狀態，即使施加壓力也不會滲漏，被吸收的水亦可二動 氣中緩緩地釋出；由於具有上述之特性，所以最早期大 於農、森林業的土壤保水劑，近年來因高吸水性樹胳的用 產技術有相當大的進步，因此也逐漸地用於衛生梯、纟生 布、褲及成人紙尿布、褲等衛生用品的吸收劑。 尿 習知用於作衛生棉、紙尿布、褲及其他吸收人趙 衛生用品的高吸水性樹脂成份材料，有澱粉丙埽骑（'之 hydrolysis starch acrylonitrile)接枝聚合物永解而 聚合物（如曰本專利公開公報昭49(1974)-43,395)，中和 經濟部中央標準局貝工消费合作社印製 f請先閲讀背面之注$頊再嗔寫本頁」The invention relates to a method for manufacturing a super absorbent resin, which is used for assisting the resin to be crushed and divided into pieces after the reaction, and is beneficial to drying and manufacturing the method. 9 Because the super absorbent resin has a strong water retention ability, it can absorb 100 times more water than its own weight. After absorbing water, it can swell and maintain a state of ^ to, even if pressure is applied, it will not leak and be absorbed. Water can also be released slowly in two moving air; due to the above characteristics, the earliest soil water retaining agent is larger than that of agriculture and forestry. In recent years, due to the considerable progress in the production technology of super absorbent trees, It is also gradually used as an absorbent for sanitary products such as sanitary ladders, sanitary cloths, pants and adult diapers, pants. Urine is known to be used as sanitary napkins, paper diapers, pants and other super absorbent resin ingredients that absorb human Zhao sanitary products. There is a hydrolyzed starch acrylonitrile grafted polymer, and a polymer ( For example, this Patent Publication No. Sho 49 (1974) -43,395), printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs f Please read the note on the back before writing this page "
-、ST 之嘏粉丙烯酸接枝聚合物（曰本專利公開公報昭51(197 125,468)，皂化丙烯醋酸丙烯脂共聚合物（日本專利公門 公報昭52(1977)-14,689)，丙埽腈共聚物或丙烯醢錢二^ 物之水解聚合物（日本專利公報昭53(1978)-15,959 )及中 和聚丙烯酸（日本專利公開公告昭55(1980)-83,304)等， 其中以使用丙烯酸及丙烯酸鹽進行交聯聚合所得之高吸^ 性樹脂最為經濟，其原因為丙烯酸可由市售取得，且製得 的高吸水性樹脂具有較高的吸水力，所以具有較高的緩濟 故益，此外此類丙烯酸系的高吸水性樹脂具有製造成未低 廉且吸水後樹脂短時間無腐爛的現象，故現已成為最普壤 2 本紙張適用中國國家樣準（CNS ) A4躲（210x297公釐） 4228 6 6 A7 B7 五、發明説明（2) 化的高吸水性樹脂。 聚合丙烯酸及丙烯酸II形成高吸水性樹脂的方法已被 廣泛地開發成功且也都應用於工業界現場生產，其方法有 鴒模聚合反應（曰本專利公告昭和48(1973)-42，466 )，於 輸送帶進行聚合反應（曰本專利公開眧和58(1983)-49,714 ，粉碎之攪拌刀片的捏拌機中進行聚合反應（日本專利公 開昭和57(1982)-34,101)，進行逆相懸浮液聚合反應（日 本專利公告昭59(1984)-37,303)或將單體噴灑或塗覆於纖 維基質上進行聚合反應（日本專利公開昭和61(1986)-275,355 及昭和62(1987)-53,309)，在特殊的容器中進行聚合反應 (日本專利公開昭和55(1980)-108,407)及在雙臂捏合機中 進行聚合反應（曰本專利公開昭和57(1982)-34，101)。 經濟部中央橾準局貞工消費合作社印製 (請先閲讀背面之注^項再填寫本頁) ,** 高吸水性樹脂雖然生產的方法繁多，但聚合反應之溶 液、應包含主要不飽和酸單髖、共聚合單體、架橋性單體 及自由基聚合反應起始劑：其單體選用除了丙烯酸外，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-丙烯胺-2-甲基丙烷磺酸等。單 體選用不特定限制只可使用一種，亦可合併多種單體一齊 使用，亦可視情沉需要添加具有不飽和雙鍵其他親水性的 單體，如：丙烯醢胺、甲基丙烯醢胺、丙烯酸2-烴基6酯 、甲基丙烯酸2-烴基乙酯、丙烯酸甲酯、丙烯酸乙酯、二 甲胺丙烯丙烯醯胺、氣化丙烯丙烯醯胺基三甲鋏但添加量 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 本纸張尺度適用中國國家標準（<^5)八4规格（210父297公釐> 經濟部中央標準局員工消費合作社印装 4228 66 A7 __ B7 五、發明説明（3) 55wt%間，適當濃度為30wt%至45η%之間，濃度在重量百 分比2〇計％以下時，聚合後水合體太軟且有黏性不利機械 加工，添加濃度在重量百分比55wt5i以上，接近飽和濃度 ，不易調配且反應太快反應熱不易控制。 含酸基單體之羧酸基應部份中和以控制成品之PE值， 使呈中性或微酸性，中和劑為氫氧化鈉、氫氧化鉀、碳酸 鈉、碳酸鉀、碳酸氫鈉、碳酸氳鉀及氨。含酸基單體之羧 酸基部份中和成鈉鹽或鉀盥或銨鹽，中和濃度莫耳百分比 為45Mol%至85Mol%，宜為50mol%至，中和濃度莫耳 百分比為45m〇U以下時成品之PH值會偏低，中和濃度莫耳 百分比為85m〇l%以上時成品之PH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。 在進行自由基聚合反應前單髏水溶液中，亦可添加水 溶性高分子以降低成本，此等水溶性高分子如：部份皂化 或完全皂化的聚乙烯醇、聚丙烯酸、聚丙烯酿胺、爽粉或 澱粉衍生物如甲基織維素，丙烯酸甲基織維素，乙基纖維 素等聚合物；此等水溶性高分子的分子量並不特別限定’ 其中較佳的水溶性高分子為澱粉、部份專化或完全專化的 聚乙烯醇等單獨或混合使用。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0.001 至lOwt%較佳，0.01至尤佳，添加超過2〇wt%時會影 響物性，使物性變差。 為確保高吸水性樹脂的生成，在進行自由基聚合&應 本紙張尺度適用中國國家標準（CNS ) A4規格（2Ι〇Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) :k. -訂 4228 6 6 經濟部中央揉準局员工消费合作社印装 A7 B7 五、發明説明（4) 前應先添加自由基聚合反應交聯劑於未反應單链溶液中， 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：雙（2-丙烯基）胺、次甲 基雙丙烯醢胺、ϊί,Ν，-攻甲基雙甲基丙烯醯胺、丙烯酸丙 烯脂、乙二醉二丙烯酸酯、聚乙二醇二丙烯酸酯、乙二醇 二甲基两烯酸酯、聚乙二醇二甲基丙烯酸酿、甘油三丙烯 酸薛、甘油三甲基丙缔酸酯' 甘油附加環氧己炫之三丙埽 酸蘸或三甲基丙烯酸酯、三甲醇丙垸附加環氧己烷之三丙 烯酸酯或三甲基丙烯酸酯、三甲酵丙烷三甲基丙烯酸酯、 三甲醇丙烷三丙烯酸脂、Ν,Ν，-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鍵、聚丙三 醇聚縮水甘油瞇、乙二醇二縮水甘油醚、二乙二醇二縮水 甘油醚、聚6二醇二縮水甘油瞇、雙丙三醇聚縮水甘油酸 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O.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O.Olwt%至3wt%之間，添加劑量在重量百分比 O.OOlwt%以下聚合後水合踫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0 聚合反應由自由基聚合反應起始劑的分解產生自由基 本紙張尺度適用中國國家榇準（CNS ) A4规格（210X297公釐） --------·Η,、裝------訂------f 一 (請先閱讀背面之注意事項再填寫本頁)-, ST's powdered acrylic acid graft polymer (Japanese Patent Publication No. Sho 51 (197 125,468), saponified propylene acetate propylene copolymer (Japanese Patent Publication No. Sho 52 (1977) -14,689), propionitrile copolymer Hydrolyzed polymers of polymers or acrylic acid (Japanese Patent Publication Sho 53 (1978) -15,959) and neutralized polyacrylic acid (Japanese Patent Publication Sho 55 (1980) -83,304), etc., among which acrylic acid and acrylic acid are used The superabsorbent resin obtained by cross-linking and polymerizing the salt is the most economical. The reason is that acrylic acid can be obtained from the market, and the superabsorbent resin produced has a higher water absorption, so it has a higher relief benefit. This type of acrylic super absorbent resin is not cheap and the resin does not rot for a short time after absorbing water, so it has become the most common soil. 2 This paper is suitable for China National Standard (CNS) A4 hide (210x297 mm) 4228 6 6 A7 B7 V. Description of the invention (2) Highly water-absorbent resin polymerized. The method of polymerizing acrylic acid and acrylic acid II to form a super-water-absorbent resin has been widely developed and is also used in industrial field production. Methods include mold polymerization (Japanese Patent Publication No. Showa 48 (1973) -42,466), polymerization on a conveyor belt (Japanese Patent Publication No. 58 (1983) -49,714, kneading machine with crushing stirring blade) Polymerization reaction (Japanese Patent Publication No. Showa 57 (1982) -34,101), reverse phase suspension polymerization reaction (Japanese Patent Publication No. Sho 59 (1984) -37,303) or spraying or coating monomers on a fiber substrate for polymerization Reactions (Japanese Patent Publications Showa 61 (1986) -275,355 and Showa 62 (1987) -53,309), polymerization is carried out in special containers (Japanese Patent Publication Showa 55 (1980) -108,407) and in a two-arm kneader Polymerization (Japanese Patent Publication Showa 57 (1982) -34, 101). Printed by the Zhengong Consumer Cooperative of the Central Bureau of Quasi-Ministry of Economic Affairs (please read the note ^ on the back before filling out this page), ** super absorbent Although there are many methods for producing resin, the solution of the polymerization reaction should contain mainly unsaturated monoacids, comonomers, bridging monomers, and radical polymerization reaction initiators. The monomers used can be in addition to acrylic acid. Use other unsaturated double bonds Water-soluble monomers, such as: methacrylic acid, maleic acid, fumaric acid, 2-acrylamine-2-methylpropanesulfonic acid, etc. There is no particular limitation on the choice of monomer, only one type can be used, and multiple types of monomers can be combined. If you use it together, you can also add other hydrophilic monomers with unsaturated double bonds, such as: acrylamide, methacrylamide, 2-alkyl 6 acrylate, 2-alkyl methacrylate, Methyl acrylate, ethyl acrylate, dimethylamine propylene acrylamide, and vaporized propylene acrylamine trimethylamidine, but the amount added is based on the principle that the physical properties of the super absorbent resin are not destroyed. Prior to the free radical polymerization reaction, the concentration of the monomer aqueous solution should be controlled at 20% by weight to the paper size. The Chinese National Standard (< ^ 5) 8.4 specification (210 father 297 mm) is applicable. Printed by employee consumer cooperatives 4228 66 A7 __ B7 V. Description of the invention (3) 55wt%, suitable concentration is 30wt% to 45η%, and the concentration is less than 20% by weight, the hydrate after polymerization is too soft and Viscosity is unfavorable for mechanical processing. The added concentration is more than 55wt5i, which is close to the saturated concentration. It is not easy to mix and the reaction is too fast. The reaction heat is not easy to control. The carboxylic acid group containing acid group monomer should be partially neutralized to control the PE value of the finished product. To make it neutral or slightly acidic, the neutralizing agents are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium carbonate, and ammonia. The carboxylic acid moiety of the acid-containing monomer is neutralized. It becomes sodium salt or potassium salt or ammonium salt. The neutralization concentration Mohr percentage is 45Mol% to 85Mol%, preferably 50mol% to. When the neutralization concentration Mohr percentage is less than 45m〇U, the PH value of the finished product will be low, medium. And the concentration of the mole percentage is above 85mol% The PH value of the product will be too high, and when the PH value of the finished product is not neutral or slightly acidic, it is not suitable and unsafe if it is inadvertently contacted with the human body. It is also unsafe before the free-radical polymerization reaction. Water-soluble polymers can be added to reduce costs. Such water-soluble polymers such as: partially saponified or fully saponified polyvinyl alcohol, polyacrylic acid, polypropylene amine, powder or starch derivatives such as methyl oryzanol, Polymers such as methacrylic acid, ethyl cellulose; the molecular weight of these water-soluble polymers is not particularly limited. Among them, the preferred water-soluble polymers are starch, partially specialized or fully specialized polyethylene Alcohol, etc. can be used alone or in combination. The appropriate weight percentage of the super absorbent resin containing these added water-soluble polymers is 0 to 20% by weight, but 0.001 to 10% by weight is preferred, 0.01 to particularly preferred, and when the amount exceeds 20% by weight It will affect physical properties and make them worse. In order to ensure the formation of super absorbent resin, the radical polymerization & should be carried out in accordance with the Chinese National Standard (CNS) A4 specification (2Ι〇 × 297mm) in the paper size (please read the back first) Attention Please fill in this page again): k. -Order 4228 6 6 Printed by the Consumers Cooperative of the Central Government Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) Free radical polymerization crosslinker should be added to the unreacted single chain before In the solution, the free-radical polymerization cross-linking agent may be selected from compounds having two or more unsaturated double bonds, such as: bis (2-propenyl) amine, methine bispropenamide, ϊ, N, -Tape methacrylamide, acrylic acrylate, ethylene diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethyl dienoate, polyethylene glycol dimethacrylate , Glycerol triacrylate, triglyceride triglyceride 'glycerol with epoxy trioxane dipropionate or trimethacrylate, trimethylolpropane trioxide or trimethacrylate Acrylate, trimethanol trimethacrylate, trimethylolpropane triacrylate, N, N, -tris (2-propenyl) amine, ethylene glycol diacrylate, dipropylene triethylene glycol, etc. Optional compounds with two or more epoxy groups, such as sorbitol polycondensation Glycerol key, polypropylene triol polyglycidol squint, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl 6 Mi, glycerol bis polyglycidol acid. After the radical reaction is performed, the super absorbent resin can have an appropriate degree of crosslinking, and the super absorbent resin colloid can have appropriate processability. The radical polymerization reaction crosslinking agent may be used singly or as a mixture of two or more kinds. The appropriate addition amount of the radical polymerization crosslinking agent is between 0.001 wt% and 5 wt% (based on the total solid content of the reactant), and a more suitable amount is between 0.01 wt% and 3 wt%. The added amount is less than 0.00lwt% after polymerization. Hydrated hydrazone is too soft and viscous after machining. The added amount is more than 5wt%. The water absorption is too low to reduce the resin performance. The polymerization reaction starts from radical polymerization. The decomposition of the initiator produces a free basic paper size that is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). f one (please read the notes on the back before filling this page)
五、發明説明（5) 經濟部中央標準局®:工消費合作杜印製 開始；自由基起始劑可選用熱分解型起始劑，適合的熱分 解型起始刺有過氧化物，如：過氧化氫、二-第三丁基過氧 化物、過氧化酿胺或過疏酸鹽（按逢、絵金屬鹽）等’及偶 氪化合物如：2.2’-偶氪基雙（2-脒基丙烷）二鹽酸逢、2.2’ -偶氪基雙（N，N-二伸甲基異丁脒）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，首先氧化運原起始劑先進行反 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_0011^%至10胃1:%(以中和丙烯酸鹽重量為基準），更 適當用量則在O.lwt%至5wt%之間，使用重量百分比〇 oQi wt%以下時，反應太慢不利經濟效益，使用重量百分比1〇 wt%以上時，反應太快反應熱不易控制。 聚合反應可於俾統批次反應容器中，或於輸送帶式反 應器上進行反應，反應所得之高吸水性樹脂，再利用至 160度溫度進行乾燥，待乾燥後進行粉碎綿選固定粒捏， 即可得粉末狀的高吸水性樹脂。 但在高吸水性樹脂的製程中，為使樹脂充份達到乾燥 效果，通常先利用切碎機、切條機、押出多孔機、螺旋切 片機或絞碎機切成直徑2〇m]n以下小凝膠體，直徑1〇lnm以下 本紙張尺度適用中國囷家標準（CNS ) A4規格（2丨0X297公釐） —-_ --------,k 裝------訂-----' ' 冰 (#先閱讀背面之注意事項再填寫本頁) 4228 β 6 經濟部中央標準局員工消費合作杜印製 A7 B7 五、發明説明（6) 更佳，再進行烘乾，但切成小凝勝艘時，因小凝膠體具有 黏性將會造成凝膠體互相凝結，此相互凝結的現象會使在 烘乾時熱氣無法透過gel層，致使無法讓每個均勻受熱 ，而影響烘乾的結果。欲改善此、種凝集現象可在押出機多 孔板內加刀，以協助gel的絞碎及分散（日本專利特許公開 昭和54 (1979)-32,176)、在押出機多孔板内加刀，並添加 矽膠乳化劑以協助gel的絞碎及分散（日未專利特許公開昭 和M(1984)-119,172)、控制gei溫度45-90度及多孔板孔 徑為6.5-1διιπη時押出（日木專利特許公開平成5(1994)_ 70,597” 利用在押出機多孔板内加刀，以協mgei的絞碎及分 散其改善gel分散效果不甚理想；在押出機多孔板内加刀 ，並添加矽膠乳化劑以協助gel的絞碎及分散，雖然可相 當有故的改善絞碎及分散性，但因添加入低親水性界面活 性劑，所以會造成吸水性質改變，致使高吸水性樹脂的吸 水速率及吸水倍數降低；利用控制gel溫度45-90度及多 孔板孔徑為6.5-18mm時押出則有gel溫度控制不易，及 降低gel凝集效果亦相當有限等缺點。 因此，本發明主要是提供一種製造高吸水性樹脂的製 造方法，該方法至少包含泽加可協助反應後樹脂絞碎及分 散，但不影饗此高吸水性樹脂吸水速度的高親水性界面活 性劑，再於溫度8(TC至160°C下進行乾燥及粉碎，而得此 高吸水性樹脂，且此高吸水性樹脂亦不會影響吸水迷度。 經由此發明所處理的小凝膠體就具有良好的分散性而有利 本紙張尺度適用中國國家標隼（CNS > A4規格（210X297公釐） --------f: ^-- (请先閲讀背面之注意事項再填寫本頁) -訂 經濟部中央標準局貝工消费合作社印製 4228 66 A7 五、發明説明（7) 於烘乾的製程，本發明所示的添加高親水性界面活性劑其 結構為： ^-[OCCKROCHCR'^Oy^4^ R1可為C2~le的直鏈或支鏈的烷基；R2及R3可個別為Η或 0Η基或甲基；R*可為h或。的直鏈或支鏈的烷基； X可為2或2以上，當X為2時Υ可為6-170 ，當 X為3或3以上時y可為3-34。其中可選用山梨醇聚 6二醇、丙二醇聚乙二酵、丁二醇聚乙二醇、己六醇聚乙 二醇、聚乙二醇、聚丙二醇、聚乙二醇及聚丙二醇共聚物 、甲基乙二醇二聚乙二醇、1,2-二甲基乙二醇二聚乙二醉 、丙三醇二聚乙二醇、丙三醇三聚6二醇、曱基丙三醇三 聚6二稃、L2-二甲基丙三醇三聚乙二醇、乙基丙三醇三 聚乙二醇、2-甲基丙三醇三聚乙二酵、2-6基丙三醇三聚 乙二醇等；所添加高親水性界面活性劑可單獨使用或二個 或二個以上混合使用，其適當的添加劑量為重量百分比為 O.OOlwtSi至l〇wt%(以中和丙烯酸鹽重量為基準），更適當 用量則在〇.1¥^%至4货1:%之間。 為顯示本發明降低小小凝膠體的黏度，而使小凝 易於分散，本發明將觀察小凝膠體的分散情形，來列 加高親水性界面活性劑所產生的故果，分散狀沉1表杀小 凝膠體出絞碎機後立即分散；分散狀沉2表示小凝勝 绞碎機後有少許凝集，經搖動後立即分散；分散狀沉3表 (請先閲讀背面之注意事項再填寫本頁) 丨裝 訂V. Description of the invention (5) Central Standards Bureau of the Ministry of Economic Affairs ®: Industrial and consumer cooperation Du printed production begins; free-radical initiators can be selected from thermal decomposition type initiators, and suitable thermal decomposition type starting materials are punctured with peroxides, such as : Hydrogen peroxide, di-third butyl peroxide, amine peroxide or peroxo acid salt (according to the metal salt), and couplers such as: 2.2'-coupler bis (2- Fluorenyl propane) dihydrochloride, 2.2'-Ethyl bis (N, N-dimethylisobutylamidine) dihydrochloride; Reducing agents can also be used to make them redox-type initiators, such as: Acidic sulfite, thiosulfate, ascorbic acid or ferrous salt; or use a combination of redox initiator and thermal decomposition initiator, firstly oxidize the transport initiator to generate free radicals, and when free The radical is transferred to the monomer to initiate the polymerization reaction. Because the polymerization reaction releases a large amount of heat, the temperature is increased. When the temperature reaches the decomposition temperature of the thermal decomposition initiator, the second stage is triggered. Decomposition of thermal decomposition type initiator, so that the entire polymerization reaction becomes more complete Full. Generally, the appropriate amount of the radical polymerization reaction initiator is 0_0011 ^% to 10 stomach 1:% (based on the weight of the neutralized acrylate), and a more appropriate amount is between 0.1 wt% and 5 wt%. When the weight percentage is below 0oQi wt%, the reaction is too slow, which is detrimental to economic benefits. When the weight percentage is above 10wt%, the reaction is too fast, and the reaction heat is not easy to control. The polymerization reaction can be carried out in a conventional batch reaction container or on a conveyor belt reactor. The superabsorbent resin obtained by the reaction can be dried at a temperature of 160 ° C. After drying, it can be crushed and fixed. , To obtain a powdery super absorbent resin. However, in the process of super absorbent resin, in order to fully dry the resin, usually use a shredder, slitter, extruder, screw slicer or mincer to cut to a diameter of 20 m or less. Small gel body, diameter below 10lnm. This paper size is applicable to Chinese Standard (CNS) A4 specification (2 丨 0X297mm) —-_ --------, k package ------ Order ----- '' Bing (#Read the precautions on the back before filling out this page) 4228 β 6 Consumption cooperation between employees of the Central Standards Bureau of the Ministry of Economic Affairs, printed by A7 B7 5. The description of the invention (6) is better, then proceed Drying, but when cut into small condensate, the small gels will cause the gels to condense each other. This phenomenon of mutual condensation will prevent the heat from passing through the gel layer during drying, making it impossible to let each gel One is evenly heated, which affects the result of drying. To improve this and agglutination, a knife can be added to the extruder's perforated plate to assist in the crushing and dispersing of the gel (Japanese Patent Laid-Open Publication Showa 54 (1979) -32,176), a knife can be added to the extruder's perforated plate, and added Silicone emulsifier to assist in the crushing and dispersing of gel (Japanese Unexamined Patent Publication Showa M (1984) -119,172), controlled when the gei temperature is 45-90 degrees, and the perforated plate pore size is 6.5-1διιπη (Nikkei Patent Publication Heisei 5 (1994) _ 70,597 ”Using a knife in the extruder's perforated plate to disintegrate and disperse the mgei to improve the gel dispersion effect is not ideal; adding a knife in the extruder's perforated plate and adding a silicone emulsifier to assist Although the crushing and dispersing of gel can improve the crushing and dispersing properties for quite some reason, the addition of low hydrophilic surfactant will cause the water absorption properties to change, which will cause the water absorption rate and water absorption ratio of the super absorbent resin to decrease. ; The use of controlled gel temperature of 45-90 degrees and the pore diameter of the porous plate is 6.5-18mm, extruding has the disadvantages of gel temperature control, and the effect of reducing gel aggregation is quite limited. Therefore, the present invention mainly provides a A method for manufacturing a superabsorbent resin is provided. The method includes at least Zeagar which can help the resin crush and disperse after the reaction, but does not affect the high hydrophilic surfactant of the superabsorbent resin's water absorption rate. Dry and pulverize at 160 ° C to obtain this super absorbent resin, and this super absorbent resin will not affect the water absorption. The small gel treated by this invention has good dispersibility and is advantageous This paper size applies to Chinese national standard (CNS > A4 size (210X297mm) -------- f: ^-(Please read the notes on the back before filling this page)-Order by the Ministry of Economic Affairs 4228 66 A7 printed by the Standard Bureau Shellfish Cooperative. V. Description of the invention (7) In the drying process, the structure of the highly hydrophilic surfactant added as shown in the present invention is: ^-[OCCKROCHCR '^ Oy ^ 4 ^ R1 may be a linear or branched alkyl group of C2 ~ le; R2 and R3 may each be a fluorene or oxo group or a methyl group; R * may be a linear or branched alkyl group of h or. X may be 2 or more, when X is 2, Υ can be 6-170, when X is 3 or more, y can be 3-34. Among them, sorbitol poly 6 can be used. Alcohols, propylene glycol polyethylene glycol, butanediol polyethylene glycol, hexamethylene glycol polyethylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol and polypropylene glycol copolymers, methyl ethylene glycol diethylene glycol Diol, 1,2-dimethylethylene glycol diethylene glycol, glycerin diethylene glycol, glycerin trimer 6 glycol, fluorenyl glycerol trimer 6 difluorene, L2- Dimethylglycerol triethylene glycol, ethylglycerol triethylene glycol, 2-methylglycerol triethylene glycol, 2-6 based glycerol triethylene glycol, etc .; The added highly hydrophilic surfactants can be used alone or in combination of two or more. The appropriate dosage is from 0.001 wtSi to 10 wt% (based on the weight of the neutralized acrylate). The appropriate amount is between 0.1 yuan ^% to 4% of the goods. In order to show that the present invention reduces the viscosity of the small gels and makes the microcoagulation easy to disperse, the present invention will observe the dispersion of the small gels, and add the causes and effects of the high hydrophilic surfactant to the dispersion. 1 sheet disperses the small gel immediately after it exits the crusher; disperse sink 2 indicates that the small agglomerate has a little agglutination after the crusher, and immediately disperses after shaking; disperse sink 3 (please read the precautions on the back first) (Fill in this page again) 丨 Binding
本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 經濟部中央搮準局貝工消費合作社印製 4228 66 A7 _B7_ 五、發明説明（g) 示小凝膠體出絞碎機後有凝集，經搖動後可分散但有少許 凝集；分散狀沉4表示小凝膠體出絞碎機後有凝集情形， 經搖動後仍無法分散。 > 高吸水性樹脂吸水迷度的判定，是以漩渦消失時間的 大小作為依據，旋渦消失時間長者吸水速度慢，反之蛛滿 消失時間短者吸水速度快，測定方法為以100ml燒杯裝遂 0,9%NaCl水溶液50ml ’加入2cm長的磁石挽拌子一顆，以 磁石攪拌器設定600rpm攪拌，加入高吸水性樹脂2g，以碼 表記時，目視溶液中光的倒影消失時間，即為漩渦消失時 間。 以下詳細地列出參考工作實例，以便說明本發明； 本發明範圍不受這些實例所限制。 實例一： 1) 100c.c圓錐瓶中加入30g丙烯酸及32.4g的水；另外 在100c.c圓錐瓶中稱取48%氫氧化鈉水溶液24.3g，& 冰冷下將氫氧化鈉水溶液緩緩加入丙烯酸水溶液中進行 中和；此時得單髖濃度42wt%水溶液，其中70mol(莫耳 比）丙烯酸部份中和為丙烯酸鈉。 2) 再加入0.1〇2g的N，N,N-三（2-丙烯基）胺及0.219g的 聚乙二醇（分子量800)妗部分中和的丙烯酸溶液，並維 持溫度於20°C左右。 3) 加入0.016g L-抗壞血酸，〇,2g過硫酸鈉及0.2g 2.2-偶氮基雙（2-脒基丙烷）二孃酸鹽以起始反應。 4) 反應後將此高吸水性樹脂利用切式絞碎機切成2mm直徑 -9 _ 本紙張尺度it财g ϋ家棣準（CNS ) Α4聽公 c請先閲讀背面之注意事項再填舄本頁) -訂· 4228 66 五、發明説明（9) A7 B7This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Central Laboratories Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperative. 4228 66 A7 _B7_ V. Description of the invention (g) shows that the small gel is crushed There is agglutination after the machine, and it can be dispersed but a little agglutinated after shaking; the dispersed state Shen 4 indicates that the small gel has agglutination after the mincing machine, and cannot be dispersed after shaking. > The superabsorbent resin's water absorption susceptibility is determined based on the size of the vortex disappearance time. The longer the vortex disappearance time is, the slower the water absorption rate is, and the shorter the spider full disappearance time is, the faster the water absorption rate is. The measurement method is to use a 100ml beaker. , 9% NaCl aqueous solution 50ml 'Add a 2cm long magnet stirrer, stir with a magnetic stirrer set at 600rpm, add 2g of super absorbent resin, and use the code table to visually observe the disappearance time of light reflection in the solution, which is the vortex. Disappear time. Reference working examples are listed in detail below to illustrate the present invention; the scope of the present invention is not limited by these examples. Example 1: 1) 30g acrylic acid and 32.4g of water were added to a 100c.c conical flask. In addition, 24.3g of a 48% sodium hydroxide aqueous solution was weighed into the 100c.c conical flask. &Amp; Add an acrylic acid aqueous solution to neutralize it; at this time, a single hip concentration of 42 wt% aqueous solution is obtained, of which 70 mol (molar ratio) acrylic acid is partially neutralized to sodium acrylate. 2) Add 0.102 g of N, N, N-tris (2-propenyl) amine and 0.219 g of polyethylene glycol (molecular weight 800) 妗 partially neutralized acrylic acid solution, and maintain the temperature at about 20 ° C . 3) Add 0.016 g of L-ascorbic acid, 0.2 g of sodium persulfate, and 0.2 g of 2.2-azobis (2-amidinopropane) dinitrate to initiate the reaction. 4) After the reaction, cut this super absorbent resin into 2mm diameter -9 with a cutter mill. _ This paper size is 财 gg 棣 家 棣 准 (CNS) Α4 Please read the precautions on the back before filling. (This page)-Order · 4228 66 V. Description of the invention (9) A7 B7
' 經多.«.0-央裙法局員二消費合作.ΐΐ-νρί 玉: 1： f Pl· $ 以下的凝膠體；分散情系畜!：， 5)以130°C溫度乾燥2小時；利用篩網篩選0.1mm〜0.85 nim固定粒徑，得粉狀高吸水性樹脂，測得液渴消失時間 為47秒。 實例二： 重覆實例一，但步驟2)改為加入0.219g的聚乙二醇（分 子量1000 )，其餘同實例一，绞碎後分散情形為1，乾 燥、粉碎、筛選後可得高吸水性樹脂，測定漩渦消失時 間為44秒。 實例三： 重覆實例一，但步驟2)改為加入0.2l9g的聚乙二酵（分 子量，其餘同實例一，絞碎後分散情形為1，乾 燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失時 間為49秒。 實例四： 重覆實例一，但步驟2)改為加入0.219g的聚乙二醇（分 子量1500 )，其餘同實例一，绞碎後分散情形為1，乾 燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失時 間為41秒。 實例五： 重覆實例一，但步驟2)改為加入0.2I9g的聚乙二醇（分 子量2000 )，其餘同實例一，絞碎後分散情形為1，乾 燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失時 間為51秒。 -10 之绝乐尺度逋用中國國家搮準（CNS ) A4iJL格（210Χ297公龙） 經濟部中央標準局員工消費合作社印策 4ZZB 6 〇 A7 B7 五、發明説明（10) 實例六： 重覆實例一，但步驟2)改為加入0.219g的聚乙二醇（分 子量6000 )，其餘同實例一，絞碎後分散情形為1，乾 燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失時 間為42秒。 實例七： 重覆實例一，但步驟2)改為加入0.219g的聚乙二醇（分 子量10000)，其餘同實例一，絞碎後分散情形為1，乾 燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失時 間為39秒。 實例八： 重覆實例一，但步驟2)改為加入0.219g的聚乙二醇（分 子量12000)，其餘同實例一，絞碎後分散情形為1，乾 燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失時 間為47秒。 實例九： 重覆實例一，但步驟2)改為加入0.219g的2-乙基丙三 醇三聚乙二醇（n=12)，其餘同實例一，絞碎後分散情形 為2,乾燥、粉碎、篩選後可得高吸水性樹脂，測定漩 渦消失時間為41秒。 實例十： 重覆實例一，但步驟2)改為加入0.219g的2-乙基丙三 醇三聚乙二醇（n=15)，其餘同實例一，絞碎後分散情形 為1，乾燥、粉碎、篩選後可得高吸水性樹脂，測定旋 -11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝------訂-----線-- 經濟部中央標準局員工消費合作社印製 4-228 6 6 A7 B7 五、發明説明（u) 渦消失時間為47秒。 實例十一： 重覆實例一，但步驟2)改為加入0.219g的2-乙基丙三 醇三聚乙二醇（n=20)，其餘同實例一，絞碎後分散情形 為1，乾燥、粉碎、篩選後可得高吸水性樹脂，測定漩 渦消失時間為43秒。 實例十二： 重覆實例一，但步驟2)改為加入0.219g的2-乙基丙三 醇三聚乙二醇（n=25)，其餘同實例一，絞碎後分散情形 為1，乾燥、粉碎、篩選後可得高吸水性樹脂，測定漩 渦消失時間為48秒。 實例十三： 重覆實例一，但步驟2)改為加入0.219g的丙三醇三聚 6二醇（n=12)，其餘同實例一，絞碎後分散情形為2, 乾燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失 時間為47秒。 實例十四： 重覆實例一，但步驟2)改為加入0.219g的丙三醇三聚 乙二醇（n=15)，其餘同實例一，绞碎後分散情形為1， 乾燥、粉碎、篩選後可得高吸水性樹脂，測定旋渦消失 時間為44秒。 實例十五： 重覆實例一，但步驟2)改為加入0.219g的丙三醇三聚 乙二醇（n=20)，其餘同實例一，绞碎後分散情形為1， -12 - 1------叫，裝------訂-------Η 一 {锖先閲讀背面之注意事項再填寫本頁) 本紙伕尺度適用中國國家標準（CMS ) A4規格（2I0X297公釐） 4228 66 經濟部中央樣準局貝工消費合作社印製 A7 B7 五、發明説明（12) 乾燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失 時間為51秒。 實例十六： 重覆實例一，但步驟2)改為加入0.219g的丙三醇三聚 乙二醇（n=25)，其餘同實例一，绞碎後分散情形為工， 乾燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消失 時間為53秒。 比較例一： 重覆實例一，但步驟·2)不加入任何界面活性剩.，其餘同 同實例一，絞碎後分散情形為3，乾燥、粉碎、篩選後 可得高吸水性樹脂，測定漩渦消失時間為46秒。 比較例二： 重覆實例一，但步驟2)加入〇,219g的硬脂酸鉀，其餘 同實例一，絞碎後分澈情形為1，乾燥、粉碎、轉選後 可得高吸水性樹脂，測定漩渦消失時間為Π8秒。 比較例三： 重覆實例一，但步驟2)加入〇.219g的六元醇脂肪酸酯 (Span-20，Sorbitan monolaurate )，其餘同實例一， 絞碎後分散情形為1，乾燥、粉碎、篩選後可得高吸水 性樹脂，測定漩渦消失時間為165秒。 實例十七： 1) 100c.c圓錐瓶中加入30g丙烯酸及32.4g的水；另外 -13 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝_ -訂' 4228 6 6 經濟部中央揉準局貝工消費合作社印裝 ΑΊ B7 五、發明説明（13) 在100c.c圓錐瓶中稱取48%氫氧化鈉'水溶液24.如’於 冰冷下將氳氧化鈉水溶液緩緩加入丙烯酸水溶液中進行 中和；此時得單體濃度42wt%水溶液，其中(莫耳 比）丙烯酸部份'中和為丙烯酸鈉。 2) 再加入0.102g的Ν,Ν-次甲基雙丙烯醯胺及〇_219g的 聚乙二酵（分子量1〇〇〇)於部分中和的丙烯酸溶液，並維 持溫度於20°C左右。 3) 加入0_016g L-杭壞血酸，〇.2g過硫酸鈉及〇.2g 2.2-偶氮基雙（2-脒基丙烷）二鹽酸鹽以起始反應。 4) 反應後將此高吸水性樹脂利用切式絞碎機切成2mm直徑 以下的凝膠體；分散情形為10 5) 以130°C溫度乾燥2小時；利用篩網篩選O.lmiD〜0.奶 顏固定粒徑，得粉狀高吸水性樹脂；測得漩渦消失時間 為41秒。 實例十八： ▼覆實例十七，但步驟2)改為加入〇.219g的聚乙二醇( 分子量6000 )，其餘同實例十七，絞砕後分叙情形為1 ，乾燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦消 失時間為49秒。 實例十九： ，覆ir例十七，但步驟2)改為加人G 219g的2_乙基丙 =醇三聚乙二醇（n=2〇)，其餘同實例十七，絞碎後分散 二形為1，乾垛、粉碎、篩選後可得高吸水性樹脂，測 定旋渴消失時間為43秒。 本紙張尺度適用中 (請先閲讀背面之注意事項再填寫本頁) 裝. ,11 ~ 14 - Λ228 6 6 A7 B7 五、發明説明（14) 實例二十： 重覆實例十七’但步樣2)改為加入〇 219g的两三醇= 聚乙二醇（n=20) ’其餘同實例十七，絞碎後分散愔形 1，乾燥、粉碎、篩選後可得高吸水性擀脂，測定漩^ 消失時間為46秒。 比較例四： 重覆實例十七，但步驟2)不加入任何界面活性劑，其餘 同同實例十七，絞碎後分散情形為3,乾燥、粉碎、薛 選後可得高吸水性樹脂，測定漩渦消失時間為42秒。 比較例五： 重覆實例十七，但步驟2)加入〇.219g的硬脂酸_ . 餘同實例十七，絞碎後分散情形為1，乾燥、粉碎-選後可得高吸水性樹脂，測定漩渦消失時間為121秒。 比較例六： 重覆實例十七，但步驟2)加入0.219g的六元醉脂肪酸 酯（Span-20，Sorbitan monolaurate )，其餘同實例十 七，絞碎後分散情形為1，乾燥、粉碎、篩選後可得高 吸水性樹脂，測定漩渦消失時間為147秒。 其 篩 (請先閲讀背面之注項再填寫本頁} -. Γ •^ 經濟部中央橾隼局負工消費合作社印裝 實例二十一： l)100c.c圓雄瓶中加入30g丙烯酸及32.4g的水；另外 在100c.c圓錐瓶中稱取48¾氳氧化鈉水溶液24.3g，於 冰冷下將氬氧化鈉水溶液緩緩加入丙烯酸水溶液中進行 15, 本紙張尺度適用中國國家梂準（CNS ) A4規格（21〇Χ297公釐） 4228 6 6 A7 B7 五、發明説明（15) 中和；此時得單體濃度42wt%水溶液，其中70mol%(莫耳 比）丙烯酸部份中和為丙烯酸鈉。 2) 再加入〇.i〇2g的丙三醇三聚乙二醇三縮水甘油醚（η二 15)及0.219g的聚乙二醇（分子量1000)於部分中和的丙烯 酸溶液，並維持溫度於20°C左右。 3) 加入0.016g L-抗壞血酸，0.2g過硫酸鈉及0.2g 2.2-偶氪基雙（2-脒基丙烷）二鹽酸鹽以起始反應。 4) 反應後將此高吸水性樹脂利用切式绞碎機切成2mm直徑 以下的凝膠體；分散情形為1。 5) 以13(TC溫度乾燥2小時；利用篩網篩選0.1mm〜0.85 mm固定粒徑，得粉狀高吸水性樹脂；測得漩渦消失時間 為45秒。 實例二十二： 重覆實例二十一，但步驟2)改為加入〇.219g的聚乙二醇 (分子量6000)，其餘同實例二十一，絞碎後分散情形為 1 ，乾燥、粉碎、篩選後可得高吸水性樹脂，測定漩渦 消失時為40秒。 實例二十三： 經濟部中央標準局員工消費合作社印製 ^ϋ' il - n^i ^^^1 ^^^1 ^^^1 ^^^1 π 1 - (請先閲讀背面之注意事項再填寫本頁) 重覆實例二十一，但步驟2)改為加入〇.219g的2-乙基 丙三醇三聚乙二醇（n=20)，其餘同實例二十一，絞碎後 分散情形為1，乾燥、粉碎、篩選後可得高吸水性樹脂 ，測定漩渦消失時間為44秒。 實例二十四： 重覆實例二十一，但步驟2)改為加入〇.219g的丙三醇 本紙張尺度適用中國國家揉準（CNS ) A4規格（2丨Ο X 2?7公釐） A7 B7 五、發明説明（16) (請先閱讀背面之注意事項再填寫本頁) 三聚乙二醇（n=20)，其餘同實例二十一，绞碎後分散情 形為1，乾燥、粉碎、篩選後可得高吸水性樹脂，測定 漩渦消失時間為39秒。 比較例七： 重覆實例二十一，但步驟2)不加入任何界面活性劑，其 餘同實例二十一，絞碎後分散情形為3，乾燥、粉碎、 篩選後可得高吸水性樹脂，測定漩渦消失時間為46秒。 比較例八： 重覆實例二十一，但步驟2)加入0,219g的硬脂酸鉀， 其餘同實例二十一，絞碎後分散情形為1，乾燥、粉碎 、篩選後可得高吸水性樹脂，測定漩渦消失時間為134 秒0 比較例九： 重覆實例二十一，但步驟2)加入0.219g的六元醇脂肪 酸酯（Span-20，Sorbitan monolaurate )，其餘同實例 二十一，絞碎後分散情形為1，乾燥、粉碎、篩選後可 得高吸水性樹脂，測定漩渦消失時間為154秒。 經濟部中央標率局貝工消費合作社印裝 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公嫠）'Jingduo. «.0-Yang skirt law bureau member two consumer cooperation. Ϊ́ΐ-νρί Jade: 1: f Pl · $ gel or less; dispersed love animals!:, 5) drying at 130 ° C for 2 hours ; Use a sieve to screen a fixed particle size of 0.1 mm to 0.85 nim to obtain a powdery superabsorbent resin. The measured time for liquid thirst to disappear is 47 seconds. Example 2: Repeat Example 1, but add 0.219g of polyethylene glycol (molecular weight 1000) in step 2), the rest is the same as in Example 1. The dispersion after crushing is 1, and it can be obtained after drying, crushing and screening. The water-absorbent resin was measured to have a vanishing time of 44 seconds. Example 3: Repeat Example 1, but step 2) instead add 0.2l9g of polyethylene glycol (molecular weight, the rest is the same as in Example 1, the dispersion after crushing is 1, and the super absorbent resin can be obtained after drying, crushing and screening. The measurement of the vanishing time of the vortex is 49 seconds. Example 4: Repeat Example 1, but add 0.219g polyethylene glycol (molecular weight 1500) in step 2), the rest is the same as in Example 1, the dispersion after crushing is 1, and dry After crushing and sieving, a super absorbent resin can be obtained, and the disappearance time of the vortex is 41 seconds. Example 5: Repeat Example 1, but add 0.2I9g of polyethylene glycol (molecular weight 2000) instead of step 2), the rest is the same as in Example 1. The dispersion after crushing is 1, and high water absorption can be obtained after drying, crushing and screening. Resin, the vortex disappearance measurement time was 51 seconds. -10's absolute joy scale, using China National Standards (CNS) A4iJL grid (210 × 297 male dragon), Central Consumers Bureau of Ministry of Economic Affairs, Consumer Cooperative Cooperative Imprint 4ZZB 6 〇A7 B7 V. Description of invention (10) Example 6: Repeated example One, but step 2) was changed to add 0.219g of polyethylene glycol (molecular weight 6000), the rest is the same as in Example 1, the dispersion after crushing is 1, after drying, crushing, and screening, a superabsorbent resin can be obtained, and the vortex disappears The time is 42 seconds. Example 7: Repeat Example 1, but add 0.219g of polyethylene glycol (molecular weight 10000) in step 2), the rest is the same as in Example 1. The dispersion after crushing is 1, and it can get high water absorption after drying, crushing and screening. Resin, the vortex disappearance measurement time was 39 seconds. Example 8: Repeat Example 1, but add 0.219g of polyethylene glycol (molecular weight 12000) instead of step 2). The rest is the same as in Example 1. The dispersion after crushing is 1, and high water absorption can be obtained after drying, crushing and screening. Resin, the vanishing time of the swirl was 47 seconds. Example 9: Example 1 was repeated, but step 2) was replaced by adding 0.219g of 2-ethyl glycerol triethylene glycol (n = 12), and the rest was the same as in Example 1. The dispersion after being minced was 2, and dried. After crushing and sieving, a super absorbent resin can be obtained, and the disappearance time of the vortex is 41 seconds. Example 10: Example 1 was repeated, but step 2) was replaced by adding 0.219g of 2-ethylglycerol triethylene glycol (n = 15), and the rest was the same as in Example 1. The dispersion after crushing was 1, and dried. Super-absorbent resin can be obtained after crushing, sieving, and measurement. -11-This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page). ------ Order ----- Line-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4-228 6 6 A7 B7 V. Description of the invention (u) The vortex disappearing time is 47 seconds. Example 11: Example 1 was repeated, but step 2) was replaced by adding 0.219 g of 2-ethylglycerol triethylene glycol (n = 20), and the rest was the same as in Example 1. The dispersion after crushing was 1, After drying, pulverizing and screening, a super absorbent resin was obtained, and the disappearance time of the vortex was measured to be 43 seconds. Example 12: Example 1 was repeated, but step 2) was replaced by adding 0.219 g of 2-ethylglycerol triethylene glycol (n = 25), the rest was the same as in Example 1, and the dispersion after crushing was 1, After drying, pulverizing, and sieving, a super absorbent resin was obtained, and the disappearance time of the swirl was measured to be 48 seconds. Example 13: Example 1 was repeated, but step 2) was replaced by adding 0.219 g of glycerol trimer 6 glycol (n = 12), and the rest was the same as in Example 1. The dispersion after crushing was 2, dried, crushed, Super-absorbent resin was obtained after screening, and the disappearance time of vortex was 47 seconds. Example 14: Repeat Example 1, but add step 2) to add 0.219g of glycerol triethylene glycol (n = 15), the rest is the same as in Example 1, the dispersion after crushing is 1, dry, crush, A super absorbent resin was obtained after screening, and the vortex disappearance time was measured to be 44 seconds. Example 15: Example 1 was repeated, but step 2) was replaced by adding 0.219 g of glycerol triethylene glycol (n = 20), and the rest was the same as in Example 1. The dispersion after crushing was 1, -12-1 ------ Call, install ------ order ------- Η 锖 (锖 Please read the precautions on the back before filling in this page) The standard of this paper is applicable to China National Standard (CMS) A4 specifications (2I0X297mm) 4228 66 Printed by A7 B7, Shellfish Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (12) Super absorbent resin can be obtained after drying, pulverizing, and screening. The disappearance time of vortex is 51 seconds. Example 16: Repeat Example 1, but add step 2) to add 0.219g of glycerol triethylene glycol (n = 25), the rest is the same as in Example 1. The dispersing condition after grinding is industrial, drying, crushing, Super-absorbent resin was obtained after screening, and the disappearance time of vortex was measured to be 53 seconds. Comparative Example 1: Repeat Example 1, but do not add any interfacial activity. The rest is the same as in Example 1. The dispersion after crushing is 3, and the superabsorbent resin can be obtained after drying, crushing and screening. The vortex disappears in 46 seconds. Comparative example two: Example 1 was repeated, but step 2) was added with 0,219 g of potassium stearate, and the rest was the same as in Example 1. After the crushing, the separation was 1 and the superabsorbent resin was obtained after drying, pulverization and conversion. The measurement of the vortex disappearance time was Π8 seconds. Comparative example three: Example 1 is repeated, but step 2) 0.219 g of a hexahydric alcohol fatty acid ester (Span-20, Sorbitan monolaurate) is added, and the rest is the same as in Example 1. The dispersion after crushing is 1, dried, crushed, Super-absorbent resin was obtained after screening, and the disappearance time of vortex was 165 seconds. Example 17: 1) Add 30g of acrylic acid and 32.4g of water to a 100c.c conical flask; otherwise -13 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back first (Fill in this page again) Packing _-Ordering '4228 6 6 Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed AΊ B7 V. Description of the invention (13) Weigh 48% sodium hydroxide' solution in a 100c.c conical flask 24. For example, "the sodium hydroxide aqueous solution is slowly added to the acrylic acid aqueous solution for neutralization under ice cooling; at this time, an aqueous solution with a monomer concentration of 42% by weight is obtained, in which the (mole ratio) acrylic acid part" is neutralized to sodium acrylate. 2) Add 0.102g of N, N-methacrylamide and 219g of polyethylene glycol (molecular weight 1000) to the partially neutralized acrylic acid solution, and maintain the temperature at about 20 ° C . 3) Add 0-016 g of L-ascorbic acid, 0.2 g of sodium persulfate and 0.2 g of 2.2-azobis (2-amidinopropane) dihydrochloride to initiate the reaction. 4) After the reaction, the super absorbent resin is cut into gels with a diameter of 2 mm or less by a cutter mill; the dispersion is 10 5) dried at 130 ° C for 2 hours; sieved with a sieve O.lmiD ~ 0 . Milk face fixed particle size to obtain powdery superabsorbent resin; measured vanishing time was 41 seconds. Example 18: ▼ Example 17 is repeated, but step 2) is replaced by adding 0.2219 g of polyethylene glycol (molecular weight 6000), the rest is the same as in Example 17, the classification is 1 after stranding, drying, crushing, screening After that, a super absorbent resin was obtained, and the disappearance time of the swirl was measured to be 49 seconds. Example 19: Example 17 is covered, but step 2) is replaced with 2_ethylpropane = alcohol triethylene glycol (n = 2〇) of G 219, the rest is the same as in Example 17, after being minced The disperse dimorph is 1, and the super absorbent resin can be obtained after dry stacking, pulverizing, and screening. The disappearance time of the thirst is 43 seconds. This paper is applicable (please read the precautions on the back before filling in this page). 11 ~ 14-Λ228 6 6 A7 B7 V. Description of the invention (14) Example 20: Repeat example 17 'but the steps 2) Add 219g of glycerol = polyethylene glycol (n = 20). The rest is the same as in Example 17. After crushing, disperse the crumb 1 and dry, pulverize, and screen to obtain a highly absorbent rolling fat. The vortex disappearance time was measured to be 46 seconds. Comparative Example 4: Repeat Example 17 but do not add any surfactant, the rest is the same as Example 17, the dispersion after crushing is 3, and the super absorbent resin can be obtained after drying, crushing and Xue Xuan. The measurement of the vanishing time was 42 seconds. Comparative Example 5: Repeat Example XVII, but step 2) Add 0.219g of stearic acid _. Identical to Example XVII, the dispersion after crushing is 1, dry, pulverized-selected to obtain super absorbent resin The measurement of the vortex disappearance time was 121 seconds. Comparative Example 6: Example 17 was repeated, but step 2) 0.219 g of a hexavalent drunk fatty acid ester (Span-20, Sorbitan monolaurate) was added, and the rest was the same as in Example 17, and the dispersion after crushing was 1, dried and crushed. 2. Super absorbent resin can be obtained after screening, and the disappearance time of vortex is 147 seconds. Its sieve (please read the note on the back before filling out this page)-. Γ • ^ Example 21 of printing by the Central Government Bureau of the Ministry of Economic Affairs, Consumer Cooperatives: l) Add 100g. 32.4g of water; In addition, weigh 24.3g of 48¾ 氲 sodium oxide aqueous solution in a 100c.c conical flask, and slowly add the sodium argon oxide aqueous solution to the acrylic acid aqueous solution under ice-cooling for 15th. ) A4 specification (21 × 297 mm) 4228 6 6 A7 B7 V. Description of the invention (15) Neutralization; At this time, a 42% by weight aqueous solution of monomer concentration was obtained, of which 70 mol% (mole ratio) acrylic acid was partially neutralized to acrylic acid. sodium. 2) Add 0.12 g of glycerol tripolyethylene glycol triglycidyl ether (η di 15) and 0.219 g of polyethylene glycol (molecular weight 1000) to the partially neutralized acrylic acid solution, and maintain the temperature Around 20 ° C. 3) Add 0.016 g of L-ascorbic acid, 0.2 g of sodium persulfate, and 0.2 g of 2.2-isofluorenylbis (2-fluorenylpropane) dihydrochloride to initiate the reaction. 4) After the reaction, the super absorbent resin is cut into gels with a diameter of 2 mm or less by a cutter mill; the dispersion is 1. 5) Dry at 13 ° C for 2 hours; sieve a fixed particle size of 0.1 mm to 0.85 mm with a sieve to obtain a powdery superabsorbent resin; measured the vanishing time of 45 seconds. Example 22: Repeat Example 2 Eleven, but step 2) was changed to add 0.219g of polyethylene glycol (molecular weight 6000), the rest is the same as in Example 21, the dispersion after crushing is 1, and the super absorbent resin can be obtained after drying, crushing and screening. It was 40 seconds when the measurement of the vortex disappeared. Example 23: Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ ϋ 'il-n ^ i ^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 π 1-(Please read the precautions on the back first Fill in this page again) Repeat example 21, but step 2) instead add 0.219 g of 2-ethyl glycerol triethylene glycol (n = 20), the rest is the same as in example 21, minced The post-dispersion condition is 1, and a super absorbent resin can be obtained after drying, pulverization, and screening. The disappearance time of the swirl is 44 seconds. Example 24: Example 21 is repeated, but step 2) is replaced by the addition of 0.219 g of glycerin. The paper size is applicable to the Chinese National Standard (CNS) A4 (2 丨 〇 X 2 ~ 7 mm) A7 B7 V. Description of the invention (16) (Please read the notes on the back before filling in this page) Triethylene glycol (n = 20), the rest is the same as in Example 21. The dispersion after crushing is 1, dry, After crushing and screening, a super absorbent resin was obtained, and the measurement of the vanishing time of the vortex was 39 seconds. Comparative Example 7: Example 21 was repeated, but no surfactant was added in step 2), and the rest was the same as in Example 21. The dispersion after crushing was 3, and a superabsorbent resin was obtained after drying, crushing, and screening. The measurement of the vanishing time was 46 seconds. Comparative Example 8: Repeat Example 21, but add 2,219 g of potassium stearate in step 2), the rest is the same as in Example 21, the dispersion after crushing is 1, and high water absorption can be obtained after drying, crushing and screening. Resin, measuring the disappearance time of vortex is 134 seconds. 0 Comparative Example 9: Repeat Example 21, but step 2) Add 0.219g of hexaol fatty acid ester (Span-20, Sorbitan monolaurate), the rest is the same as Example 21. The dispersion after crushing is 1, the super absorbent resin can be obtained after drying, crushing, and screening, and the vortex disappearance time is 154 seconds. Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies to the Chinese National Standard (CNS) A4 (210X 297 cm)