1332517 九、發明說明： 【發明所屬之技術領域】 發明係有關於一種高吸水性樹脂的製造方法，尤其是一種可溶 物含量低的吸水性樹脂的製造方法。 【先前技術】 高吸水性樹脂具有強大的保水力，可吸收百倍甚至於千倍於本 身重量的水’且吸水後可膨潤具有保持不流動的狀態，即使施加 壓力也不會滲漏’且被吸收的水可缓緩地在大氣中釋出。由於具 有上述之特性，所以最早使用於農森林業的土壌保水劑，近年因 兩吸水性樹脂的生產技術有相當大的進步，所以也廣泛地運用於 •衛生用品如尿布、成人失禁用品及婦女衛生用品的吸水劑及保存 食物用的保鮮應用等。1332517 IX. Description of the Invention: The present invention relates to a method for producing a super absorbent resin, and more particularly to a method for producing a water-absorbent resin having a low soluble content. [Prior Art] The super absorbent resin has a strong water retention capacity, can absorb 100 times or even thousands of times its own weight of water' and can swell after being absorbed to maintain a non-flowing state, even if pressure is applied, it will not leak. The absorbed water can be slowly released in the atmosphere. Due to the above characteristics, the earliest soil water retaining agent used in the agricultural forestry industry has been widely used in recent years due to considerable progress in the production technology of two water-absorbent resins. It is also widely used in sanitary products such as diapers, adult incontinence products and women. Water absorbing agent for sanitary products and preservation application for preserving food.
南吸水性樹脂的成分材料有遇水分解型的殿粉丙稀猜 (hydrolyzed starch-acryl〇nitriie)接枝聚合物（日本專利公開 公報昭49(1974)-43,395)，中和之殿粉丙稀酸接枝聚合物（日本 專利公開公報昭51 (1976)-125,468)，皂化乙___共聚 ^ ( 利公開公報昭52〇977)'14, _，水解丙稀腈共聚物 或丙細fe胺共聚物（曰本專利公郝 八I 寻才“報昭53 (簡)-15,959)，及部 ^中和聚嫩（日綱公叫SS55(麵w)等。 使㈣馳及⑽_進行交卿合所得之·水性樹w x^25i7 佔最大部份也最為歸，其相為㈣射魏岭棘得，且 ，得的高吸雜_射高的财能力，及具絲造成本低廉且 取具經濟效益，故絲最#触的高财性樹脂。The component material of the south water-absorbent resin is a hydrolyzed starch-acryl〇nitriie graft polymer (Japanese Patent Laid-Open Publication No. Sho 49 (1974)-43,395). Dilute acid graft polymer (Japanese Patent Laid-Open Publication No. Sho 51 (1976)-125, 468), saponified B___ copolymer ^ (Lin published bulletin 52 977) '14, _, hydrolyzed acrylonitrile copolymer or acrylic Fe amine copolymer (曰本专利公八八 I 寻才" reported Zhao 53 (Jane) -15, 959), and the Ministry of Zhonghe and the tender (Japanese version of the public called SS55 (face w), etc.. (4) Chi and (10) _ The water-based tree wx^25i7, which is the result of the payment of the Qinghe, is the most important part. The phase is (4) the Weiling Ridge is obtained, and the high-yielding _ high-powered ability and the low cost are achieved. And take economic benefits, so the silk is the most high-yield resin.
聚合丙烯酸及丙稀酸鹽形成高吸水性樹脂的方法已被多方面 :開發成功’对多種已剌於1界生產，其聚合方法有禱膜 聚合反應（曰本專利公開公報昭48(1973) —42，傷），於輸送帶上 進行聚合反應（日本專利公開公報昭58(聰卜级Μ)，粉碎之 f掉刀片的捏拌射進行聚合反應（日本專利公開公報昭 7(1982)-34,1G1) ’進行逆相懸浮液聚合反應（日本專利公開公 7 59(1984)-37，_’或將單财觀«賊絲質上、進行 聚合反應（日本專利公開公報昭62⑽7)_53，㈣。 【擬解決之課題】 • 战聚合方法大多是將聚合單體、聚合引發劑與交聯劑等反應 原料1進行自由絲合反應而歧職_，如此整個聚合反 應不易控制，可溶物含量也較高。鑑於此，本發明提供-種高吸 尺f生麻的缺方法’其聚合反應過程相對來說較為穩^，反應 熱也不致於過高，除了改善操作環境之外，更提高了產品質量。 本發明所提母的製造方法至少包括·· 1)使中和率5〇船ie%以上之含酸基單體水溶液與聚合反應 /¾ J於g線切留’作自由基聚合反應得黏賴預聚 物其A基早體係選自丙稀酸或曱基丙稀酸或2-丙稀胺 -2-曱基丙烧續酸或其混合物； 長鏈㈤親水性的多元環氧基化合物於黏稠預聚物 、、糊光起始合財錢—步生成娜狀固體； 3以脈度100 c至250〇C熱風進行乾燥、粉碎、筛選； 4) 表面交聯劑塗覆處理； 5) 再以溫度8G°C至23Gt加熱表面處理； 6) 添加惰性無機鹽粉末。 。。上述之預U反應可以在—個預聚合反應器中進行 5該反應 器需具備能夠錄合反應·混合均勻且進行麟合的作用。預 聚合反應ϋ除了可以採用—般安財狀直立式反應槽外， 也可以㈣-觀式的肢容器，巾心絲有錢料單向流動的 擾拌水|螺#或並列之雙螺桿，這樣可以保證反應物料單向向 則運動而不出現回流的現象，從而避免了聚合反應物料在反應器 令停留時間過長而形成凝膠狀固體。細，上述類型之反應器通 常採用批次人料的方式，較不利於工業化生產。 【解決課題之技術手段】 鑑於此，本發明提供一種可連續生產具備低可溶物含量之高 吸水性樹朗方法，其舰在m，使單體絲於管線中 坪留’並將聚合w發劑加人至管線中，使含酸基單體進行自由基 聚合反應而成_的高分子。第二步，黏_預聚物與多元環^ 1332517 基化合物混合之後，可連續加人至皮帶反應器上，其上方利用各 聚物轉變成硬化成凝膠狀固體。 、 於管線中進行鮮合除了較—般直立歧賴韻狀容哭節 省空間外’更能夠確保反應單體水溶液紐先出的原則，使得預 聚合過程裡纽料_留於#、針，進轉錄合反應過度的 情形發生。反應單體水溶·管射的滞留咖是控制預聚合反 應的重要时之-，如滞留時間長，咖聚合反應越完全，賊 ㈣度與分子量也越高，成品的可溶份也較低，但較容易發生於 管線中過度聚合的現象；㈣㈣間短，咖料黏度與分子量 較低’成品可溶份較高，但發生過度聚合的機會較少。此外，反 應單體溶液與聚如丨㈣，乃至照歧應前之縣物與架橋劑的 混合均勻性也是辟縣合絲無光反應的重要因素。為 高上述各流體彼此之_混合效果，财可朗下财法:⑴於 管線中通人雜氣體，如：氮氣、或：氧化碳、或氦氣、或氖氣、 或其此合讀’在工業界為節省成本及考慮便於取得，通常使用 氮氣或二氧化碳混合氣體。此外，惰性氣體_力要高於管 線内壓力’柯賴性氣體·注人含單體水溶液管線内而使各 反應流體軸_絲’⑵好線巾加朗_或具混合效 果的填充物如：拉西環、或波耳環，⑶使用汽液型靜態混合器。 光起始聚合技術發展純熟，顧也相當廣泛，例如：塗裝、 1332517 印刷業、PCB/LCD製程、鞋業等等。利用照光引發聚合的方式具有 许多優勢，如：縮短製程、提昇產能與節省能源等等。光源種類 繁多，包括紫外線、紅外線、χ—射線或7_射線等等，一般以紫外 線最為大眾所使用，它具有波長較短⑽.nm)，穿透力強的特 性。值得注意的是’一般製程用的紫外線燈源強度為l60W/cm〜The method of polymerizing acrylic acid and acrylic acid salt to form a super absorbent resin has been variously developed: a successful development of a variety of products that have been produced in the first boundary, and a polymerization method of which has a film polymerization reaction (Japanese Patent Publication No. Sho 48 (1973) -42, Injury, the polymerization reaction was carried out on a conveyor belt (Japanese Patent Laid-Open Publication No. SHO 58 (Cong Bu-grade), and the kneading of the pulverized blade was carried out to carry out polymerization reaction (Japanese Patent Laid-Open Publication No. Sho 7 (1982)- 34,1G1) 'Performed reverse phase suspension polymerization (Japanese Patent Publication No. 7 59 (1984)-37, _' or will be a single view of the thief silky, carry out polymerization reaction (Japanese Patent Laid-open Publication No. 62 (10) 7) _53 (4) [Problems to be solved] • Most of the polymerization methods are free-strand reaction of the reaction raw material 1 such as a polymerization monomer, a polymerization initiator, and a crosslinking agent, so that the entire polymerization reaction is difficult to control and soluble. In view of the above, the present invention provides a method for the lack of a high-sucking ruler, and the polymerization process is relatively stable, and the heat of reaction is not too high, in addition to improving the operating environment. Increased product quality. The method for producing the mother of the present invention at least includes: 1) making an aqueous solution of an acid group-containing monomer having a neutralization rate of 5 〇% or more and a polymerization reaction/3 J The La-based prepolymer has an A-based early system selected from the group consisting of acrylic acid or mercaptoacrylic acid or 2-propylamine-2-mercaptopropenic acid or a mixture thereof; long chain (f) hydrophilic polybasic epoxy compound In the viscous prepolymer, paste light starts to make money - step to produce a nasty solid; 3 dry, pulverize and screen with a hot air of 100 c to 250 〇C; 4) surface crosslinker coating treatment; Then heat the surface treatment at a temperature of 8G ° C to 23 Gt; 6) Add an inert inorganic salt powder. . . The pre-U reaction described above can be carried out in a prepolymerization reactor. 5 The reactor needs to have a function of recording and mixing, uniform mixing, and merging. The prepolymerization reaction can be carried out in addition to the upright reaction tank of the same type of money, or the (four)-view type of limb container, the towel core has a one-way flow of the disturbing water | screw # or juxtaposed twin-screw, This ensures that the reaction material moves in one direction and does not reflow, thereby avoiding the polymerization reaction material from being too long in the reactor to form a gelatinous solid. Fine, reactors of the above type are usually used in batches, which is not conducive to industrial production. [Technical means for solving the problem] In view of the above, the present invention provides a method for continuously producing a highly water-absorbent tree having a low soluble content, wherein the ship is at m, so that the monomer filaments are laid in the pipeline and aggregates w The polymer is added to the pipeline to polymerize the acid group-containing monomer by radical polymerization. In the second step, after the viscous prepolymer is mixed with the polycyclic ring 1332517-based compound, it can be continuously added to the belt reactor, and the above-mentioned polymer is converted into a gel-like solid by using the respective polymer. In addition to the erect erected in the pipeline, the principle of “preparing the ambience of the singularity of the singularity” is to ensure the principle of the first-in-first-out reaction of the monomer in the reaction, so that the pre-polymerization process is left in #, needle, and A situation in which transcriptional overreaction occurs. The residual monomer of the water-soluble tube of the reaction monomer is important for controlling the pre-polymerization reaction. For example, if the residence time is long, the coffee polymerization reaction is more complete, the thief (four) degree and the molecular weight are higher, and the soluble fraction of the finished product is also lower. However, it is more likely to occur in the phenomenon of excessive polymerization in the pipeline; (4) (4) is short, the viscosity of the coffee material and the molecular weight are lower, and the finished product has a higher soluble fraction, but the chance of excessive polymerization is less. In addition, the mixing uniformity of the reaction between the monomer solution and the polyruthenium (IV), and even before the application of the county and the bridging agent, is also an important factor in the photosynthetic reaction of the county. In order to increase the mixing effect of each of the above fluids, the company can use the following methods: (1) introducing a heterogeneous gas in the pipeline, such as nitrogen, or: carbon oxide, or helium, or helium, or a combination thereof. In order to save costs and consider easy to obtain in the industry, a nitrogen or carbon dioxide mixed gas is usually used. In addition, the inert gas _ force is higher than the pressure in the pipeline 'Kelly gas · injection in the monomer-containing aqueous solution line so that each reaction fluid axis _ wire ' (2) good wire towel plus _ or mixed effect of the filler such as : Raschig ring, or wave earrings, (3) using a vapor-liquid static mixer. The light-initiated polymerization technology is well developed and widely used, such as: painting, 1332517 printing, PCB/LCD manufacturing, footwear, etc. There are many advantages to using photo-induced polymerization, such as shortening processes, increasing productivity, and saving energy. There are many kinds of light sources, including ultraviolet rays, infrared rays, xenon rays or 7-rays, etc., which are generally used by the ultraviolet rays, and have a short wavelength (10). nm) and strong penetrating power. It is worth noting that the intensity of the ultraviolet light source for general process is l60W/cm~
200W/cm ’這往往對承載工作物的輸送帶造成嚴重的耗損。如此— 來’輸送帶就必須經常性的更換，生產成本也跟著增加。鐘於此， 本發明所叙光起錄合係將絲分為_，錄輸送帶前段為 紫外線’後段則為紅外線。由於—般輸送帶的表面材質為销脂， 可耐…至150 200 C，且具有抗沾黏與耐化學藥劑的特性，’铁而々 不具耐光性。本㈣前段先使时透力_料絲服單體溶 液由底層向上地進行聚合反應，而後段則使収長較長 (_-1〇_、穿透力較弱’但加熱效果佳的紅外線光源來完成整 個聚合反應，使位於輸送帶上的鄕物轉變成賴。如此一來， 工作物照射紫外光的時間可以縮短或減低紫外光的照射強度，相 f也也減低了輸送帶的耗損。重要的是，紅外線不需熱介質的傳 工作物加熱，效率極高’所以並不會'因前段照射時 間、祕而降低了反應速率。此外，其單位面積内的熱傳輸量大， 故照=靖使得驗間過大，且溫度的控制容易、迅速， 燈源關閉後即停止加熱，安全性較高。 本發明所製造之 高吸水性樹脂所需的含 酸基單體除了丙婦酸 1332517 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、或馬林酸、或富馬酸、或2_丙烯胺_2_甲基丙烷磺酸等。單體 選用不特定關?、可使用—種，亦可合併多鮮體—齊使用，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：丙稀酿 胺、甲基丙烯酿胺'丙稀酸2_烴基乙醋、甲基丙稀酸2—烴基乙g旨、 丙烯酸甲i旨、丙烯酸乙s旨、二甲胺丙烯丙烯酿胺、氣化丙稀丙稀 鲁 _安基三甲銨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%間，適當漠度為30_至杨找之㈤，濃度在重 :·量百分比2〇wt%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55wt%以上’接近飽和濃度，不易調配 -- 且反應太快反應熱不易控制。 含酸基單體之紐基應部份中和以控制成品之四值，使呈中 •性或微酸性’中和劑為氫氧化鐘、氫氧化納、氫氧化钟、碳酸鐘、 碳酸鈉、碳酸卸、碳酸纽、碳酸油、碳酸氫鉀及氨。含酸基 單體之_基將部份中和成鐘鹽或鈉贼鉀贱銨鹽或兩種2 混合鹽類，中和濃度莫耳百分比為45m〇1%至85m〇1%，適當濃度為 50mol%至75m〇l%’中和濃度莫耳百分比為45m〇1%以下時成品之四 值會偏低’中和濃度莫耳百分比為85m〇1%以上時成品之pH=會偏 高，成品PH值若非呈中性或微酸性時，不慎與人體接觸時均不太 適合也較不安全。 /員聚合反應由聚合引發_分解產生自由基開始。聚合引發劑 I選用熱分解㈣始劑，適合的熱分解魏始财過氧化物，如： 過乳化氫、二-第三τ基魏化物、過氧化_或過硫酸鹽(録鹽、 驗金屬鹽）等，及偶氮化合物如：2. 2, _偶氮基雙(2_脒基丙燒)二 鹽酉夂鹽、2.2’ -錢基雙(Nn?基異頂)二賊鹽；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 代邊鹽、抗壞血酸或亞鐵鹽；或將氧化還原型起始劑和熱分解 型起^劑合併使用，首先氧化還原起始航進行反應產生自由 基’當自由基轉移至單體上㈣發聚合反應的進行，由於聚合反 應進行時會觀出大f的熱量而使溫度升高，當溫制達熱分解 型起始劑的分解溫餅，又料發第二段熱分解型起始劑的分 解杂而使個聚合反應更臻於完全。—般自由絲合反應起始劑 適當用量為重量百分比為〇屬wt%至(以中和丙稀酸鹽重量 二土準）更適虽用量則在〇. lwt%至5的%之間，使用重量百分比 、ooiwt%以下時’反應太慢不利經濟效益；使用重量百分比衞伐 以上時，反應域反應财㈣制且容易聚合過度而形成凝膠狀 固體。 α進行光起始聚合反應前應添加交聯劑於黏稠預聚物中，交聯劑 σ i^用/、有兩個或兩個以上不餘和雙鍵的化合物，如：Ν，ν_雙（2— 埽基)胺、Ν，Ν 次曱基雙丙烯酿胺、Μ ‘―次甲基雙曱基丙稀 月女丙烯酸丙烯酷、乙二醇二丙烯酸酿、聚乙二醇二丙烯酸酿、 1332517 乙二醇二曱基丙烯酸酯、聚乙二醇二曱基丙烯酸酯、甘油三丙烯 酸酉a、甘油二曱基丙烯酸酯、甘油附加環氧乙烷之三丙烯酸酯或 三甲基丙烯酸略、三曱醇丙烷附加環氧乙烷之三丙烯酸酯或三曱 基丙烯酸酯、三曱醇丙烷三曱基丙烯酸酯、三曱醇丙烷三丙烯酸 酯、Ν，Ν’ N-三（2-丙烯基）胺、二丙烯酸乙二醇酯、二丙烯三甘醇 酉曰等，亦可選用具·有兩個或兩個以上環氧基的化合物，如山梨醇 聚縮水甘油趟、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 父聯度，而使高吸水性樹脂膠體有適當的加工性。自由基聚合反 應父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〇. 〇〇1社％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^伐至加伐之 間，添加劑量在重量百分比O.OOlwt%以下聚合後水合體太軟且有 黏性不利機械加工，添加劑量在重量百分比5wt%以上吸水性太 低’降低樹脂性能。、 黏稠預聚物可於輸送帶式反應器上或裝有攪拌葉之橫式反應 器中進行二段式光起始聚合反應，製備出之高吸水性凝膠體先利 用絞碎機切成粒徑20麵以下小凝膠體，粒徑10咖以下更佳，再 進行烘乾。 棋乾溫度可於1G(TC至25(TC下進行乾燥，乾燥溫度則以12〇 1332517 -°〇至18G°C進行餘為宜’當烘乾溫度溫度丨默以下聽乾時間 太久不具_效益’烘乾溫度⑽。C以上烘紐交聯舰早進行交 聯反應’使得㈣的乾燥過財，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、騎固定粒徑，再進行表面交聯劑塗覆處 理篩m疋粒控以0 06刪至L 〇〇麵間為宜，以至 • 0.850mm P3較佳’她〇 〇6咖以下細粉使成品粉塵提高，粒徑 1. 00mm以上粒子使成品吸水速率變慢。 吸水性樹脂為不溶解化之親水性聚合體，樹脂内部具有均勾性 ’: 的*橋、’、《構’-般為了改善品質如：提高吸收速率、提高膠體強 ;度、提南抗結塊性、液體滲透性等，會在樹脂的表面再作進—步 ·架橋，此表面交赌理即彻具魏與酸基反應之多官能基交聯 劑，在此之前已有許多專利提出；如：分散高吸水性樹脂與交聯 φ 劑於有機溶劑中進行表面交聯處理（JP-A_56-131608、 JP-A-57-碰27、L-117222)使用無機粉 末直接將交聯劑與交聯劑溶液混入高吸水性樹脂處理 (JP-A6G-163·、；P-A-6G-255814)，添加交聯劑後以蒸氣處理 UP-A-1-1134G6)，使用有機溶劑、水及多满進行表面處理 (JP-A-63-270741、了P-A-64-5G7G7、P-A+292GG4)使用有機 溶液、水、醚（ether)化合物（jP_a_2-153903)等；這些表面 處理的方法雜提高吸收速率提高壓力下吸水倍率，但將造成保 丄叫：)17 持力下降衫的不良縣，降低實際翻之性能。200W/cm 'This often causes serious wear and tear on the conveyor belt carrying the work. In this way, the conveyor belt must be replaced frequently and the production cost will increase. In this case, the light-receiving system of the present invention divides the yarn into _, and the front section of the recording belt is ultraviolet ray, and the latter section is infrared ray. Since the surface of the conveyor belt is made of pin-fat, it can withstand ... to 150 200 C, and it has anti-stick and chemical resistance properties, and it is not light-resistant. In the front section of this (4), the first time is the first time. The monomer solution of the wire is polymerized from the bottom layer upwards, while the latter stage is made to have a long length (_-1〇_, weak penetration force) but good heating effect. The light source completes the entire polymerization reaction, and the sputum on the conveyor belt is converted into a smear. Thus, the time when the workpiece is irradiated with ultraviolet light can shorten or reduce the irradiation intensity of the ultraviolet light, and the phase f also reduces the loss of the conveyor belt. It is important that the infrared rays do not need to be heated by the heat transfer medium, and the efficiency is extremely high. Therefore, the reaction rate is not lowered due to the irradiation time and the secret of the front stage. Moreover, the heat transfer amount per unit area is large, so Photographing = Jing makes the inspection room too large, and the temperature control is easy and rapid, and the heating is stopped after the light source is turned off, and the safety is high. The acid-containing monomer required for the super absorbent resin produced by the present invention is not limited to the acid. In addition to 1332517, other water-soluble monomers having unsaturated double bonds such as methacrylic acid, or marlinic acid, or fumaric acid, or 2-propenyl-2-methylpropanesulfonic acid may be used. Monomer selection is not specific? It can also be used in combination with multiple fresheners. It is also possible to add other hydrophilic monomers with unsaturated double bonds, such as acrylamide, methacrylic amine, and acrylic acid. Ethyl vinegar, methacrylic acid 2-hydrocarbyl group, acrylic acid, acrylic acid, dimethylamine propylene acrylamide, gasified propylene propylene benzoate, but not added The principle of destroying the physical properties of the superabsorbent resin is as follows: Before the radical polymerization reaction, the concentration of the aqueous monomer solution should be controlled between 20% by weight and 555% by weight, and the appropriate indifference is 30_ to Yang (5), and the concentration is heavy: · When the percentage is less than 2〇wt%, the hydrated body after polymerization is too soft and sticky, which is unfavorable to mechanical addition; the added concentration is above 55wt% by weight 'close to saturation concentration, difficult to mix--and the reaction is too fast. It is not easy to control. The base of the acid-containing monomer should be partially neutralized to control the four values of the finished product, so that the neutral or slightly acidic 'neutralizer' is hydrogen hydroxide, sodium hydroxide, hydrogen hydroxide, carbonic acid , sodium carbonate, carbonic acid unloading, carbonated carbon, carbonated oil, potassium hydrogencarbonate and The base of the acid-containing monomer will be partially neutralized into a clock salt or a sodium thief potassium cerium ammonium salt or two mixed salts, and the concentration of the neutralizing concentration of the molar percentage is 45 m 〇 1% to 85 m 〇 1%, suitably When the concentration is 50mol% to 75m〇l%, the percentage of the molar concentration of the molar concentration is 45m〇1% or less, and the four values of the finished product will be low. The neutralization concentration of the molar percentage is 85m〇1% or more, and the pH of the finished product will be biased. High, if the PH value of the finished product is not neutral or slightly acidic, it is not suitable or safe when it is inadvertently contacted with the human body. / The polymerization reaction starts from the polymerization initiation _ decomposition to generate free radicals. The polymerization initiator I chooses thermal decomposition. (4) Starting agent, suitable for thermal decomposition of Wei Shicai peroxide, such as: over-emulsified hydrogen, di-third tau-based weide, peroxidized or persulfate (recorded salt, metal salt), etc., and azo compounds such as : 2. 2, _ azobis(2_mercaptopropene) disodium salt, 2.2'-keki bis (Nn? based isotop) thief salt; can also be used to reduce oxidation a reducing initiator such as an acidic sulfite, a thio-salt salt, an ascorbic acid or a ferrous salt; or a redox-type initiator and a thermal decomposition type The first use of the redox initiation reaction to generate a radical 'when the radical is transferred to the monomer (4), the polymerization proceeds, and the temperature of the large f is increased due to the polymerization reaction, and the temperature is raised. The decomposition of the hot cake of the thermal decomposition type initiator, and the decomposition of the second stage thermal decomposition type initiator, make the polymerization more complete. The amount of the free silk reaction reaction initiator is preferably in the range of wt. lwt% to 5% by weight, based on the weight percent of the genus genus (to neutralize the weight of the acrylate salt). When the weight percentage is less than or less than ooiwt%, the reaction is too slow and the economic benefit is unfavorable; when the weight percentage is used above, the reaction domain reaction is (4) and it is easy to polymerize excessively to form a gelatinous solid. Before the photo-initiation polymerization of α, a crosslinking agent should be added to the viscous prepolymer, and the cross-linking agent σ i^ can be used with two or more compounds having two or more double bonds, such as: Ν, ν_ Bis(2-indenyl)amine, hydrazine, hydrazine bis- bis bis acrylamide, Μ '-methine bis-mercapto propylene propylene, acrylic propylene, ethylene glycol diacrylate, polyethylene glycol diacrylate Stuffed, 1332517 ethylene glycol dimercapto acrylate, polyethylene glycol dimercapto acrylate, glycerol triacrylate glycerol, glyceryl dimercapto acrylate, glycerin plus ethylene oxide triacrylate or trimethacrylic acid Slightly, triterpene propane plus ethylene oxide triacrylate or tridecyl acrylate, triterpene propane tridecyl acrylate, triterpene propane triacrylate, hydrazine, Ν 'N-three (2- Acryl)amine, ethylene glycol diacrylate, dipropylene triethylene glycol oxime, etc., also optional. Compounds with two or more epoxy groups, such as sorbitol polyglycidoxime, polyglycerol Polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene Diglycidyl ether, glycerol polyglycidyl bis glycidyl ether and the like. After the radical reaction, the superabsorbent resin can have an appropriate degree of parenting, and the superabsorbent resin colloid can have appropriate processability. The radical polymerization reaction parent-linking agent may be used singly or in combination of two or more. The amount of the appropriate additive of the radical polymerization crosslinking agent is between 5% and 5% by weight (based on the total solids of the reactants), and the appropriate amount is in the amount of 〇. Between the additions, the amount of the additive is less than 0.001% by weight of the hydrate. The hydrate is too soft and viscous to be unfavorably mechanically processed. The amount of the additive is less than 5 wt% by weight. The water absorption is too low to lower the resin properties. The viscous prepolymer can be subjected to two-stage photoinitiation polymerization on a conveyor belt reactor or a horizontal reactor equipped with a stirring blade, and the prepared superabsorbent gel is first cut into a particle size by a mincer. A small gel below 20 faces, with a particle size of 10 or less is better, and then dried. Chess dry temperature can be 1G (TC to 25 (dry under TC, drying temperature is 12〇1332517 - °〇 to 18G °C for the rest is appropriate) when the drying temperature is silent, the listening time is too long, not _ Benefit 'drying temperature (10). C and above cross-linking ship cross-linking reaction early 'making the dryness of (4) too much, because the degree of cross-linking is too high to effectively remove residual monomers, to reduce the effect of low residual monomers After drying, pulverize, ride the fixed particle size, and then apply the surface cross-linking agent to treat the sieve. 疋 疋 疋 0 0 0 0 0 0 删 删 删 删 删 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 The fine powder below the coffee increases the dust of the finished product, and the particle size of 1. 00 mm or more makes the water absorption rate of the finished product slower. The water-absorbent resin is an insoluble hydrophilic polymer, and the resin has a homogenous hook: '* bridge, ', "Construction" - in order to improve the quality, such as: increase the absorption rate, improve the strength of the gel; degree, anti-caking property, liquid permeability, etc., will be further on the surface of the resin - step bridge, this surface gambling That is, the polyfunctional crosslinking agent which reacts with the acid and the acid group has been Many patents are proposed; for example, dispersing superabsorbent resin and cross-linking φ agent in surface treatment in organic solvent (JP-A_56-131608, JP-A-57-Touch 27, L-117222) using inorganic powder directly The cross-linking agent and the cross-linking agent solution are mixed with a superabsorbent resin (JP-A6G-163·, PA-6G-255814), and a cross-linking agent is added, and the UP-A-1-1134G6 is treated with steam, and an organic solvent is used. , water and multiple full surface treatment (JP-A-63-270741, PA-64-5G7G7, P-A+292GG4) using organic solution, water, ether compound (jP_a_2-153903), etc.; these surfaces The treatment method is mixed to increase the absorption rate and increase the water absorption rate under pressure, but it will cause the protection to be called :) 17 holding force to lower the poor county of the shirt, reducing the actual turning performance.
k 口疋Ί後’根據本發明於可表面處理時朗時進行反應 ::交聯劑可為多元醇如:丙三醇、乙二醇、二乙二醇、三乙二醇、 +乙一酉子、丙二_、l4 丁二醇、三烴基甲基丙炫、山梨醇等；或 可使用多元胺如：乙二胺、二乙二胺、三乙二胺、聚乙二胺;或 可使用具有兩個或兩個以上環氧基的化合物如：山_聚縮水甘 油鱗、聚丙三醇聚縮水甘_、乙二醇二縮水甘㈣、二乙二醇 -2水甘賴、聚乙二醇二聚縮水甘崎、雙丙三醇聚縮水甘油 謎等；亦可使用碳酸亞烴酯如：乙二醇碳酸_、心甲基3_二氧 雜環戊烧-2,、4, 5-二曱基-丨，3-二氧_蛾相、4 4_二甲 基一1，3-二氧雜環戊烧-2_酮、4_乙基' 3_二氧雜同、 1’ 3-二氧雜環己龄酮、4, 6_二曱基_丨，3_二氧雜環己^同或 U-二氧雜環庚烧-2—酮[表面處交聯劑_法可單獨使用或兩 種以上混合使帛。表面處交咖㈣#添加料在重量百分比 0. OOlwt%至l〇wt%之間（以反應物總固形份為基準），更適當的用量 在0.005wt%至5wt%之間，表面處交聯劑添加劑量在重量百分比 〇·ooiwmx下時無法顯出效果，表錢交聯劑添加缝在重量百 分比10wt%以上時，吸水性太低，降低樹脂性能。 表面交聯劑塗覆處理時’表面交聯劑之添加可為表面交聯劑直 接添加’或調絲面交義水紐添加，_成表面交聯劑親水 性有機溶劑水溶液添加，親水性有機溶劑如曱醇、乙酡、丙醇、 15 2 丁醇、_、㈣、乙崎沒有特殊限制，可形成溶液即可， 二中Μ、乙醇較佳。表面交聯劑添加時高吸水樹脂中可添加 =ϋ無機餘末，以幫助溶液分散，舰錢鹽粉末可為硫酸銘、 或&氧化石夕’或氧化銘，或氧化鎮等或其混合物。其中以硫酸銘、 一乳化梦較佳。舰無類财添加範圍在重量百分比G.〇05wt% 至10.0wt%之間，其中以0. oiwn至4. Owt%較佳。 進行表面交聯継覆處爾，再㈣。以23(rc純處理，使 表面交聯舰進行交聯反應，並使内部交制進行交聯反應而達 1 本翻之效果。處理溫度貌以下㈣反應日销太久，不具經 1處理/皿度g23〇c時，樹脂易劣化影響品質。至於處理時 門貝m 2〜150分鐘為宜’依處理溫度調整，溫度高則時間短，溫 度低則時間長。 由〜吸水性樹脂具有吸濕後結塊的現象，為避免在高濕度地 區使用高财㈣齡有縣赌塊導致加王獨，-般會在高 吸Μ生翻日表面細惰性無機鹽粉末或界面潍劑，使表面略且 親油㈣使高财性樹脂财雜後不易結塊的特性 ，此惰性無 f鹽粉末可選、或二氧切、或氧德、或氧化鎮、或 氧化#5 ^領土、或碳酸約、或石炭酸鎮等或其混合物；通常此 h I·二機4末的杨量與無機鹽粉末顆粒粒徑大小有關，若顆 、、·；.旦車D機鹽粉末比表面積較大’所以有效躲無機鹽粉 末用里可lx小’其惰性無機鹽粉末添加範圍為重量比百分比 < 5wt/。至ίο. 〇wt%之間’其中以ο. _%至4. 較佳，惰性無 機贿末其粒徑為〇.咖至，若選用顆粒小於◦.觀〆 的热機鹽粉末則成本過高不利於工業化生產，若選用顆粒大於 100M的無機鹽粉末财添加量過絲響高吸水性樹脂吸收力的 門喊。惰性無_粉末可單獨添加或可伴隨界面活性劑或具枯度 有機化合物加人’其界面活,_丨或跡度有機化合物可選用· 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、 或陽離子型界面活性劑、或陰陽兩性型界面活性劑、或其混合物， 通常界面活性劑或具粘度有機化合物可使用甘油、乙二醇、己六 醇、聚氧乙烯醇、或聚乙二醇、或硬脂酸聚乙二醇酯、或硬脂酸 來乙二醇己六酯、或聚氧化乙烯壬苯醚、或聚氧化乙烯辛苯醚、 或聚氧化乙烯十二笨醚、或聚氧化乙烯烷基醚、或聚氧化乙烯月 k峻等此界面活性劑或具粘度有機化合物可調配成水溶液型態加 入或單獨加入’適當的界面活性劑或具粘度有機化合物添加劑量 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。 17 1332517 【發明内容】 /月提卩種可連續生產具低可溶物含量之高吸水性樹脂 的方式，其特徵在於：第-步，使含酸鲜體水溶液與聚合引發 Ik於長官線中，而此長管線之約Μ及^處各設有導入 2及…刀解型起始劑;距出σ處約85公分處設有2支導入偶氮化 合物或環氧化合物進行自由基聚合反應域_的預雜。第二 φ 7預承物與夕元環氧基化合物混合之後連續加入至皮帶反應器 ’、上方以剞^又為紫外光，後段則為紅外線二種不同的光源引 發黏稠預聚物轉變硬化成凝膠狀固體。本發明所提供之上述生產 ::方式具有下列特點：⑴預聚物相對於液體反應物料的黏度明顯提 ' -门’瓜動性降低，更谷易與之後的皮帶反應器相匹配，而且使整 .•個聚合反應穩定度提高，反應熱不至於過高，⑵使用管線反應 器除了節省空間外，且更能夠確保反應流體先進先出的原則，而 鲁 達到連續式生產的目的，（3)使用二段式照光的作法，減少紫外 線對於輸送皮帶的照射時間與強度，降低耗材更換的成本，（4) 紅外線加熱效率極佳，可節省能源並具有操作簡便與安全性高的 優點，（5)縮短製程、提升產能並提高產品質量，尤其是降低可 溶物的含量。 為顯示本發明之高吸水性樹脂的低可溶物含量之特性，其可 溶物含量的測定步驟如下：先秤取0.5 g高吸水性樹脂，再加入 〇. 9%食鹽水I85g，在500rpm轉速下攪拌一個小時後，以滤紙過 1332517 -渡出SAP萃取液。最後’秤取該萃取液20 g，先以〇. 1N議滴 定，再使用0. IN HC1進行反滴定以求出SAp可溶物的含量。 【實施方式】 以下以實施例說明本發明’但本發明之技術及專利範圍不受這 些實施例所限制。 貫施例一： 籲⑴先於中和槽中加入⑽重量份的丙烯酸及2263 ?重量份的 水’之後於冰浴下將1476. 3重量份的氫氧化鈉水溶液(濃度為 45%)緩緩加入上述丙烯酸水溶液中。此時得到單體濃度為 : 38.6wt%的水溶液，其中有68 mol%的丙烯酸中和為丙烯酸鈉。 (2)中和程序元成後，利用水調溫控制部分中和之丙稀酸鈉鹽水溶 液為20°C左右。 鲁 （3)°周·上述早體溶液的流量為1〇〇公升/小時，使其通過一支直 k為5么欠、總長度為26. 35米的不傭鋼管。在不鑛鋼管入端 5公分與1〇公分處側邊分別連接一支直徑0· 5與〇. 9公分的不 鏽鋼管。前者導入氮氣’流量控制為2〇〇公升/小時，後者則 通入過硫酸鉀/亞硫酸氫鈉= 1/1(重量比），流量控制為2毫升 /小時。預聚和反應溫度控制在20°C，最後所得之預聚物黏度 為 80cps。 (4)距離管線出口端85公分處側邊連接二支直徑〇· 9公分的不鏽 19 1332517 " 鋼管’一支導入偶氮二異庚月青’流量控制為20亳升/小時， 另一支則導入丙三醇聚乙二醇三縮水甘油_(η=7)，流量控制 為15毫升/小時。 (5) 將(4)所述之反應流體加入到傳送帶上，傳送帶上方裝置有紫 外線與紅外線燈管，前段利用紫外線照射上述混合液體5秒， 後段則使用紅外線照射30秒，使其硬化成膠體。 (6) 利用切式絞碎機切成2刪粒徑以下的凝膠體。 ⑺以130°C溫度乾燥2小時；利用筛網_選〇. lmm〜〇· 85mm固定 粒徑，得粉狀高吸水性樹脂。 _ : (8)秤取此向吸水性樹脂l〇〇g，加入硫酸鋁粉末lg，待混合均勻 :’ 後再加入乙二醇碳酸酯/水/甲醇= 1/1/1(重量比）溶液4g，以 -. 215°C溫度加熱處理1〇分鐘。 ⑼冷卻後，加入1§碳_(台塑公司生產品名：Ns_2〇〇〇)及娜 # 甘'由水〆合液2g ’均勻混合後即得高性能高吸水性樹脂。測定保 持力=33. 7g/g ’ 49 g/cm2壓力下吸水倍率= 23. Gg/g，可溶物 含量=7. 5%。 實施例二： ()重複Λ知例’但則段照射時間為1Q秒，後段照射時間為別 秒’結果所得之高吸水性樹脂的保持力則為犯·敏，仙 壓力下吸水倍率= 22. 3g/g，可溶物含量=8. 7%。 實施例三： 丄J丄/ (1)重複實施例一，但前段照射時間為〗 /L 3秒’後段照射時間為30 ^ ^^ 3l ^ ^ ^ 壓力下吸水倍率= 22. 4g/g，可溶物含量— 實施例四： · 〇 (1)重複實施例一，但不鏽鋼管長度改 ^ . 9ln 為52米’出料之預聚物黏 3= Γ結果所得之高吸水性樹腊的保持力則為 35· 9g/g ’ 49 g/cm壓力下吸水倍率 5.4%。 23.9·可溶物含量= 實施例五： (1)重複實施例四，但前段照射時間 私钻里& 馬10秒’後段照射時間為30 果所得之高吸水性樹脂的保持力則為㈣ £力下吸水倍率=23.5g/g，可溶物含量咳跳。 實施例六： 料姆_…，咖射時間為3〇 心、.'σ果所付之高吸水性樹 壓力下吸水倍率, 實施例七： ⑴重複實施例-’但前段照射 秒，妊要邮/曰 ^ 1 後段照射時間為30 心、果所狀高吸水性樹脂的 壓力下吸水倍率=241_ p 1為35.lg/g，49g/cin +幻g/g，可溶物含量。 21 1332517 實施例八： (1)重複實施例七，但前段照射時間為丨和，， 秒’結果所得之高吸水性樹脂的保持力則灸W射日守間為40 pr. , _ 、、為 36· 7g/g，仙 σ/mi2 歷力下吸水倍率=23.8g/g，可溶物 9g 3里二氏丹％。 實施例九： (1)重複貫施例七，但前段照射時間為丨 秒，結果所得之高吸水性樹脂的保 射時間為50 壓力下吸水倍率=23.2g/g，可溶物含m5的，49_2 實施例十： _ 0 ° (1)重複實施例七，但不鏽鋼管長度為5 為21〇CPS ;結果所得之高吸水性樹__^3^度 一 49錢力下吸水倍率，。•可溶物含^ 實施例十一： ⑴重複=料，㈣卿_丨秒，物綠時間為仙 U所得之高吸水性樹脂 ’·，、 壓力下吸水m Ί / ^^^37.8g/g，49g/cm2 及队羊―23. lg/g，可溶物含量 實施例十二： (1)重複貫施例十，但前段昭射時 秒，，士果所爾1秒，後段照射時間為5〇 、、，。果所传之向吸水性樹脂的保持力 壓力下吸水倍率L可溶物含量=74% g49_ 22 1332517 比較例一： α)重複實施例一，但僅使用前段紫外線照射2〇秒，結果所得之 高吸水樹脂的保持力為30. 5g/g，49g/cm2壓力下吸水倍率= 22. lg/g，可溶物含量= 10.1%。 比較例二： (1)重複實施例一，但不鏽鋼管長度改為52米，出料之預聚物黏 度為210cps，而前段僅使用紫外線照射20秒，結果所得之高 吸水樹脂的保持力為32. 7g/g，49g/cm2壓力下吸水倍率= 23. 9g/g，可溶物含量=8. 7%。 【圖式簡單說明】 益〇 4 ΜΛ 【主要元件符號說明】 無0 23After k-mouthing, the reaction is carried out according to the invention in the case of surface treatment: the crosslinking agent may be a polyhydric alcohol such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, + ethane , propylene di-, l4 butanediol, trihydrocarbylmethyl propylene, sorbitol, etc.; or polyamines such as: ethylenediamine, diethylenediamine, triethylenediamine, polyethylenediamine; or The use of compounds having two or more epoxy groups such as: mountain _ polyglycidol scale, polyglycerol polycondensation _, ethylene glycol diglycidyl (tetra), diethylene glycol-2 water lag, polyethylene Glycol dimerization and shrinkage of glycyrrhizin, diglycerin polyglycidol mystery, etc.; alkylene carbonate such as: ethylene glycol carbonate _, cardiomethyl 3 dioxane-2, 4, 5 may also be used. -dimercapto-indole, 3-dioxo-moth phase, 4 4 dimethyl-1,3-dioxol-2-one, 4-ethyl' 3 dioxane, 1 ' 3-Dioxacyclohexanone, 4,6-diindenyl-hydrazine, 3-dioxolidine or U-dioxepane-2-one [crosslinking agent at the surface_ The method may be used alone or in combination of two or more. The surface of the coffee (four) #Additional material in the weight percentage of 0. 00lwt% to l〇wt% (based on the total solids of the reactants), a more appropriate amount between 0.005wt% and 5wt%, the surface is handed over The amount of the joint additive cannot show an effect when the weight percentage is 〇·ooiwmx, and when the weight of the cross-linking agent is added at a weight percentage of 10% by weight or more, the water absorption is too low, and the resin property is lowered. When the surface cross-linking agent is applied, the addition of the surface cross-linking agent can be directly added to the surface cross-linking agent or the surface of the cross-linking cross-linking water is added, and the surface cross-linking agent is added with a hydrophilic organic solvent aqueous solution, hydrophilic organic Solvents such as decyl alcohol, ethyl hydrazine, propanol, 15 2 butanol, _, (d), and ethyl acetonide are not particularly limited, and a solution may be formed, and bismuth and ethanol are preferred. When the surface cross-linking agent is added, the super-absorbent resin may be added with ϋ inorganic residual to help the solution to disperse. The powder of the ship's salt can be sulphuric acid, or & oxidized stone, or oxidized, or the like. . Among them, it is better to use sulfuric acid and an emulsified dream. Owt%优选。 Owt% to 4. Owt% is preferably in the range of G. 〇 05wt% to 10.0% by weight. Perform surface cross-linking and then (4). With 23 (rc pure treatment, the surface cross-linked ship is cross-linked, and the internal cross-linking reaction is carried out to achieve a cross-linking effect. The treatment temperature is below (4) The reaction is sold for too long, and there is no treatment by 1 When the degree of g23〇c is reached, the resin is easily deteriorated and affects the quality. As for the treatment, the door is m 2 to 150 minutes, which is suitable for the treatment temperature adjustment. The high temperature is short, and the temperature is low for a long time. The phenomenon of agglomeration after wet, in order to avoid the use of high-yield (four) age in the high-humidity area, the county gambling block leads to the addition of Wang Duo, and the surface will be finely inert inorganic salt powder or interface tincture on the surface of the high-suction Slightly and oleophilic (4) makes the high-yield resin difficult to agglomerate after the miscellaneous, this inert non-f salt powder can be selected, or dioxo, or oxygen, or oxidized town, or oxidized #5 ^ territory, or carbonic acid About, or carbolic acid town, etc. or a mixture thereof; usually the amount of yang at the end of this h I·2 machine is related to the particle size of the inorganic salt powder particles, if the particles, the surface of the powder of the machine D have a larger specific surface area Therefore, it is effective to hide the inorganic salt powder with Like lx small 'its inert inorganic salt powder The range is the weight ratio percentage < 5wt /. to ίο. 〇wt% between 'where ο. _% to 4. Preferably, the inert inorganic bribe has a particle size of 〇. coffee to, if the particle size is less than ◦. Guanyu's heat engine salt powder is not costly and is not conducive to industrial production. If the inorganic salt powder with a particle size larger than 100M is used, the amount of the inorganic salt powder is excessively high. The inertia is not added. Accompanying surfactants or with dry organic compounds plus 'interface viability, _丨 or trace organic compounds can be selected · Values above 12 nonionic surfactants, or water-soluble anionic surfactants, or cationic interfaces An active agent, or an yin-yang-type surfactant, or a mixture thereof, usually a surfactant or a viscous organic compound may be used with glycerin, ethylene glycol, hexahexaol, polyoxyethylene alcohol, or polyethylene glycol, or stearic acid. Acid polyethylene glycol ester, or stearic acid to ethylene glycol hexahexate, or polyoxyethylene decyl ether, or polyoxyethylene octyl phenyl ether, or polyethylene oxide dodecanide, or polyoxyethylene alkyl Ether, or polyethylene oxide month k The amount of the surfactant or the viscous organic compound may be adjusted to form an aqueous solution, or the amount of the appropriate surfactant or the viscosity of the organic compound may be added in an amount of from 0.001% by weight to 5% by weight (by total reactants). The solid content is based on the basis), and the more appropriate amount by weight is between 〇1wt% and 3wt%. 17 1332517 [Summary of the Invention] The lyophilized product can continuously produce a highly water-absorbent resin having a low soluble content. The method is characterized in that: in the first step, the aqueous acid-containing aqueous solution and the polymerization-initiated Ik are in the permanent line, and the long-distance pipelines are provided with the introduction 2 and the ... knife-type initiator; At about 85 cm from the σ, two pre-dots of the azo compound or the epoxy compound were introduced to carry out the radical polymerization reaction zone. The second φ 7 pre-filled material is mixed with the epoch epoxy compound and continuously added to the belt reactor ', above, and then ultraviolet light, and the latter part is infrared light, two different light sources, causing the viscous prepolymer to be hardened into Gelatinous solid. The above-mentioned production: method provided by the present invention has the following characteristics: (1) the viscosity of the prepolymer relative to the liquid reaction material is remarkably improved, and the kineticity of the 'gate' is reduced, and the valley is more compatible with the subsequent belt reactor, and The stability of the polymerization reaction is increased, the heat of reaction is not too high, and (2) the use of the pipeline reactor not only saves space, but also ensures the principle of first-in and first-out of the reaction fluid, and Lu achieves the purpose of continuous production, (3) The use of two-stage illumination reduces the exposure time and intensity of UV to the conveyor belt and reduces the cost of consumable replacement. (4) The infrared heating efficiency is excellent, energy saving and easy to operate and safe. 5) Shorten the process, increase production capacity and improve product quality, especially reduce the content of solubles. In order to show the low soluble content of the superabsorbent resin of the present invention, the soluble matter content is determined as follows: 0.5 g of a highly water-absorptive resin is first weighed, and then 9% of a saline solution of I85 g is added at 500 rpm. After stirring for one hour at the rotation speed, the filter solution was passed through 1332517 - the SAP extract was taken out. Finally, 20 g of the extract was weighed, first titrated with 〇. 1N, and then back titrated with 0. IN HC1 to determine the content of SAp solubles. [Embodiment] The present invention is described below by way of examples, but the technical and patent scope of the present invention is not limited by the embodiments. Example 1: (1) Adding (10) parts by weight of acrylic acid and 2263 parts by weight of water prior to the neutralization tank, then substituting 1476. 3 parts by weight of aqueous sodium hydroxide solution (concentration: 45%) in an ice bath It is slowly added to the above aqueous acrylic acid solution. At this time, an aqueous solution having a monomer concentration of 38.6 wt% was obtained, in which 68 mol% of acrylic acid was neutralized to sodium acrylate. (2) After the neutralization process is completed, the sodium sulphate brine solution neutralized by the water temperature control portion is about 20 °C. Lu (3) ° week · The flow rate of the above-mentioned early body solution is 1 〇〇 liter / hr, so that it passes through a straight steel, which is 5 owed, and the total length is 26.35 meters. A stainless steel pipe with a diameter of 0.5 and 9 cm is connected to the side of the non-mineral steel pipe at 5 cm and 1 cm. The former introduces nitrogen gas flow rate of 2 liters liter / hour, while the latter introduces potassium persulfate / sodium hydrogen sulfite = 1 / 1 (weight ratio), and the flow rate is controlled to 2 ml / hour. The prepolymerization and reaction temperature were controlled at 20 ° C, and the resulting prepolymer viscosity was 80 cps. (4) Connect the two sides of the pipe at the exit of the pipe at the side of 85 cm. The diameter of the pipe is 9 325 9 cm. 13 1332517 " The pipe is introduced into the azo diisoheptide. The flow control is 20 liters per hour. One is introduced with glycerol polyethylene glycol triglycidyl _ (η = 7), and the flow rate is controlled to 15 ml / hour. (5) The reaction fluid described in (4) is added to a conveyor belt. The upper part of the conveyor belt is provided with ultraviolet and infrared lamps. The front section is irradiated with ultraviolet rays for 5 seconds, and the latter stage is irradiated with infrared rays for 30 seconds to harden it into a colloid. . (6) Cut into a gel having a particle size of 2 or less by a cutter. (7) Drying at a temperature of 130 ° C for 2 hours; using a sieve _ 〇 〇. lmm~〇· 85 mm fixed particle size to obtain a powdery superabsorbent resin. _ : (8) Weigh this water-absorbent resin l〇〇g, add aluminum sulfate powder lg, and mix until uniform: 'Add ethylene glycol carbonate / water / methanol = 1 / 1 / 1 (weight ratio) 4 g of the solution was heat-treated at -215 ° C for 1 Torr. (9) After cooling, a high-performance superabsorbent resin is obtained by adding 1 § carbon _ (former product name: Ns_2 台) of Formosa Plastics Co., Ltd. and Nag #甘's 2 from water mash. 5%。 The holding capacity = 33. 7g / g ‘ 49 g / cm 2 under pressure of water absorption = 23. Gg / g, soluble content = 7. 5%. Example 2: () Repeating the known example 'but the irradiation time is 1Q seconds, the latter irradiation time is other seconds' results the retention of the super absorbent resin is guilty, the water absorption ratio under the pressure of the fairy = 22 7%。 Soluble content = 8.7%. Example 3: 丄J丄/ (1) The first embodiment is repeated, but the irradiation time of the previous stage is 〖 /L 3 seconds', the irradiation time of the latter stage is 30 ^ ^^ 3l ^ ^ ^, the water absorption ratio under pressure = 22. 4g / g, Soluble content - Example 4: · 〇 (1) Repeat Example 1, but the length of the stainless steel tube is changed. 9ln is the 52 m 'precipitated prepolymer stick 3 = Γ the result of the high water absorption of the wax The holding force was 35. 9 g/g '49 g/cm under water pressure 5.4%. 23.9·soluble content = Example 5: (1) Repeat the fourth example, but the pre-irradiation time of the private drill and the horse's 10 seconds' rear irradiation time is 30. The retention of the superabsorbent resin obtained is (4) The suction capacity under the force of force is 23.5g/g, and the soluble content is cough. Example 6: The raw material _..., the coffee shot time is 3 〇 heart, . σ fruit paid by the high water absorption tree under water pressure, Example 7: (1) Repeat the example - 'but before the second exposure, pregnancy Post/曰^ 1 The irradiation time in the subsequent stage is 30. The water absorption capacity under the pressure of the superabsorbent resin is 241_ p 1 is 35.lg/g, 49g/cin + magic g/g, soluble content. 21 1332517 Example 8: (1) Example 7 is repeated, but the irradiation time of the previous stage is 丨,, and the retention of the superabsorbent resin obtained by the second result is 40 pr., _ , , It is 36·7g/g, the absorption capacity of the sigma/mi2 is 23.8g/g, and the soluble matter is 9g 3%. Example 9: (1) Repeating the seventh embodiment, but the irradiation time of the first stage is leap seconds, and the resulting superabsorbent resin has a retention time of 50% under water pressure = 23.2 g/g, and the soluble matter contains m5. , 49_2 Example 10: _ 0 ° (1) Repeat Example 7, but the length of the stainless steel tube is 5 〇CPS; the result is a high water absorption tree __^3^ degrees a force of 49 under the force of water absorption. • Soluble matter contains ^ Example 11: (1) Repeat = material, (4) Qing _ 丨 second, the material is green time is the high water-absorbent resin obtained from the fairy U '·,, under water pressure m Ί / ^^^37.8g / g, 49g/cm2 and team sheep - 23. lg / g, soluble matter content Example 12: (1) repeated application of ten, but the first paragraph of the first shot of the second, the fruit of the fruit 1 second, the latter stage of illumination The time is 5〇, ,,. The water absorption ratio of the water-absorbent resin to the water-absorbent resin is L-soluble content = 74% g49_ 22 1332517 Comparative Example 1: α) Example 1 is repeated, but only the front-stage ultraviolet irradiation is used for 2 sec seconds, and the result is obtained. The holding power of the super absorbent resin was 30. 5 g/g, and the water absorption ratio under pressure of 49 g/cm 2 was 22. lg/g, and the soluble matter content was 10.1%. Comparative Example 2: (1) Example 1 was repeated, but the length of the stainless steel tube was changed to 52 m, the viscosity of the prepolymer discharged was 210 cps, and the front stage was only irradiated with ultraviolet rays for 20 seconds, and the retention of the obtained super absorbent resin was 7%。 The water absorption ratio = 23. 9g / g, soluble content = 8.7%. [Simple description of the diagram] Benefits 4 ΜΛ [Main component symbol description] None 0 23