6 200900439 九、發明說明： 【發明所屬之技術領域】 Γ%吸水性樹脂廣泛地運用於農業或園藝方面的水保持1、 建築材料中的抗露珠凝結劑，移除石油中水份的材料，或作為電鏡 線中的外層防水包覆劑,以及用之於衛生用品如尿布、婦女衛生用 品、拋棄式的擦巾等。 【先前技術】 在本技蟄界已知具高吸水性樹脂成分的材料，有遇水分解型 的灰各丙烯腈(hydrolyzed starchacrylonitrile)接枝聚合物 (日本公開特許公報昭49(1974)_43,395)，中和之崎—丙稀 酉夂接枝聚合物（日本公開特許公報昭51 (1976)_125，伽），息化 乙烯醋酸- 两烯酯共聚物（日本公開特許公報昭6 200900439 IX. Description of the invention: [Technical field to which the invention pertains] Γ% water-absorbent resin is widely used for water conservation in agriculture or horticulture, anti-dew coagulant in building materials, and material for removing moisture from petroleum. Or as an outer layer waterproofing agent in the electron microscope wire, and used in sanitary articles such as diapers, feminine hygiene products, disposable wipes, and the like. [Prior Art] A material having a highly water-absorptive resin component is known in the art, and there is a water-decomposable ash-hydrogenated starch acrylonitrile graft polymer (Japanese Laid-Open Patent Publication No. SHO 49 (1974)-43, 395), Nakasaki-Azolla-grafted polymer (Japanese Laid-open Patent Publication No. Sho 51 (1976) _125, Gam), and polyvinyl acetate-dienyl ester copolymer (Japanese Open Patent Gazette
52(1977)-14, 689)，水解㈣腈共聚物或㈣雜共聚物（日本 特+ a報日α 53 (1978)-15, 959)，及部份中和聚丙烯酸（日 本公開特許公報日S 55(_)歲3Q4) #。其核粉—丙稀腈接 枝聚合物的原料中，因為含有越的高分子—澱粉，料起腐爛 =二無法長時間的保存；再者，其製造方法十分複雜， —、" 丨生柯知之製備方式以使用丙稀酸及丙稀酸鹽進 仃交聯聚合所得之离 阿及水性樹脂佔最大部份也最為經濟。其原因 為丙烯酸鹽共聚物 Λ, _ 專枓—丙烯酸可迅速由商場上購得，且製得 的鬲吸水性樹脂具有 ：于 ^ 负偎鬲的吸水能力，及具有製造成本低廉以及 曰 4爛眭的分解且最具經濟效益，故成為最普遍化的高吸 6 200900439 水性樹脂。 聚合丙烯酸及丙烯酸鹽形成高吸水性樹脂的方法可由數種 已知的方法f得’如水減聚合反應、逆相鮮液聚合反應、乳 化聚合反應或將單體倾或塗覆於纖絲f上進行聚合反應等方 法。在這些方法中，逆相懸浮液聚合反應以及乳化聚合反應必須 使用到有機賴，但若無法有效的控織合反鱗的溫度，有機 V'溶繼造献應系統溫度以及壓力的增加，產生敎甚至祕爆 炸，進而威脅到操作現場人員的安全以及造成環境污染問題^ 成品也有有機溶劑殘留的疑慮。 高吸水性樹脂林溶解化之親水性聚合體，翻旨内部呈有均 句性的架橋結構，—般為了改善品質如:㈣速率、提高膠體 強度、提減結塊性、液體滲透性等，會在生絲丙烯酸系的高 吸水性樹瞒，_熱處理方式對财性樹脂齡表面進行交聯 處理’以降低吸水性樹脂被水性液體潤_形成凝膠以及凝聚。 當吸水性脑表_成凝科，纽塞㈣舰水_脂表面向 對嶋霞力外，還会 =性舰嫩嶋，技—她赚樹脂的吸收 能力。 技蟄界味許乡賴高吸搞樹縣面交祕理的方法被開 二，如：分散㈣水性樹脂財聯劑於有機關中崎表面交聯 处理（JP_A—56—131608、JP仰,27、JP+58_42602、 7 200900439 JP-A58-U7222 ) ’使用無機粉直接將交聯劑與交聯劑溶液混入高 吸水性樹祕理（】P-A6(M63956 m255814)，添加交聯 d後以?减處理（JP-A-H134Q6) ’使用有機溶劑、水及多元醇 進行‘4處理（JP-A-63-27G74WP-A-64-50707、IP-A-1-292004)， ^用有機溶液、水，（ether)化合物Up_A_2—1539Q3)，利用 夕^水甘油基轉、多官能基胺這—類雙官能基化合物（美國專利 4’ _，983號）’及添加多元醇做為惰性溶劑對吸水性樹脂進行交 «理的方法（美國專利4, 507, 438、4, 541，871號），另有使用 高速混合機將表面交聯的溶劑與吸水性樹脂混合（美國專利 5，140’_號），亦有使用N—(經烧基)_甲基氨基丙酸g旨喷灑於吸 水性樹脂表面進行熱處理（錢專利5, 229，備號），以及使用亞 烷基碳酸鹽進行熱處理的方法（美國專利5，働，771號）等，其 他已經公财關於高吸水性樹脂表面交聯處_專利；如美國專 卜利 4289814、4295978、4500670、4732968、4758617、4824顚、 4954562及5026800號，這些熱處理的美國專利方法雖_ 速率，即提縫力下吸水鲜，但將造餘持力下㈣多的不良後 果，降低實際應用之性能。 【發明内容】 龜於上述本發明係提供—種製造高吸水性樹脂的方法，該方 法月b使產ασ具有尚吸收力以及尚壓力下吸收倍率，以及低凝膠阻 塞現象，使得吸收性製品具有易乾燥性以及低玫漏性。 8 200900439 製造本發明之高吸水性樹脂所需的水溶性不飽和單體，除了 二烯酸外尚可使用其它具有酸性基_不飽合雙鍵的水H單 體’如：甲基丙烯酸、馬林酸、富馬酸、2-丙稀胺-2-曱基丙貌確 酸、順丁稀二酸、順丁烯二酸酐、反丁稀二酸、反丁烯二酸軒等: 单體之選用不特定限制只可使用—種，亦可合併多種單體一齊使 用’亦可視情況需要添加具有不飽和麵之其他親水性的單體， 如：丙烯醯胺、甲基丙烯醯胺、丙烯酸2-羧基乙酯、甲基丙烯酸 2-羧基乙酯、丙烯酸甲酯、丙烯酸乙酯、二甲胺丙烯丙烯醯胺、 氯化丙烯丙烯醯胺基三f銨（美國專利4, 057, 521號、4, 〇62幻7 號、4, 525, 527 號、4, 286, 082 號及 4, 295, 987 號），但添加量以 不破壞高吸水性樹脂之物性為原則。 在進行自由基聚合反應前，單體水溶液濃度宜控制在重量百 分比20wt%至55wt%間，適當濃度為30wt%至45wt%之間，濃度在 u 重1百分比2〇被％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。 含酸基單體之羧酸基應部份中和以控制成品之pH值，使呈 中性或微酸性’中和劑為週期表中鹼金族或鹼土族的氫氧化物或 是石炭酸化合物，如：氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸钟、碳 酸氫鈉、碳酸氫鉀或氨類化合物；中和劑可單獨使用一種或多種 混合使用。含酸基單體之缓酸基部份中和成納鹽或鉀鹽或錢鹽， 9 200900439 中和浪度莫耳百分比為45m。職δ5_，宜為別祕至 75mol% ’中和濃度莫耳百分比為45_以下時成品之邱值會偏 低，中和濃度莫耳百分比為85111〇1%以上時成品之pH值會偏高， 成品PH值非呈中性或微酸性時，若不慎與人體接觸日^不^適 合’也車父不安全。 在進行自由基聚合反應前，單體水溶液中亦可添加水溶性高 分子以降贼本，此等水雜高分子如：部份純衫全息化的 聚乙烯醇、聚乙二醇、聚丙烯酸、聚丙稀_、救粉或殿粉衍生 物如曱基纖維素，丙烯酸曱基纖維素，乙基纖維素等聚合物；此 等水溶性高分子的分子量並不制限定，其巾較健水溶性高分 子為澱粉、部份皂化或完全皂化的聚乙烯醇等單獨或混合使用。 尚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Q至i〇wt%較佳’ 〇至5wi：%尤佳，添加超過2〇wt%時 會影響物性，使物性變差。 在進行自由基聚合反應前應先添加自由基聚合反應交聯劑 於未反應單體溶液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：N，N，-雙（2-丙烯基）胺、 Ν，Ν’ -次甲基雙丙烯醯胺、N，N，—次曱基雙曱基丙烯醯胺、丙烯 酸丙烯酯、乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、乙二醇二 曱基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、甘油三丙烯酸酯、甘 油二甲基丙坤酸酯、甘油附加環氧乙烧之三丙稀酸g旨或二曱基丙 10 200900439 烯酸酯、二甲醇丙烷附加環氧乙烷之三丙烯酸酯或三p基丙烯酸 酯、二甲醇丙烧二T基丙婦酸酯、三子醇丙烧三丙烯酸酯、N，队 二（2-丙烯基）|女、一丙烯酸乙二醇酯、三丙烯酸聚氧乙稀甘油 酯、二丙烯酸二乙基聚氧乙烯甘油酯、二丙烯三甘醇酯等，亦可 遥用具有兩個或兩個以上環氧基的化合物，如山梨醇聚縮水甘油 醚、聚丙三醇聚縮水甘油醚、乙二醇二縮水甘油醚、二乙二醇二 縮水甘油醚、聚乙二醇二縮水甘油醚、雙丙三醇聚縮水甘油醚 等。在進行自由基反應後就可使高吸水性樹脂具有適當交聯度， 而使向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 添加齊彳里在重量百分比〇· 〇〇1的％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Q. _%至3wt%之間。添 加劑量在重量百分比〇. 001wt%以下聚合後水合體太軟且有黏性 不利機械加工，添加劑量在重量百分比5被％以上吸水性太低，降 低樹脂性能。 本發明之聚合反應由自由基聚合反應起始劑的分解產生自 由基開t。自由基起始冑彳可選帛熱分貞帽起始劑’適合的熱分解 型起始劑有過氧化物，如：過氧化氫、二—第三丁基過氧化物、 過氧化醯胺或過硫酸鹽（銨鹽、鹼金屬鹽）等，及偶氮化合物如： 2.2’ -偶氮基雙（2_脒基丙烷）二鹽酸鹽、2.2，-偶氮基雙(n，n_ -伸曱基異丁脉）二鹽酸鹽；亦可使用還原劑’使成為氧化還原 200900439 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·和熱分翻起始劑合併制。首先氧化還 原起始獻進行反應產生自由基，當自域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㈣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_分解，而使整個聚合聽更臻於完全。 -般自由基聚合反應起始劑之適當用量為重量百分比 至l〇wt%(以中和丙烯酸鹽重量為基準），更適當用量則在〇.^伙 至5wt%之間’使用重量百分比〇. 〇〇1.以下時，反應太慢不利 經濟效^ ’使職量百分比1Qwtte上時，反應太快反應熱不易 控制。 本發明之聚合反應可於傳統批次反應容器中，或於輸送帶式 反應器上進行反應，反應所得之高吸水性樹脂，先利用絞碎機切 成直徑20mm以下小凝膠體，直徑1〇mm以下更佳，再進行篩選。 篩選固定粒徑之凝膠體直徑以2. 〇〇臟以下為宜，以〇. 〇5咖 至1. 50 間較佳，粒徑大於2· 00 _之凝膠體則重新送回絞碎 機進行再次切碎。粒徑〇. 〇3mm以下之凝膠體進行烘乾、粉碎吏 理後，易產生成品細粉量提高，粒徑2· 〇〇刪以上之凝膠體進疒 洪乾時，容易因為熱傳導效果不佳，導致成品殘存單體偏高及其 他物性表現不佳之缺點。 、 200900439 依據本發明，丙稀酸鹽凝膠體的顆粒大小分佈越窄，不僅可 使凝膠體在烘乾後物性表現達到最佳狀態，而且有利於控制烘乾 的時間及溫度，篩選完成後再進行烘乾。 烘乾溫度以溫度100C至18(TC進行烘乾為宜。烘乾溫度 100 C以下烘乾，時間會太久不具經濟效益，烘乾溫度1刖。〇以上 烘乾’會使交聯劑提早進行交聯反應，使得後續的乾燥過程中， 因父聯度過高而無法有效的去除殘存單體而達到降低殘存單體 之效果。 乾燥後進行粉碎、篩選固定粒徑，再進行表面交聯劑塗覆處 理篩述固定粒徑以〇.〇6mm至i.〇〇mm間為宜，以q· 麵至 〇· 850mm間較佳’粒徑〇· 06mm以下之細粉使成品粉塵提高，粒徑 1. 00mm以上之粒子使成品u及水速率變慢。依據本發明，丙稀酸鹽 聚合物的顆粒大小分佈越窄越好。 高吸水性儀為不鱗化之親水性聚合體，樹脂内部具有均 ^性的架橋結構…般為了改善品質如:提高吸歧率、提高膠 體強度、提高抗結塊性、液體參透性等，會在樹脂的表面再作進 一步架橋。 根據本發明，於熱處理時同時進行架橋反應，其表面交聯劑 為二為多元醇如：丙三醇、乙二醇、二乙二醇、三乙二醇、聚乙 户兩―醇、L4-丁一酉子、二烴基曱基丙烧、山梨醇等；或可 200900439 使用具有兩個或兩舰上環氧基的化合物如：山梨醇聚縮水甘、、由 醚、聚丙三醇聚縮水甘油_、乙二醇二縮水甘油 —乙二醇二 齡甘油醚、聚乙二醇二聚縮水甘_、雙丙三醇聚縮水甘油鍵 等；亦可使用石炭酸亞烴酿如：乙二醇碳酸醋、4_甲基七_ Μ 喊院-2-_、4,5_二甲基心，3^氧雜環戊烧_2_酮、Μ二甲基_ι孓 -氧雜壤錢·2_®§]、4_乙基_：ι，3_二氧雜環姚_2,、丨，二氧雜 %己燒·2-酮、4,6·二甲基]，3_二氧雜環己烧_2__或^•二氧雜環 庚12,等。此交聯劑的適當添加劑量在重量百分比⑽= 至l〇wt%之間（以反應物總固形份為基準），更適當的用量在° 〇.嶋wt%至5wt%之間，交聯劑添加劑量在重量百分比Q.謝里wt% 以下k無法顯出效果’交聯獅加劑量在重量百分比以上 時，吸水性太低，降低樹脂性能。 〇52(1977)-14, 689), hydrolyzed (tetra) nitrile copolymer or (tetra) hetero copolymer (Japan special + a newspaper date α 53 (1978)-15, 959), and partially neutralized polyacrylic acid (Japanese Open Licensing Gazette Day S 55 (_) years old 3Q4) #. The raw material of the nuclear powder-acrylonitrile graft polymer, because it contains the higher polymer-starch, it is expected to be rotten=two can not be preserved for a long time; further, the manufacturing method is very complicated, -, " twins Kochi's preparation method is the most economical with the use of acrylic acid and acrylate to crosslink polymerization. The reason is that the acrylate copolymer Λ, _ special 枓 - acrylic acid can be quickly purchased from the market, and the obtained 鬲 water-absorbent resin has: water absorption capacity of the negative 偎鬲, and has low manufacturing cost and 曰 4 rot The decomposition of hydrazine is the most economical, so it has become the most popular high-absorbent 6 200900439 water-based resin. The method of polymerizing acrylic acid and acrylate to form a superabsorbent resin can be obtained by several known methods such as water-reduction polymerization, reverse phase fresh liquid polymerization, emulsion polymerization or pouring or coating a monomer onto the filament f. A method such as a polymerization reaction is carried out. In these methods, the reverse phase suspension polymerization and the emulsion polymerization must use organic lysate, but if the temperature of the anti-scale is not effectively controlled, the organic V' dissolution should be increased by the system temperature and pressure. The cockroaches and even the secret explosions threaten the safety of the personnel on the operating site and cause environmental pollution. ^ The finished product also has doubts about the residual organic solvent. The hydrophilic polymer dissolved in the superabsorbent resin forest has a uniform bridge structure inside, and generally improves the quality such as: (4) rate, improvement of colloid strength, reduction of agglomeration, liquid permeability, etc. In the raw silk acrylic high-absorbency tree, the heat treatment method cross-links the surface of the resin-based resin to reduce the water-absorbent resin from being hydrated by the aqueous liquid to form a gel and agglomerate. When the water-absorbent brain table _ Cheng Ningke, New Zealand (four) ship water _ grease surface to the Xia Xia Li, will also = sex ship tenderness, technology - she earns the absorption capacity of resin. The technique of Xu Yi Lai Gao, who is the leader of the technology industry, has been opened up for two methods, such as: Dispersing (4) Waterborne Resin Co., Ltd. in the surface of the cross-linking process (JP_A—56—131608, JP Yang, 27 , JP+58_42602, 7 200900439 JP-A58-U7222 ) 'Inorganic powder directly mixed the cross-linking agent and cross-linking agent solution into the superabsorbent tree mystery (P-A6 (M63956 m255814)), after adding cross-linking d ?Subtractive treatment (JP-A-H134Q6) 'Use of organic solvents, water and polyols for '4 treatment (JP-A-63-27G74WP-A-64-50707, IP-A-1-292004), ^ with organic Solution, water, (ether) compound Up_A_2-1539Q3), using a sulphur-glycol-based, polyfunctional amine such a bifunctional compound (US Patent 4' _, No. 983) and adding polyol as inert A method in which a solvent absorbs a water-absorbent resin (U.S. Patent No. 4,507,438, 4,541,871), and a surface-crosslinking solvent is mixed with a water-absorbent resin using a high-speed mixer (U.S. Patent 5, 140'_ No.), also using N-(alkyl)-methylaminopropionic acid g to spray on the surface of the water-absorbent resin for heat treatment (money Lie 5, 229, spare number), and the method of heat treatment using alkylene carbonate (U.S. Patent No. 5, 働, No. 771), etc., other public finances regarding the surface cross-linking of superabsorbent resin _ patent; Specialized Bu Li 4298814, 4295978, 4500670, 4732968, 4758617, 4824顚, 4954562 and 5026800, these heat treatment of the US patent method _ speed, that is, the lifting force under the lifting force, but will be more than the rest of the (four) Consequences, reducing the performance of the actual application. SUMMARY OF THE INVENTION The present invention provides a method for producing a super absorbent resin in the above-mentioned invention, wherein the method b has an absorption capacity of ασ and an absorption ratio under pressure, and a low gel blocking phenomenon, so that the absorbent article It has easy drying and low frosting. 8 200900439 A water-soluble unsaturated monomer required for producing the super absorbent resin of the present invention, in addition to a dibasic acid, other water H monomers having an acidic group-unsaturated double bond such as methacrylic acid, Marlinic acid, fumaric acid, 2-acrylamide-2-mercaptopropyl acid, cis-butane diacid, maleic anhydride, anti-butadiic acid, fumarate, etc.: single The selection of the body is not limited to only one type, and a plurality of monomers may be used together. It is also necessary to add other hydrophilic monomers having an unsaturated surface, such as acrylamide, methacrylamide, or the like. 2-Carboxyethyl acrylate, 2-carboxyethyl methacrylate, Methyl acrylate, Ethyl acrylate, Dimethylamine propylene decylamine, Propylene propylene acrylamide tris-ammonium (US Patent 4, 057, 521) No. 4, 〇62 幻7, 4, 525, 527, 4, 286, 082 and 4, 295, 987), but the addition amount is based on the principle of not impairing the physical properties of the superabsorbent resin. Before the radical polymerization, the concentration of the aqueous monomer solution is preferably controlled between 20% by weight and 55% by weight, and the appropriate concentration is between 30% and 45% by weight. When the concentration is less than 1% by weight, the concentration is less than 2%. The hydrated body is too soft and sticky. It is unfavorable for mechanical processing. The added concentration is above 55 wt% by weight, close to the saturation concentration, difficult to formulate and the reaction is too fast. The reaction heat is not easy to control. The carboxylic acid group of the acid group-containing monomer should be partially neutralized to control the pH of the finished product, so that the neutral or slightly acidic 'neutralizer' is an alkali metal or alkaline earth hydroxide or a phenolic acid compound in the periodic table. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid clock, sodium hydrogencarbonate, potassium hydrogencarbonate or ammonia compound; the neutralizing agent may be used alone or in combination of one or more. The slow acid group of the acid group-containing monomer is neutralized to form a sodium or potassium salt or a money salt, and the percentage of neutralized wave molars is 45 m. Job δ5_, should be secret to 75mol% 'The concentration of neutralization concentration is 45_ or less, the value of the finished product will be low, and the percentage of neutral concentration of the molar is 85111〇1% or more. The pH value of the finished product will be high. When the PH value of the finished product is not neutral or slightly acidic, if it is inadvertently in contact with the human body, it is not suitable for 'the car is not safe. Before the radical polymerization reaction, a water-soluble polymer may be added to the aqueous monomer solution to reduce the thief, such as a part of the pure shirt holographic polyvinyl alcohol, polyethylene glycol, polyacrylic acid, Polypropylene _, powder or temple powder derivatives such as fluorenyl cellulose, yttrium acrylate cellulose, ethyl cellulose and other polymers; the molecular weight of these water-soluble polymers is not limited, the towel is more water soluble The polymer is starch, partially saponified or fully saponified polyvinyl alcohol or the like, used alone or in combination. The water-absorbent resin preferably has a weight percentage of the water-soluble polymer added to 2020% by weight, but preferably from Q to i〇wt% is preferably 〇 to 5wi:%, and the addition of more than 2% by weight may affect Physical properties make physical properties worse. Before the radical polymerization reaction, a radical polymerization crosslinking agent should be added to the unreacted monomer solution. The radical polymerization crosslinking agent can be selected from compounds having two or more unsaturated double bonds, such as: N. ,N,-bis(2-propenyl)amine, hydrazine, Ν'-methine bis acrylamide, N,N,-decyl bis-decyl acrylamide, acryl acrylate, ethylene glycol diacrylate Ester, polyethylene glycol diacrylate, ethylene glycol dimercapto acrylate, polyethylene glycol dimethacrylate, glycerin triacrylate, glyceryl dimethyl propionate, glycerin plus epoxy Tripropylene acid g or dimercaptopropyl 10 200900439 enoate, dimethanol propane plus ethylene oxide triacrylate or tri-p-acrylate, di-methanol-propylated di-t-propionate, three Alcohol-acrylic triacrylate, N, bis(2-propenyl)|female, ethylene glycol monoacrylate, polyoxyethylene glyceryl triacrylate, diethyl polyoxyethylene glyceryl diacrylate, dipropylene A glycol ester or the like can also be used as a compound having two or more epoxy groups, such as Phenol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycerin polyglycidyl ether, etc. . After the radical reaction, the superabsorbent resin can have an appropriate degree of crosslinking, and the water-absorbent resin colloid can have appropriate processability. The radical polymerization crosslinking agent may be used singly or in combination of two or more. The free radical polymerization cross-linking agent is appropriately added between 5% and 5% by weight of 彳·〇〇1 (based on the total solids of the reactants), and a more appropriate amount by weight is in Q. _% Between 3wt%. The dosage is 5% by weight or less. 001 wt% or less The hydrate is too soft and viscous after polymerization. Unfavorable mechanical processing, the amount of the additive is less than 5% by weight, and the water absorption is too low, which lowers the resin properties. The polymerization of the present invention produces a free radical t from the decomposition of the free radical polymerization initiator. Free radical start 胄彳 optional 贞 hot split cap starter 'suitable thermal decomposition type starter has peroxide, such as: hydrogen peroxide, di-tert-butyl peroxide, guanidinium peroxide Or persulfate (ammonium salt, alkali metal salt), etc., and azo compounds such as: 2.2'-azobis(2-amidinopropane) dihydrochloride, 2.2,-azobis (n, n_ - Dimethyl sulfonate dihydrochloride; can also be used as a redox 200900439 type initiator, such as: acid sulfite, thiosulfate, ascorbic acid or ferrous salt; or will be oxidized The reduction type and the heat separation initiator are combined. First, the redox initiation is carried out to generate a radical, and when the self-domain is transferred to the monomer, the polymerization reaction is initiated, and as the polymerization proceeds, a large amount of heat is released to raise the temperature, and when the temperature reaches the thermal decomposition type. When the decomposition temperature of the initiator starts, the second stage of thermal decomposition is initiated, which causes the whole polymerization to be more complete. The appropriate amount of the radical polymerization initiator is from 5% by weight (based on the weight of the neutralized acrylate), and the appropriate amount is between 伙 and 5% to 5% by weight 〇 〇〇1. When the reaction is too slow, the economic effect is not good. When the percentage of the job is 1Qwtte, the reaction is too fast and the reaction heat is not easy to control. The polymerization reaction of the present invention can be carried out in a conventional batch reaction vessel or on a conveyor belt reactor, and the superabsorbent resin obtained by the reaction is first cut into a small gel body having a diameter of 20 mm or less by a mincer, and the diameter is 1 〇mm or less is better, and then screening. Screening the diameter of the gel with a fixed particle size is 2. The following is suitable for sputum, 〇. 〇5 coffee to 1. 50 is preferred, and the gel with a particle size greater than 2·00 _ is returned to the minced The machine is shredded again. Particle size 〇. 凝胶3mm or less of the gel after drying and pulverizing, it is easy to produce a fine powder of the finished product, and the particle size of 2· 〇〇 以上 以上 之 之 以上 以上 以上 以上 以上 容易 容易 容易 容易 容易Poor, resulting in high residual monomer and poor performance of other physical properties. According to the present invention, the narrower the particle size distribution of the aluminate gel, not only allows the gel to perform optimally after drying, but also facilitates control of drying time and temperature, and screening is completed. Then dry it. Drying temperature is preferably 100C to 18 (TC is suitable for drying. Drying temperature is below 100 C for drying, the time will be too long, no economic benefit, drying temperature is 1 刖. Drying above ' will make the cross-linking agent early The cross-linking reaction is carried out, so that the effect of reducing residual monomers can not be effectively removed due to excessive parental association during the subsequent drying process. After drying, the powder is pulverized, the fixed particle size is screened, and surface cross-linking is performed. The coating treatment is carried out by screening the fixed particle size to be between 〇6 mm and i.〇〇mm, and the fine powder of the particle size 〇·06 mm or less is preferably increased from q·face to 〇·850 mm, so that the finished dust is improved. Particles having a particle diameter of 1.00 mm or more slow the rate of the finished product u and water. According to the present invention, the particle size distribution of the acrylic acid polymer is as narrow as possible. The high water absorption meter is a non-scaling hydrophilic polymer. The resin has a uniform bridging structure inside. In order to improve the quality, such as: improving the absorption ratio, improving the strength of the colloid, improving the anti-caking property, liquid permeability, etc., further bridging is performed on the surface of the resin. According to the present invention, Simultaneous bridging during heat treatment Should be, the surface cross-linking agent is two polyols such as: glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylidene alcohol, L4-butane, dihydrocarbyl mercapto , sorbitol, etc.; or 200900439, a compound having two or two epoxy groups on the ship, such as: sorbitol polyglycol, ether, polyglycerol polyglycidol _, ethylene glycol diglycidyl - ethylene Alcohol two-aged glyceryl ether, polyethylene glycol dimerized glycine _, diglycerin polyglycidyl bond, etc.; can also be used to make carbolic acid alkylene such as: ethylene glycol carbonate, 4_methyl seven _ Μ -2-_, 4,5_ dimethyl heart, 3 oxacyclopentan-2-one, dimethyl _ 孓 氧 氧 氧 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ι,3_Dioxa heterocycle Yao_2, 丨, dioxa% hexanone, 2-keto, 4,6·dimethyl], 3_dioxane _2__ or ^•2 Oxepane 12, etc. The appropriate amount of this crosslinker is between 10% by weight and 10% by weight based on the total solids of the reactants, more suitably in ° 〇.嶋wt% Between 5wt%, the amount of crosslinker additive is in the weight percentage Q. Shear wt% below k can not The effect of 'lion dosage crosslinked at% or more by weight, the water-absorbing too low, reducing the performance of the resin. Billion
表面父聯劑在塗f處理時’其表面交制之添加方式，分 表^又1啦齡加，或戰表面交·水減添加，或調成表 面錢水性有機溶劑水溶液添加。親水性有機溶劑如甲醇、 2、丙_、異丁醇、_、曱_、⑽等沒有特殊限制，可形 ’其中以，乙醇較佳。表面交_加時高吸水 添加雜無機餘末，以幫助溶液分散。祕無機鹽粉 、或：氧切，或氧她，或氧化鎂等或其混合物， 用^Ji!s、二氧化雜佳。惰性無機鹽粉末的用法可單獨使 、併兩種以上混合使用。惰性無機鹽粉末添加範圍在重量百 14 15 200900439 分比0. 005wt%至l〇. 〇wt%之間，其中以〇. 〇iwt%至4. Owt%較佳。 進行表面交聯劑塗覆處理後’再以12(TC至230°C範圍内進 行加熱處理’使表面交聯劑能均勻而且快速的進行交聯反應，並 使内部交聯劑進行交聯反應而達到本發明之效果。熱處理溫度 12〇 C以下父聯反應時間太久，不具經濟效益，熱處理溫度23〇。〇 以上樹脂易劣化影響品質，熱處理時間以2分鐘至120分鐘為 ( 宜’依紐獲制祕處觀綠熱纽溫度碰，熱處理溫度 问則熱處理日守間短’熱處理溫度溫度低時，則熱處理溫度時間長。 表面父聯熱處理後，於高吸水樹脂中添加水不溶性微粉， 订抗結塊處理。本發明為增加高吸水樹脂顆粒之間關隙，使 吸水樹脂在吸_氣後補高流祕。水秘性微粉添加方式 直接添加，或再利_著織水不溶性微粉黏著於高吸水樹月旨 面水不/合性祕粉包括；硫酸銘、硫酸鎮 化鋅、碳峰軸、_、術 彿石、喊土、膨土、活性碳、二氧切、二氧化鈦之無機魄 末’及如纖維素粉末、《、聚乙烯、聚氣乙烯、聚苯乙缚之 機粉末。上叙水不雜微财，叫加錢餘末的效果 好。無機麵末的用法可單獨使㈣合併_以上混合使用。 力口^在重量百分比〇._至lMwt%之間，其中以 。林雜婦*子大喊料讀10咖， U的大小為G. 6 mm以下。黏著劑可為多搞如：丙三醇、 15 200900439 乙二醇、山梨醇等；或可使用聚乙稀亞胺。黏著劑的用法可單獨 6 使用或合併兩種以上混合使用。黏著劑的適當添加劑量在重量百 分比0. OOlwt%至l〇wt%之間（以反應物總固形份為基準），更適者 的用量在0. 005wt°/。至5wt%之間，黏著劑添加劑量在重量百分比 ◦ .OOlrtto下時無法錢性無健粉末完全轉於高吸水樹脂 表面。黏著劑添加劑量在重量百分比l〇wt%以上時，吸水性變低， 降低樹脂性能。 本發明混合樹脂及無機鹽之過程中所利用的混合裝置，必須 能夠產生大的混合力，其混合始㈣充分均勻。狀於本發明的' 混合裝置可以V-型混合器、柱式混合n、高魏拌混合器、螺旋 式混合器、氣流混合ϋ臂捏合機、雙臂錐形混合器、螺條混 合器'密壁式混合ϋ、粉碎捏合機、旋轉混合如及螺桿播出機。 【實施方式】 { j 本發明之目的在提供-種粉狀、不溶於水，可吸收水液或尿 液及血液，並具有在賴上降低減理溫度，且義其熱處理時 間的高吸水性樹脂，具有高保持力，而且在較高的壓力下具有較 高吸收倍率特性。本發明之製造方法至少包括： (a)使用-種含有丙烯酸(鹽）與/或丙驗胺（鹽）的水溶性不 飽和單體’中和比率在45至85莫耳%之範圍内，不飽和單體 水溶液的濃度在20至55重量份之範圍； 200900439 ⑹反應後生成的凝膠體切碎，在溫度靴至跳範圍_ 風乾燥、粉碎、筛選； (C)以又:Mb D物與魏垸_酸鹽的混合水溶液再進 交聯塗覆處理；及 ⑷溫度12(TC至23(TC加熱熱處理： 用之於本發明之交聯化合物與環氧烧基鱗酸鹽的混合水溶 Γ液的表面張力值最好不高於_/m,優先選㈣-綱/m之間。 若混合水溶液的表面張力值高於3_m，則會造成噴灑於吸水性 樹脂時，吸水性樹脂有膨脹的現象發生，使得吸水性樹脂有聚集 的現象產生，因為，當混合水溶液的表通力值高於細仏，混 合水溶液就無法均句的分散於吸水性樹脂的表面，造成表面改質 後，吸水性樹脂吸水能力降低。 < 就本發明而言，_絲張力錄於％_!較聯化合物 i與環魏基魏_混合水溶液倾於吸水性翻旨，並經由溫度 12〇°C至纖論I，即可製造具有高保持力，而且在較高的^ 力下具有較高触倍率的高吸水性細旨林判之最大特點。用 來相合於上述的水溶性减和單體的步職無特殊之限制。 要經由本個之方法製稍得之高吸水性樹脂，賴翻於各種 型式的衛錢品、農業用及食品保鮮關吸水劑。 為言正明本發明之高吸水性樹脂的壓力下吸水倍率，本發明人 17 200900439 is 利用叉壓吸收量（壓力負荷：2〇g/cm2及49g/cm2)來測定。其受题 吸收量係根據歐洲專利0339461 A號說明書第七頁中所描述的方 法測定；將初始重量的高吸水性樹脂放在有篩網底部的圓柱體 中，對粉體加以20g/cm2及49g/cm2的壓力，接著將此圓柱體置於 吸收性需求測試器上，讓此高吸水性樹脂吸收請的氯化納水溶 液一小時，再將測吸水重量，將所得數值除以高吸水性樹脂的重 量’即得受壓吸收量數值。 本發明所稱之保持力，係利用茶袋試驗法測定，則以五次量 測結果去除最高似及最健後，取平均值；將❿的高吸^ 性樹脂裝在茶紐，並浸泡於_ N幻水溶㈣分鐘，狹後 將此魏後的絲置於·機暢心（直彳嫌丨、轉速丨彻_ -刀知後秤重。所得之雜先減去未充填高吸水性樹脂的空白植 茶袋重（以相同步驟操作)再除以聚合物重即得保持力數值。、 本發明所稱之表面張力，係利用㈣财,型表面張力洲 賴，取侧《置於舰品的杯巾，職樣品杯置於表面張力 ，_嶋蝴張力測定儀的懸臂 ”、、< 台至白金板處使白金板在液體表面下，按下測 ^關5;可獲得被測液體的表面張力值；表面張力值單位為 識，測⑽度為2峨，重覆測定至少3次，取其平均值。 【實施例】 200900439 >、下例挪本發明’但本發明之專利及技術範圍不 受這些實施例所限制。 參考例： υ取峨氧化納水溶液218.7g緩慢加人訓祕酸及2㈣ 的水的5〇〇c. c圓錐槪中，氫氧化納/丙稀酸的滴加比率在〇.奶 • 95 $il圍内滴加時間為2小時，並保持瓶内中和反應系統 度在20 C至40 C$(l_ ;此日轉單體濃度伽%水溶液， 其中7QmQl%(莫耳比)之丙稀酸部份中和成為丙稀酸鈉。 )再力入G.414g的N，N -次曱基雙丙烯軸於水溶性不飽和單 體溶液，溫度維持於2(TC左右。 3)加入0· 144g雙氧水，:i. 8 g亞硫酸氫鈉及i 8 g過硫酸錄起 始劑反應。 (4)將反應後生成的凝膠體湘切式粉碎機切碎，㈣選出粒徑 大小為2mm直徑以下的凝膠體。 5)再以跳溫度乾燥2小時；利用G. lmnH)· 85mm蚊粒徑筛網 筛選，得粉狀吸水性樹脂，其測定保持力為42._，咖心2 壓力下吸水料6. 3g/g，49g/cm2壓力下吸水倍率6. lg/g。 實施例一 秤取參考綱製得吸水性樹脂1{%，加人乙二醇及環氧乙烧 19 20 200900439 烷基磷酸鹽（松本油劑公司製造，商品名：A_512A)混合水溶液 1. 5g ’表面張力值=33. 4 mN/m，以140。(：溫度加熱處理1小時， 冷卻後，即得高性能高吸水性樹脂。其測定保持力為32. lg/g， 20g/cm2壓力下吸水倍率27. 5g/g，49g/cm2壓力下吸水倍率 19. 3g/g。 實施例二： 重覆實施例一，但加入甘油及環氧乙烷烷基磷酸鹽混合水溶液 1. 5g，表面張力值=32· 5mN/m，以14(Tc溫度加熱處理丨小時，即 得高性能高吸水性樹脂。其測定保持力為314g/g，2〇g/cm2壓力 下吸水倍率26. 8g/g，49g/cm2壓力下吸水倍率19. 7g/g。 實施例三： 重覆實施例一，但加入二乙二醇及環氧乙烷烷基磷酸鹽混合水 溶液丨· 5g，表面張力值=31. 3 mN/m，以14〇t溫度加熱處理1小 時，即得高性能高吸水性樹脂。其測定保持力為3〇. lg/g，2〇g/cm2 壓力下吸水倍率25. 2g/g，49g/cm2壓力下吸水倍率17. 9g/g。 實施例四： 重使η例一，但加入乙二醇碳酸酯及環氧乙烷烷基磷酸鹽混合 水溶液1. 5g，表面張力值=33. 9 mN/m，以14〇。〇溫度加熱處理i J日寸’即仵面性能高吸水性樹脂。其測定保持力為32.9g/g， 20 21 21200900439 20g/cm2壓力下吸水倍率25. 7g/g，49g/cm2壓力下吸水倍率 16. 5g/g。 實施例五： 重覆實施例一，但加入聚乙二醇二縮水甘油醚(Nagase公司製 造，商品名：EX-810)及環氧乙烷烷基磷酸鹽混合水溶液15g , 表面張力值=33.1 mN/m ’以ii(TC溫度加熱處理1小時，即得高 性能高吸水性樹脂。其測定保持力為31. 7g/g，2〇g/cm2壓力下吸 水倍率23. 4g/g ’ 49g/cm2壓力下吸水倍率15. 2g/g。 實施例六： 重覆實施例一 ’但以18(TC溫度加熱處理1〇分鐘，即得高性 能高吸水性樹脂。其測定保持力為33. lg/g，2〇g/cm2壓力下吸水 倍率22. 9g/g ’ 49g/cm2壓力下吸水倍率16. 3g/g。 實施例七： 秤取參考例一所製得高吸水性樹脂1〇〇g，加入硫酸鋁粉末 1·〇g，待混合均勻後再加入乙二醇碳酸酯及環氧乙烷烷基磷酸 皿此&水’谷液i.5g，以140C溫度加熱處理1小時，冷卻後， 即得同性能尚吸水性樹脂。其測定保持力為ig/g，2〇g/cm2 壓力下吸水倍率24. 5g/g，49g/an2壓力下吸水倍率18· 3g/g。 21 22 200900439 實施例八: 二醇碳酸酯及環氧乙烷烷基磷酸鹽（松When the surface of the parental agent is applied to the f treatment, the method of adding the surface to the surface is added, and the surface is added to the surface of the surface, or the surface is added with water, or added to the aqueous solution of the aqueous solvent. The hydrophilic organic solvent such as methanol, 2, propylene, isobutanol, _, 曱_, (10) and the like are not particularly limited, and are preferably exemplified. Surface cross-additional high water absorption Add hetero-inorganic residue to help disperse the solution. Secret inorganic salt powder, or: oxygen cut, or oxygen her, or magnesium oxide or a mixture thereof, with ^Ji!s, good oxidization. The inert inorganic salt powder may be used singly or in combination of two or more. Owt%优选优选。 The inert inorganic salt powder is added in a range of from 1500% by weight to 5% by weight. Between 5% by weight and 〇% by weight. After the surface cross-linking agent coating treatment, 'heat treatment in the range of TC to 230 ° C' enables the surface crosslinking agent to carry out the crosslinking reaction uniformly and rapidly, and the internal crosslinking agent is cross-linked. The effect of the invention is achieved. The heat treatment temperature is below 12 〇C, and the parent reaction time is too long, and the economical heat treatment temperature is 23 〇. The resin above is easy to deteriorate and affects the quality, and the heat treatment time is 2 minutes to 120 minutes. When the heat treatment temperature is low, the heat treatment temperature is long. When the surface is heat treated, the water-insoluble fine powder is added to the super absorbent resin. The invention relates to anti-caking treatment. The invention is to increase the gap between the superabsorbent resin particles, so that the water-absorbent resin can replenish the flow after the absorption of the gas. The water-based micro-powder is added directly, or the water-insoluble fine powder is added. Adhesive to the super-absorbent tree, the water surface is not suitable for the secret powder; sulfuric acid, sulfuric acid zinc, carbon peak, _, surgery Buddha stone, shouting soil, bentonite, activated carbon, dioxane, dioxane Inorganic bismuth of titanium and such as cellulose powder, ", polyethylene, polyethylene, polystyrene, powdered machine powder. On the water is not mixed with micro-finance, called the effect of adding money to the end. Inorganic surface The usage can be combined separately (4) combined with the above. The force mouth ^ is between 重量._ to lMwt% by weight, among them. Lin Miscellaneous* is shouting to read 10 coffee, the size of U is G. 6 mm The following adhesives can be used for: glycerol, 15 200900439 ethylene glycol, sorbitol, etc.; or polyethyleneimine can be used. The adhesive can be used alone or in combination of two or more. Adhesive The amount of the appropriate additive is between 0.001% by weight and 3% by weight (based on the total solids of the reactants), and more preferably between 0.005wt% and 5% by weight of the adhesive additive. When the amount is 重量 OOlrtto, the non-toxic powder is completely transferred to the surface of the superabsorbent resin. When the amount of the adhesive additive is more than 10% by weight, the water absorption becomes low, and the resin property is lowered. And the mixing device used in the process of inorganic salts, must It is capable of generating a large mixing force, and the mixing is started (4) sufficiently uniform. The mixing device of the present invention can be a V-type mixer, a column mixing n, a high-mix mixer, a spiral mixer, a gas flow mixing arm kneading. Machine, double-arm conical mixer, ribbon mixer 'dense wall mixing crucible, pulverizing kneader, rotary mixing, and screw-on-line machine. [Embodiment] { j The object of the present invention is to provide a powder type, Insoluble in water, it can absorb water or urine and blood, and has a high water-absorbent resin which lowers the temperature of degradation and has a heat treatment time. It has high retention and high pressure under high pressure. Absorbance rate characteristic. The manufacturing method of the present invention comprises at least: (a) using a water-soluble unsaturated monomer containing acrylic acid (salt) and/or alanine (salt), the neutralization ratio is 45 to 85 mol% Within the range, the concentration of the aqueous solution of the unsaturated monomer is in the range of 20 to 55 parts by weight; 200900439 (6) The gel formed after the reaction is chopped, in the range of temperature boots to hops _ air drying, pulverization, screening; (C) In addition: Mb D and Wei Wei _ acid salt mixed water soluble Re-crosslinking coating treatment; and (4) Temperature 12 (TC to 23 (TC heat treatment: the surface tension value of the mixed aqueous solution of the cross-linking compound and the epoxy sulphate used in the present invention is preferably not Above _/m, prefer between (four)-class/m. If the surface tension value of the mixed aqueous solution is higher than 3 mm, the phenomenon that the water-absorbent resin is swollen when sprayed on the water-absorbent resin occurs, so that the water-absorbent resin is aggregated because the surface of the mixed aqueous solution has a high KP value. In the fine mash, the mixed aqueous solution cannot be uniformly dispersed on the surface of the water-absorbent resin, and after the surface is modified, the water absorbing ability of the water-absorbent resin is lowered. < In the context of the present invention, the _ silk tension is recorded in %_! compared to the mixed compound i and the cyclo-Wei-Wei-mixed aqueous solution is poured into the water-absorbing property, and can be produced by the temperature of 12 ° C to the fiber I It has the highest retention characteristics, and it has the high retention capacity and the high water absorption under the higher force. There is no particular limitation on the step size used to match the above water-soluble monomer. To obtain a slightly high water-absorbent resin by this method, it is necessary to turn over various types of money-saving products, agricultural products and food preservation water-absorbing agents. In the present invention, the inventors 17 200900439 are measured by the amount of fork pressure absorption (pressure load: 2 〇g/cm 2 and 49 g/cm 2 ) in order to clarify the water absorption ratio under pressure of the superabsorbent resin of the present invention. The amount of absorption by the subject is determined according to the method described in the seventh page of the specification of European Patent No. 0339461 A; the initial weight of the super absorbent resin is placed in a cylinder having a bottom of the sieve, and the powder is 20 g/cm 2 and At a pressure of 49 g/cm2, the cylinder was placed on an absorbent demand tester, and the superabsorbent resin was allowed to absorb the aqueous sodium chloride solution for one hour, and then the water absorption weight was measured, and the obtained value was divided by the high water absorbability. The weight of the resin is the value of the pressure absorption amount. The retention force referred to in the present invention is determined by the tea bag test method, and the highest and the most healthy after removal are taken for five times, and the average value is taken; the high-absorption resin of the enamel is placed in the tea and immersed in _ N phantom water soluble (four) minutes, after the narrow, put the silk behind the Wei in the machine. (Direct 彳 丨 丨 丨 丨 丨 丨 _ - - 刀 刀 刀 刀 刀 刀 刀 刀 刀 刀 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The blank tea plant bag weight (operating in the same step) is divided by the polymer weight to obtain the retention force value. The surface tension referred to in the present invention is based on (four) wealth, type surface tension, and the side is placed on the ship. The cup towel, the sample cup is placed on the surface tension, the cantilever of the tension gauge, and the white gold plate is placed under the liquid surface. Press the test 5 to obtain the liquid to be tested. The surface tension value; the surface tension value unit is the identification, the measured (10) degree is 2 峨, and the measurement is repeated at least 3 times, and the average value is taken. [Examples] 200900439 >, the following example of the present invention 'but the patent of the present invention And the technical scope is not limited by these examples. Reference example: 峨 峨 峨 峨 峨 纳 纳In the 5〇〇c. c cone of 218.7g of slow-added training acid and 2 (4) of water, the molar ratio of sodium hydroxide/acrylic acid is 2 hours in the milk • 95 $il And keep the neutralization reaction system in the bottle at 20 C to 40 C$ (l_; this daily conversion monomer concentration gamma aqueous solution, wherein 7QmQl% (mole ratio) of the acrylic acid part is neutralized to become acrylic acid Sodium.) Re-enter G.414g of N,N-decyldipropene on a water-soluble unsaturated monomer solution, the temperature is maintained at 2 (TC or so. 3) Add 0·144g hydrogen peroxide, i. 8 g The sodium bisulfite and the i 8 g persulfate are reacted with the initiator. (4) The gel formed by the reaction is chopped, and (4) a gel having a particle size of 2 mm or less is selected. The squeezing of the water-absorbing material under the pressure of 2. 3g /g, the water absorption ratio under the pressure of 49g / cm2 6. lg / g. Example 1 of the reference to obtain a water-absorbent resin 1 {%, adding ethylene glycol and ethylene oxide 19 20 200900439 alkyl phosphate ( Made by Matsumoto Oil Company, Product name: A_512A) Mixed aqueous solution 1. 5g 'surface tension value = 33. 4 mN / m, to 140. (: heat treatment for 1 hour, after cooling, to obtain high performance super absorbent resin. Its measurement retention is 32 Lg/g, 20g/cm2 under water pressure absorption ratio of 27. 5g / g, 49g / cm2 under water pressure absorption rate of 19. 3g / g. Example 2: Repeat Example 1, but add glycerin and ethylene oxide The base phosphate mixed aqueous solution 1. 5 g, surface tension value = 32 · 5 mN / m, and 14 (Tc temperature heat treatment 丨 hours, that is, a high performance super absorbent resin. 7克/克。 The measured retention of the force is 314g / g, a water absorption ratio of 2 〇g / cm 2 pressure of 26. 8g / g, 49g / cm2 under water pressure absorption rate of 19. 7g / g. Example 3: Example 1 was repeated, but a mixed aqueous solution of diethylene glycol and ethylene oxide alkyl phosphate was added, 5 g, surface tension value = 31. 3 mN/m, and heat treatment was carried out at a temperature of 14 〇t. In hours, it is a high-performance superabsorbent resin. 9克/克。 Under the pressure of the water absorption ratio of 17. 9g / g. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 〇 Temperature heat treatment i J day inch' is a high-absorbency resin with a kneading performance. The measurement retention is 32.9 g/g, and the water absorption ratio under the pressure of 20 21 21200900439 20 g/cm 2 is 25. 7 g / g, and the water absorption ratio under the pressure of 49 g / cm 2 is 16. 5 g / g. Example 5: Example 1 was repeated, but polyethylene glycol diglycidyl ether (manufactured by Nagase Co., Ltd., trade name: EX-810) and an aqueous solution of an ethylene oxide alkyl phosphate mixed solution of 15 g were added, and the surface tension value was 33.1. 4g/克 ' 49g 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The water absorption ratio is 15.2 g/g under the pressure of /cm2. Example 6: Repeating Example 1 'but with 18 (TC temperature heat treatment for 1 minute, the high-performance superabsorbent resin is obtained. The measured retention is 33. Lg/g, 2〇g/cm2 under water pressure absorption ratio 22. 9g / g ' 49g / cm2 under water pressure absorption ratio of 16. 3g / g. Example 7: Weighing reference example 1 obtained super absorbent resin 1〇 〇g, add aluminum sulfate powder 1·〇g, after mixing evenly, add ethylene glycol carbonate and ethylene oxide alkyl phosphate dish to this & water's solution i.5g, heat treatment at 140C for 1 hour After the cooling, the same performance as the water-absorbing resin is obtained. The measured retention is ig/g, and the water absorption ratio under the pressure of 2 〇g/cm 2 is 24. 5 g / g, and the pressure is 49 g / an 2 Water ratio 18·3g/g. 21 22 200900439 Example 8: diol carbonate and ethylene oxide alkyl phosphate (pine
比較例一: 重覆實例一 ’但加入乙二 本油劑公司製造，商品名： 重覆實施例-’但添加乙二醇水溶液丨.5g，表面張力值=5〇. 5Comparative Example 1: Repetitive Example 1 'But added to the second oil company, trade name: Repetitive Example - 'but add a solution of ethylene glycol 丨. 5g, surface tension value = 5 〇. 5
水性树I。其測疋保持力為41. lg/g，20g/cm2壓力下吸水倍率 9. 3g/g，49g/cm2壓力下吸水倍率& 8g/g。 比較例二： 重覆比較例一 ’提咼溫度至18(Tc加熱處理1小時，冷卻後， 即得高性能高吸水性樹脂。其測定保持力為4〇. 9g/g，2〇g/cm2 壓力下吸水倍率9. 4g/g，49g/cm2壓力下吸水倍率7. 〇g/g。 【圖式簡單說明】 【主要元件符號說明】 22Water-based tree I. The enthalpy retention was 41. lg/g, and the water absorption ratio under pressure of 20 g/cm 2 was 9. 3 g/g, and the water absorption ratio under pressure of 49 g/cm 2 was 8 g/g. Comparative Example 2: Repeating the comparison example 1 to raise the temperature to 18 (Tc heat treatment for 1 hour, after cooling, to obtain a high-performance superabsorbent resin. The measured retention is 4 〇. 9g / g, 2 〇 g / The water absorption ratio under the pressure of cm2 is 9. 4g/g, and the water absorption ratio under the pressure of 49g/cm2 is 7. 〇g/g. [Simple description of the figure] [Main component symbol description] 22