6 200918581 九、發明說明： 【發明所屬之技術領域】 本發明係關於-種對水溶液吸收良好的吸水物，此高吸水 性樹脂廣泛地運餘農業或崎方面的水保制、建築材料中的 抗露珠凝結伽及移紋油巾水份㈣料，或是電齡中的外層 =水包覆劑以及衛生用品如尿布、婦女衛生用品、抛棄式的擦巾 ^ 〇 y 上述的高吸水性樹脂經聚合製程後，尚須經轉體绞碎， =絞碎後之小膠體均勻散佈於乾燥财，高吸水性樹脂散佈不 句時’會造成乾燥不完全，從而降低整個製程之效率，為了逆加 ^燥效率，就必高乾燥溫度，—旦乾雜度提高，將影^物 性，如：粒徑、茶袋保持力、壓力下吸收倍率等等。 工業化之特 水性樹脂不僅要滿足上列的物理性質外，尚需具有 、 性0 〆、 【先前技掏·】 於知的高吸水性樹脂的成分材料有，遇水分解型的殿 ^丙稀腈接«合物（日本專利公開公報昭鄉叫43則， 中和之婦-枝聚合物（ 報 ί=Γ_14,689)，娜騎絲㈣攀==日 :=二夭5Γ叫84,3G4)等。其中概—丙稀腈接技聚合 無法長時_保存；再者，料造方、、腐雕的讀’所以 吸水性樹+ 方法十分複雜，所以現今高 他之袅備方式均以使用丙婦酸及丙婦酸鹽 7 200918581 合所製得之高吸水性樹脂佔最大部份也最為經濟，其原因為丙烯 酸鹽共聚物原料一丙烯酸可迅速由商場上購得， 性樹脂具咖吸偏，㈣恤懈 以及不會5丨起賴性的分解，故成為最f遍化的高吸水性樹脂。 聚合丙触及㈣酸娜成高吸水性翻旨的方法可由數種 已知的方法製得’如水溶液聚合反應、逆相懸浮液聚合反應、乳 化聚合反應或將單射灑或於纖維基f上進行聚合反應等方 ^在魏方种，逆相祕«合反細及乳崎;反;必須 2用到有機溶劑，但若無法有效的控制聚合反應時的溫度，有機 溶劑將造成反齡統之溫度以及壓力的增加，會產生敎現象甚 至^發爆炸，進而威脅到操作現場人員的安全以及造成環境污染 問題，其成品也有有機溶劑殘留的疑慮。 一 ^製造高吸水性樹脂無論是以水溶液聚合反應、逆相懸浮液 聚合反應、乳化聚合反應或將單體魏或塗覆於纖絲質上進行 聚合反應等方法’最終都必須將之乾燥，而一般都是利用刚至 i說高溫的—姐乾齡式；錄_，須先料合反應所得之 大塊膠體’峨碎擠財成小麵（逆姆浮絲合反應除 外）’再將小顆粒膠體均勻散佈於乾燥機中，以利乾燥。 【擬解決之技術課題】 技藝界粉碎高吸水性樹脂_的方法，主要以多孔板配合 切刀’以_螺桿方讀壓膠體，使之粉碎，目前已開發出 多種防止粉碎後膠體絲成團的方法，如日本積水化公司成利用 7 200918581 ==土，進行膠體分散，此_物使用前須_適當大8 之β石私’於大膠體粉碎成小膠體的 Γ= 存在著_大缺陷：—是在粉碎的過程^、 ⑼機鹽類礦土長期與粉碎機刀盤的磨擦，使得1刀❹ =短::是礦土粉體對高吸水顺^ 2收’增加製造工藝難度，三是粉塵對人體的健 康有危害，尤其是開放式的製程。 有其它方式來改善高吸水性樹脂的分散性、降低 邊SU ’或疋減少粉碎機刀盤所受阻力的方法，如特公平 3-_號公報、特開平2_細號公報，利用擠壓機編^ ’添加離_ H二氧切麵场末，藉_少高吸水 凝聚成_象；特公平1-麵號公報亦細水溶性 不佳，甚至不溶於水之離型劑（黏著防止劑）來解決此種現象， 包括雜在200〜靴之石油分館物、高分子量之脂職旨化物、 黏度在10〜5x10 V/Sec之妙油。但此類水溶性不佳，甚至不溶於 火之離以（黏著防止劑）亦存在著一個嚴重的問題-表面張力， _此方式所得之高吸水性樹脂，其表面張力會大幅度降低，提 高尿布回滲的可能性。 …特開平11-188726號公報中，利用親水性表面活性劑如聚乙 -醇類之化合物’添加賊切製㈣過程中，但此 200918581 種親水性表面活性劑通常含有醇 9 過低時，高吸水性樹脂反而更容__=仏添加置 【解決問題之技術手段】 為解決上述之問題’本發明係利用水溶性之 =體分散在=面分散劑水溶液可在三種情況下加人‘ς ί、二成小顆粒的過程中，二、於小顆粒製成後： 顆粒的過程中與小顆粒製成後，而此水溶性 性列條件:一、為避免表面分散劑與高吸水 含醇ϊ 基(_)反應，表面分散劑之成份不可為 土魏基專易與幾基反應之化合物，二、為避免盈離 旨羧基根_反應’表面分散劑之餘不可為 =有夕&之金屬離子鹽，三、為避免表面張力過低，表面分气 Ϊ現ΓΓ水溶液表面張力應在25dyne細2以上，四、為提升^ f見張力，可於表面分散劑水溶中添加不大於5Gwt%之财 ，劑，親水性有機溶劑如甲醇、乙醇、丙醇、異有 甲醚、乙醚等。 * 【發明内容】 製造本發明之高吸水性樹脂所需的水雜不飽和單體，除 丙稀酸外’尚可㈣其它具有酸性翻的不飽和雙鍵的水溶性 體士甲基丙烯酸、馬林酸、富馬酸、2丙稀胺_2甲基丙燒續酸、 順丁烯二酸、順了稀二贿、反了烯二酸、反讀二峡等 用不特定限似可使用-種，亦可合併多種單體—齊使用， 200918581 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·丙埽 酸月女、曱基丙烯酸胺、丙稀酸2-缓基乙酯、曱基丙稀酸2_叛基乙 醋、丙稀酸曱g旨、丙烯酸乙_、胺丙稀_醯胺、氣化丙婦 丙蝉醯胺基二甲銨但添加量以不破壞高吸水性樹脂之物性為原 I1] ° '、' 本發明在進行自由基聚合反應時，單體水溶液濃度並沒有特 別的限制，但較佳濃度宜控制在重量百分比2〇加％至55加％間， 適當濃度為3Gwt%至45wt%之間，濃度在重量百分比2_%以下 時，來合後水/郝太軟且有黏性不利機械加X，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，不飽和單體水溶液pH值不低於5 5，若低於5 5 時，聚合後水凝膠體内殘存單體含量過高，導致高吸水性樹脂之 物性不佳。 含酸基單體之繼基’應該部份巾和以㈣成品之阳值使 其呈中性紐酸性。巾和劑為聊表巾驗金族紐土麵氣氧化 物或是魏化合物，如：氫氧化鈉、氫氧化卸、碳酸鈉、碳酸钟、 碳酸氫鈉、礙酸氫卸或氨類化合物；中和劑可單獨使用一種或多 種混合仙。含單體之誠基部份巾和成_或鉀鹽或銨 鹽，中和濃度莫耳百分比為45mol%至85m〇1%，宜為5〇m〇1%至 75md%。中和濃度莫耳百分比為45ηι〇1%αι^成品之pH值會 偏低’中和濃度莫耳百分比為85m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，若不慎與人體接觸時均不 太安全。 在進行自由絲合反應前’單體水溶液中亦可添加水溶性高 11 200918581 分子=降低成本。此等水溶性高分子如：部份息化或完全息化的 聚乙稀醇、聚乙二醇、聚丙稀酸、聚丙婦_、殿粉或殿粉衍生 物如甲基纖維素，丙烯酸曱基纖維素，乙基纖維素等聚合物；此 等水溶性高分子的好量並不特舰定，射較仙水溶性高分 子為，粉。部份皂化或完全皂化的聚乙烯醇等可單獨或混合使 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 0至20wt% ’但以〇至10wt%較佳，〇至5加％尤佳，添加超過 20wt%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 於未反應之單體溶液中，此自由絲合反應交侧可顧罝有兩 個或兩個以上不飽和雙鍵的化合物，如 聊-次甲基雙丙刺胺' N，N，.次f基雙f基丙騎:基丙)=酸 丙烯酉曰、乙二醇二丙烯酸g旨、聚乙二醇二丙烯酸_、乙二醇二甲 ，丙烯酸自旨、聚乙二醇二甲基丙烯_旨、甘油三輯酸酯、甘油 ”酯、甘油附加環氧乙烷之三丙烯酸酯或三甲基丙烯 ^酯―、三甲丙_加環氧乙烧之三丙稀酸喊三曱基丙稀酸 酿、三曱醇秘三甲基丙烯酸S旨、三甲醇丙烧三_酸®旨、N,N，N-=(2-丙烯基)胺、二丙埽酸乙二醇酯、三丙稀酸聚敦乙稀甘油醋、 -丙燁U基聚氧乙烯甘㈣、二丙婦三甘_旨等，亦可選用 f有兩個或兩伽上環氧基的化合物，如山梨醇聚縮水甘_、 及丙三醇聚縮水甘_、乙二醇二縮水甘油醚、二乙二醇二縮水 •^由_、聚乙二醇二縮水甘油醚、雙丙三醇聚縮水甘㈣等。在 2自由基反應·可使高吸水性樹脂具當交聯度，而使高 =水性樹轉财適當的加1性。自由絲合反應交聯劑可單獨 用或兩種以上昆合使用。自由基聚合反應交聯劑適當的添加劑 11 200918581 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〇.〇lwt%至3wt%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。 — "6 200918581 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a water-absorbent material which absorbs well in an aqueous solution, and the superabsorbent resin is widely used in water conservation and building materials in agriculture or Kazakhstan. Anti-dew beads condensation and water-repellent oil towel (4) material, or outer layer in battery age = water coating agent and sanitary products such as diapers, feminine hygiene products, disposable wipes ^ 〇y The above super absorbent resin After the polymerization process, it is still necessary to be twisted by the rotating body. The small colloid after the crushing is evenly distributed in the dry money. When the super absorbent resin is scattered, it will cause the drying to be incomplete, thereby reducing the efficiency of the whole process. When the drying efficiency is increased, the drying temperature will be high, and the dryness will increase, and the physical properties such as particle size, tea bag retention, and absorption under pressure will be observed. Industrialized special water-based resin not only needs to meet the physical properties listed above, but also needs to have a property of 0 〆, [Previous technology] The composition of the superabsorbent resin is known to be water-decomposable Nitrile-based compound (Japanese Patent Publication No. 43 in Zhaoxiang, Neutralizing Women-Branch Polymer (Report ί=Γ_14,689), Na Risi (4) Climb==Day:=2夭5Γ84,3G4 )Wait. Among them, the acrylonitrile graft polymerization cannot be used for a long time _ preservation; in addition, the material is made, and the rot is read. So the water absorption tree + method is very complicated, so nowadays, the preparation method is high. Acid and propionate 7 200918581 The high water-absorbent resin produced by the company is also the most economical, because the acrylic copolymer raw material acrylic acid can be quickly purchased from the market, and the resin is biased. (4) It is the most highly water-absorbent resin that is the most widely used in the disintegration of the shirts. The method of polymerizing C-contact (tetra) acid to high water absorption can be obtained by several known methods such as aqueous solution polymerization, reverse phase suspension polymerization, emulsion polymerization or single shot or on fiber base f. The polymerization reaction is carried out in the Weifang, the reverse phase is secreted, and the organic solvent is used. However, if the temperature of the polymerization reaction cannot be effectively controlled, the organic solvent will cause the anti-age system. The increase in temperature and pressure can cause paralysis or even explosion, which threatens the safety of personnel at the operating site and causes environmental pollution problems. The finished product also has doubts about residual organic solvents. A method for producing a superabsorbent resin, whether it is an aqueous solution polymerization reaction, a reverse phase suspension polymerization reaction, an emulsion polymerization reaction, or a polymerization reaction of a monomer or a coating on a fibril, must be dried. In general, the use of the high temperature is just to say that the high temperature is the same as the age of the sister; the _, the bulk of the colloid obtained from the first reaction, the smashed into small noodles (except for the reverse mound reaction) The small particle colloid is evenly dispersed in the dryer for drying. [Technical issues to be solved] The method of smashing superabsorbent resin in the art world mainly uses a perforated plate with a cutter to smash the colloid by _screw, and has developed a variety of colloidal filaments to prevent pulverization. The method, such as the Japanese Sekisui Chemical Co., Ltd. uses 7 200918581 == soil, for colloidal dispersion, this _ thing must be used before _ appropriate large 8 β stone private 'in large colloid pulverized into small colloid Γ = there are _ big defects: - is in the process of smashing ^, (9) machine salt minerals long-term friction with the pulverizer cutter, so that 1 knife ❹ = short:: is the mineral powder for high water absorption 顺 ^ 2 collection 'increased manufacturing process difficulty, three Dust is harmful to the health of the human body, especially the open process. There are other ways to improve the dispersibility of the superabsorbent resin, reduce the side SU' or reduce the resistance of the cutter head, such as the special fair 3-_ bulletin, the special Kaikai 2_ fine bulletin, using extrusion Machine editing ^ 'Adding _ H dioxo surface field end, borrowing _ less high water absorption condensed into _ elephant; special fair 1- face number bulletin also fine water-soluble poor, even insoluble in water release agent (adhesion preventive agent ) to solve this phenomenon, including miscellaneous oil in the 200 ~ boots oil, high molecular weight lipids, viscosity in the 10 ~ 5x10 V / Sec oil. However, such water-soluble is not good, even insoluble in the fire (adhesion preventive agent) also has a serious problem - surface tension, _ this method of super absorbent resin, its surface tension will be greatly reduced, improve The possibility of diaper rewet. In Japanese Laid-Open Patent Publication No. Hei 11-188726, a hydrophilic surfactant such as a compound of a polyethyl alcohol is added during the process of cutting a thief (4), but the 200918581 hydrophilic surfactant usually contains an alcohol 9 which is too low. Superabsorbent resin is more __=仏 Adding [Technical means to solve the problem] In order to solve the above problems, the present invention utilizes water-soluble body dispersion in the form of an aqueous solution of a dispersant which can be added in three cases. ς ί, two small particles in the process, two, after the small particles are made: after the particles are made with small particles, and the water solubility column conditions: First, to avoid surface dispersants and high water absorption Alcohol oxime (_) reaction, the composition of the surface dispersing agent can not be a compound which is easy to react with a few groups of the soil Weiji, and the second is to avoid the surplus of the carboxyl group _reaction 'surface dispersing agent can not be = eve & amp The metal ion salt, three, in order to avoid the surface tension is too low, the surface gas is Ϊ Ϊ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ ΓΓ 5Gwt% of the money, agent, An aqueous organic solvent such as methanol, ethanol, propanol, iso there ether, diethyl ether and the like. * [Summary of the Invention] The water-unsaturated monomer required for producing the super absorbent resin of the present invention, in addition to acrylic acid, is a water-soluble body methacrylic acid having an acidic double-bonded unsaturated double bond. Marlinic acid, fumaric acid, 2 propylene amine 2 methyl propyl sulphuric acid, maleic acid, succinct bribes, anti-enediic acid, anti-reading two gorges, etc. Use - kinds, can also be combined with a variety of monomers - use, 200918581 may also need to add other hydrophilic monomers with unsaturated double bonds, such as · acetaminophen, methacrylic acid amine, acrylic acid 2- Sulfhydryl ethyl ester, mercapto acrylic acid 2 _ thioglycolic acid, acrylic acid 曱 g, acrylic acid _, amine propylene amide, gasification, propyl methacrylate, but the amount added The physical properties of the superabsorbent resin are not destroyed as the original I1] ° ', ' In the present invention, the concentration of the aqueous monomer solution is not particularly limited in the radical polymerization, but the preferred concentration is preferably controlled to 2% by weight. Between 55 and 5%, the appropriate concentration is between 3Gwt% and 45wt%, and the concentration is less than 2% by weight. /Hao is too soft and sticky, unfavorable mechanical plus X, the added concentration is above 55Wt% by weight, close to saturation concentration, difficult to mix and react too fast. The reaction heat is not easy to control, and the pH value of the unsaturated monomer aqueous solution is not lower than 5 5 . If it is less than 5 5 , the residual monomer content in the hydrogel after polymerization is too high, resulting in poor physical properties of the super absorbent resin. The thiol group containing the acid group monomer should be partially neutralized and the (4) positive value of the finished product made it neutral neutral. The towel and the agent are the gas mask oxides or the Wei compounds, such as: sodium hydroxide, hydroxide dehydration, sodium carbonate, carbonic acid clock, sodium hydrogencarbonate, acid-depleted hydrogen or ammonia compounds; The neutralizing agent may be used alone or in combination with one or more kinds. The monomer-containing portion of the monomer and the potassium or ammonium salt have a neutralizing concentration of the molar percentage of from 45 mol% to 85 m〇1%, preferably from 5 μm to 1% to 75 md%. The neutralization concentration of the molar percentage is 45ηι〇1%αι^ The pH value of the finished product will be low. The neutralization concentration of the molar percentage is 85m〇1% or more, the pH value of the finished product will be high, and the finished product pH is not neutral or When it is slightly acidic, it is not safe if it is inadvertently contacted with the human body. High water solubility can also be added to the aqueous monomer solution before the free silk reaction. 11 200918581 Molecule = reduced cost. Such water-soluble polymers such as: partially or fully-interested polyethylene glycol, polyethylene glycol, polyacrylic acid, polyacrylonitrile, palace powder or temple powder derivatives such as methyl cellulose, strontium acrylate Base cellulose, ethyl cellulose and other polymers; the amount of these water-soluble polymers is not special, the shot is more water-soluble polymer, powder. The partially saponified or fully saponified polyvinyl alcohol or the like may be used singly or in combination. The water-absorbent resin preferably contains 0 to 20% by weight of the water-soluble polymer added. However, it is preferably 〇 to 10% by weight, preferably 5% to 5%. When added over 20% by weight, the physical properties are affected. Getting worse. Before the radical polymerization reaction, a radical polymerization crosslinking agent should be added to the unreacted monomer solution, and the free silk reaction reaction side can take a compound having two or more unsaturated double bonds. Such as Liao-methine bis-propionamide 'N, N,. f-based double f-based C riding: base C) = acid propylene oxime, ethylene glycol diacrylate g, polyethylene glycol diacrylate _, Ethylene glycol dimethyl, acrylic acid, polyethylene glycol dimethyl propylene, triglyceride, glycerol ester, glycerol plus ethylene oxide triacrylate or trimethyl propylene ester - Trimethyl propylene _ plus Ethylene ethoxide triacrylic acid shouting triterpene acrylic acid brewing, triterpene alcohol trimethic acid S, trimethyl propylene triacetate, acid, N, N, N-= (2-propenyl)amine, ethylene glycol dipropionate, tripropylene glycol glycerin vinegar, -propyl ketone U-based polyoxyethylene glycol (tetra), di-propyl glycerol Select compounds with two or two ethoxy groups of epoxy groups, such as sorbitol polycondensate _, and glycerol polycondensed water _, ethylene glycol diglycidyl ether, diethylene glycol condensed water ^ ^ by _ Polyethylene glycol Glycidyl ether, diglycerin polycondensation (4), etc. In the 2-radical reaction, the superabsorbent resin can be made to have a degree of crosslinking, and the high = water-based tree can be appropriately added. The crosslinking agent may be used singly or in combination of two or more. The radical polymerization crosslinking agent appropriate additive 11 200918581 is between 0.001% by weight and 5% by weight based on the total solids of the reactants, A more suitable amount by weight percentage is between wt1wt% and 3% by weight, and 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, and the amount of the additive is more than 5% by weight. The water absorption is too low to reduce the resin properties. — "
聚合反應由自由基聚合反應起始劑的分解產生自由基開 始。自由基起始劑可選用熱分解型起始劑，適合的熱分解型起始 劑有過氧化物’如：過氧化氫、二.第三丁基過氧化物、過氧化酿 胺或過硫酸鹽(錄鹽、驗金屬鹽)等，及偶氮化合物如：2.2,_偶氮 基雙(2-脒基丙烧)二鹽酸鹽、2 2，_偶氮基雙(Ν，Ν_二伸甲基異丁 二鹽酸鹽；亦可使闕原劑，使成域化還原型起始劑，如：酸 性亞硫酸鹽、硫代硫Μ、抗壞域或亞纏；或籠化還原型 起始劑和熱分解型起始劑合併使用，首先氧倾原起始劑先進行 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，由於聚合反錢行時會觀妓4的·而使溫度升高，當 溫度到達熱分解型起始劑的分解溫度時，又料發第二段熱分解 型起始劑的分解，而使整個聚合反應更療於完全。—般自由基聚 合反應起始_相量為重量百分比為_wt%至胸％(以中 口=酸鹽重量為基準），更適當用量則在0她至5邊之間， 百分比咖讓以下時，反應太慢不利經濟效益，使用 重里百h比lGwtm時’反應太快反應熱不易控制。 聚合反應可於傳統批次反應容器中，或於輪送 進仃乾知，必須先經由絞碎機將凝膠體製 12 200918581 佈於乾燥履帶上以進行烘乾，根據本發明 之刀 ，，過程中，所遭受之阻力，並增加膠體== 於 刀、，水洛液，表面分散劑水溶液之濃度以001〜观較佳，f t散。劑水溶液添加量對吸水性樹轉體之重量百分、 」〜5〇%較佳；但此表Φ分散劑並分限定於水溶液聚人 縣 汙專其他方式聚合所得吸水性樹脂膠向芯 性樹脂膠分散、流動性時，皆可翻。^ ^切加吸水 佈不麟紅過針，純水性樹脂散 植 從而降低整個製程之效率，為了 曰加乾燦效率，就必須提高賴溫度，— 、 二 的細粉量’使量物縣現不佳，更降低產能。妝门產。。 乾溫至18叱進行棋乾為宜，棋 以上會仙物職早嫩度中1 ==果峨侧姆糊殘她:達到二 加埶晋通的乾燥11或加減，適用於本發明的 臺i乾^ it t:隨道式齡賴11、槪式乾燥器、 _化床乾燥器、氣流式乾燥器以及紅外線乾燥器等。 同吸水性樹脂為不溶解之親水性聚合體，樹脂内部具有均句 14 14200918581 性的架橋結構，一般為了改折 度、提高抗結塊性，以如=:==強 步架橋。此表面交聯處理㈣用具有t :’在㈣已有許多專利提出;如分散=;= 於有機㈣中進行表面交料理（jp.a_5=;^: 直接將交聯劑與交聯劑’使用無機粉 (JP-A60-163956 ^ ；； f ^ ^ ^ #ί ^ ^ 11 (JP-A-M13406)，,? 5 (购-292004、美國專利6=9 $多元醇進行表面處理 Mm / 寻J 6346569號），使用有機溶液、水、 此、^ /_!各2_1539()3)等；這些表面處理的方法雖能提高吸 專率、提高壓力下吸水倍率，但將造成保持力下降過多 後果’降低實際應用之性能。 於表面處理時能同時進行反應的交聯劑可為多元醇如：丙三 -于、乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇、工4 丁 三腔基甲基服、山梨醇等；或可使用多元胺如：乙乂胺、 胺、三乙二胺、聚乙二胺；或可使用具有_或兩個以上 二乳基的化合物如：山梨醇聚縮水甘_、聚丙三醇聚縮水甘油 纩乙一醇一&水甘油越、二乙二醇二縮水甘油Μ、聚乙二醇二 甘相1 n㈣縮水甘㈣等；亦可使用碳酸亞煙醋 乙一g;碳旨、4_甲基]，3_二氧雜環戊二曱基 二氧雜環戊m 4,4-二曱基仏二氧雜環戊烧姻、4_乙基 一_一氧雜環戊烷-2-酮、1，3-二氧雜環己烷_2_酮、4,6_二甲基义孓 環说2刪1>二氧雜環膝2·崎。交·的用法可 早獨使用或兩種以上混合使用。交聯劑的適當添加劑量在重量百 14 200918581 分比0.001wt〇/o至i〇wt〇/0之間（以反應物總固 的用量在_減至憾⑽，交雜 O.OOlwt%以下時無法顯出效果，交聯獅加紐在重量百= l〇wt%以上時，吸水性太低，降低樹脂性能。 刀 表面交聯劑塗覆處理時’表面交聯劑之添加方式則 =的義，嫩㈣細編σ，_編交聯劑 ^液添加，或調絲面交聯醜水財機溶财溶_加 性有機溶劑如甲醇、乙醇、丙醇、異丁醇、丙酮、曱醚、乙 特殊限制，可形成溶液即可，其中以甲醇、乙醇較佳(美國 :二表面交聯劑添加時高吸倾脂中可添加惰性無機 里叔末，以幫助溶液分散，惰性無機鹽粉末可為硫酸鋁、或二氧 化石夕’或氧化紹’或氧傾等或其混合物。其中以硫酸銘、:氧 =石夕較佳。惰性無機鹽粉末的用法可單獨使㈣合併兩種以上混 。使用。惰性無機鹽粉末添加範圍在重量百分比0005wt%至 l〇.〇wt%之間’其中以〇 〇lwt%至4 〇wt%較佳。 進行表面交聯劑塗覆處理後，再以9(TC至230°c範圍内進行 加熱處理’使表面交聯織均勻而且快速的進行交聯反應，並使 内部交_丨同時進行交聯反應而達到本發明之效果^處理溫度 ' C =下父聯反應時間太久，不具經濟效益，熱處理溫度 二上树月曰易劣化影響品質，熱處理時間以3〇分鐘至15〇分鐘為 一依,系浴人獲得到的表面處理效果做熱處理溫度調整，熱處理溫 度问則熱處理Β相短，減理溫度彳叫，則減理溫度時間長。 使用普通的乾燥器或加熱爐即可完成熱處理的步驟，適用於 务明的熱處理裝置有包括：隧道式混合乾燥器'轉鼓式乾燥 15 200918581 ^臺式乾燥器、流化床乾騎、氣流式乾聽以及紅外線乾燥 行熱處理後’於高吸水樹脂中添加水不溶性微粉，進 水ί她命水樹麵&之_隙，使高吸 接财高軸性。水不雜微粉添加方式為直 ‘二勢，销將水不紐微粉黏著於高吸水樹脂表面； 石山^ί ^括硫_、硫酸鎂、氧脑、氧化鎮、氧化鋅、 、姚+魏鋇、魏土、軟土、黏土、滑石粉、滞石、 土、活性碳、二氧化石夕、二氧化鈦之無機鹽粉末，及 !s''^ 〇 a 7不/秦ί政粉中，以添加無機鹽粉末的效 ，末_法可單賊岐合併兩種以上混合使用。添加範圍= 里百分比〇.〇〇祕至10.0wt%之間，其中以〇伽％至4細城 佳。水不溶性微粉之粒子大小最好不大於10麵，更適當的大小 為0.6 mm以下。黏著劑可為多元醇如：丙三醇、聚乙二醇、山 梨酵等；或可使用聚乙烯亞胺。姆_用法可單獨使用或合併 兩種以上混合使用。黏著劑的適當添加劑量在重量百:比 O.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_5wt%至5wt%之間，黏著劑添加劑量在重量^分比 O.OOlwt。/。以下時無法使惰性無機鹽粉末完全黏著於高吸水樹脂 表面’黏著劑添加劑量在重量百分比1Qwt%以上時，吸水性太低， 降低樹脂性能。 ^ 本發明之目的，在利用添加分散劑於膠體顆粒的方式，提高 生產效率、提升產品物性’以產生-種粉狀、不溶於水，可吸收 16 17 17200918581 ΐ液或尿液及錢，具有高保持力、低殘存未反應單體，且在較 =的壓力下尚具有較高吸收倍率特性的高性能高吸水性樹脂，其 乂造方法至少包括： (a)中和比率在45至85莫耳%之範_，不飽和單體水溶液的 濃度在20至55重量份之範圍； ⑹中和後聚合生成之高财性樹脂水凝膠，先將大塊水凝膠 塊經由絞切機製成小顆粒凝勝體，此過程中可加入表面分 散劑之水溶液； (c) 噴灑表面分制水溶祕小齡凝賴，使之混合均勾丨 (d) 經乾燥、粉碎、篩選； (e) 表面交聯劑塗覆；及 ⑴溫度90。〇至23(TC加熱表面改 質處理。 除逆相懸浮聚合外，於聚合後生產之高吸水性樹脂’皆需經 ^刀條機、健機或製粒機等機^，將大塊高吸水㈣脂膠體粉 ¥成!、顆粒之樹脂’而在擠墨製粒㈣程中，吸水性樹轉體有 =生變::阻礙擠壓螺旋桿之運轉’ 一旦阻力過大甚至會發生跳 =正個製程的運轉，在乾燥前，均勻散佈樹脂 =2送帶缺-重要事項，若分佈不均，驗高吸水性樹_ t 使其縣效果不彰，造成部分關難仍為未乾之狀 題:Γ衫響後續製程之進行，若以提高乾燥溫度來解決此問 ㈣使其乾燥、粉碎後的細粉量增多。當高吸水性樹脂在高溫 、速乾燥㈣讀樹_部水分容易因躲微逸出，而 17 200918581 在内部膨服形成氣泡，氣泡空洞越多，在 18 :::越容易造成氣泡空_的高吸水性樹脂：： 及生物體產生-定程度之影響，尤其是空氣中的縣== 吸水性樹η/外代細4之大小適合商使用的高 里減少’回收的細粉量愈多，將減低生產效率並增加 【實施方式】 為捸視本發明對細粉之影響，可藉由下述步驟檢驗。首先將單體 中和’加人觸媒聚合得高吸水性樹脂水凝膠，將水凝膠與分散劑 同加入&£機（美利德公司之產品，型號為嫩T_SCN_2S型） 中製粒，其包含一至數組刀具與多孔盤，孔捏為施m至3麵 不等，另設有電流感·置，可監測漏螺桿所承受之朦體阻 力在匕左機後’連接一滾筒製粒機，將所擠塵產生的小顆粒樹 脂，直接導人滾筒巾，並於其上增加分㈣之_歧入裝置， 用以增加膠體之分散性，並於出口處，取戰膠體做膠體分散 a夺間之檢驗’其餘膠體以履帶輸送至乾職（千銳似公司之產 口口，型5虎為DVTO型；或美利德公司之產品，型號為 200918581 型），經乾燥機以130〜靴進行完全烘乾，將乾燥後之高吸水 樹脂顆粒粉碎磨，以標準__出並計算各粒㈣分佈比例，檢 測不同乾燥溫度對_生成量㈣響，並進行比較，峨料影 響。 、 ，本發明中檢驗分散時間的方式，係取乾燥前之高吸水性樹脂 顆^卿2 ’將之放人長、寬、高為5αη、5αη、咖之透明壓克 ,力筒中（此筒之上、下兩端為開放式），以法碼加壓方式，在高吸 W生树月曰顆粒上以加兩壓1〇psi加壓1〇秒後，拿起壓克力筒與加 壓法碼後’觀察壓緊後高吸水性樹賴，由方卿脹、散裂至雜 平於地面上所需之時間。 、 本务W利用JIS標準篩網來檢驗細粉的生成量。根據 EDANA檢财法第wsp22().聊)號所描述的方法；將底部且有 :盤_網置於震動器中，篩網排列順序為網孔小者在下，啟動 (展動器，其震幅為Μ麵，10分鐘後停止震動器，篩選分類出 不同粒控的面吸水性樹脂後秤重，並利用下列方程式計算出各粒 #的分佈比率。 粒徑分佈比率=每—層篩網内之高吸水性樹脂重量 所有篩網内高吸水性樹脂重量之總和*100% 本么月為便於篩選性能的評估，將高吸水性樹脂中，粒徑小於 、06_卿標準篩網為14Gmesh)視為細粉，糊其所占比率的增 咸來判斬乾燥溫度對細粉的影響。 19 20 200918581 因表面張力Μ高低將影響尿_渗絲;見，為彰顯本發明之 高吸水性樹脂的高表面張力值，本發明以表面張力儀則％ Processor Tensi0meter κ卿來測定表面張力值；初始抒取重量 〇.5g的高吸水性樹脂放在燒杯中，加入4〇毫升〇 9%食鹽水，磁 石轉子以600聊授伴3分鐘，再將〇 9%液體以遽紙過遽，以表 面張力儀檢測濾液之表面張力。 本拥之倾力（CRC)係侧茶袋試驗法測定，並以五次 制結果’去除最高值以及最健後，取平均值；將G 2g的高吸 水性樹脂裝在茶袋裡，並浸泡於〇 9%的NaC1水溶液2〇分鐘，然 後將此浸泡後的茶袋置於離心機中離心(直徑23咖、轉速14〇〇_ 二分知後秤重。所得之紐先減去未域高吸水脂的空白組 茶袋重(以相同步驟操作)再除以聚合物重即得保持力數值。 低殘存^體的測定是利用液相層析儀（肌c)分析。先精科取 ,〇.5〇〇g高吸水性樹脂於150cc錐形瓶中，加人〇.524% NaC1水溶液 ί 10,及2cm的攪拌子一顆，以5〇〇rpm轉速攪拌一小時，加入 20^2(8〇4)3水溶液5g，再利用2μιη濾紙過遽，將滤液打入液相 曰析儀内分析，把所得之訊號和校正曲線相比對即可得到殘存單 體量。 以下以貫施例說明本發明；但本發明之專利及技術範圍則不 受這些實施例所限制。 【實施例】 實施例一: 20 21 21200918581 1) 取48°/。氫氧化納水溶液8〇2g及l〇69.2g的水置入於4000c.c圓 錐瓶中，緩慢加入330g丙烯酸並保持瓶内令和反應系統的溫度 在40°C以下’中和後之水溶性不飽和單體pH值為12 6。靜置 5分鐘後，再將660g丙烯酸加入部份中和完成的水溶性不飽和 單體中，其完全中和後之水溶性不飽和單體{)11值為5 6。此時 得水溶性不飽和單體濃度42wt°/。水溶液，其中7〇m〇l%(莫耳比) 丙烯酸部份中和為丙烯酸鈉。 2) 再加入1.518 g的N，N’-次甲基雙丙烯醯胺於水溶性不飽和單 體溶液，並維持溫度於20°C左右。 3) 加入0.528g雙氧水，6.62 g亞硫酸氫納及6 62 g過硫酸錢以 起始反應。 4) 利用切式粉碎機將反應生成的凝膠體切碎，並於此時加入非離 子型之表面分散冑-聚乙二醇二硬醋酸醋（中日合成化學股 限A司提供），其濃度為1%，1〇/。分散劑對粉碎夥體之使用旦 20%，觀察擠壓機電流變化（請參閱表一）。 里馮 5) 將上述粉碎之膠體倒入製粒滾筒中，並於此時加入1%玫 醇二硬_酸酷水溶劑，1%分散麵粉碎膠體之使用量=一 於筒中混合約5分鐘後，取出觀察其膠體分散時間之變二 參閱表一）。 、°月 6) 再以130。(：溫度乾燥2小時。 7) 經研磨後，利用JIS標準篩網（網目為⑽ 震動器震«間為1G分鐘騎所得之細粉量:_)， 2. 02% (請參閱表一）。 之比例為 8) 料磨所得大於购m之高吸水性樹脂，進行殘存單體測試、 21 22 200918581 保持力(CRC)測試與表面張力測試（請參閱表一）。 實施例二： 1) 重覆實施例-步驟υ~8)，但聚乙二醇二硬紐s旨濃度改為 10% ’ 1G%分散劑對粉碎膠體之使用量皆降為5%。 2) 其賴機電流、膠體分散時間、細粉量、殘存單體、保持力 與表面張力值，如表—所示。 實施例三： 1) 重覆實施例-步驟υ〜8)，但在丨％聚乙二醇二硬驗醋水溶 液中加入1%乙醇。 2) 其擠壓機電流、腰濟公 " 政蚪間、細粉量、殘存單體、保持力 與表面張力值’如表—所示。 實施例四： 垔復貫施例一步 醇二硬_旨，改為 =〜^非離子型之表面分散劑-聚乙二 ㈣（中日⑽乙塌細硫酸 2)其擠_電流、膠體 ’、 與表面張力值，如表1卞間、細粉量、殘存單體、保持力 實施例五： 1)重覆實施例四步驟丨） ’位離子型之表面分散劑_聚乙二醇 23 200918581 烷基醚硫酸銨鹽濃度改為10%，1〇%分散劑對粉碎膠體之使 用量皆降為5%。 2)其顧機電流、膠體分散時間、細粉量、殘存單體、保持力 與表面張力值，如表一所示。 實施例六： 1) 重覆實施例四步驟1)〜2)，但在〖％聚乙二醇絲醚硫酸銨 鹽水溶液中加入1%乙醇。 2) 其擠壓機電流、膠體分散時間、細粉量、殘存單體、保持力 與表面張力值，如表一所示。 實施例七： υ重覆實施例-步驟υ〜8) ’但非離子型之表面分散終聚乙二 醇二硬|旨酸g旨，改為離子型之表面分散劑-丁二酸二辛醋續酸 鈉（中日合成化學股份有限公司提供 2)其擠壓機電流、交體分散時間、細粉量、殘存單體、保持力 與表面張力值，如表一所示。 實施例八： 1)重覆實施例七步驟υ〜2)，但離子型之表面分散劑-丁二酸二 辛㈣酸納濃度改為10%，10%分散劑對粉碎膠體之使_ 皆降為5%。 2)其擠壓機電流、賴分散時間、細粉量、殘存單體、保持力 23 24 24200918581 與表面張力值，如表一所示。 實施例九： 1) 重覆實施例七步驟1)〜2)，但在1 %丁二酸二辛酯磺酸鈉水溶 液中加入1%乙醇。 2) 其擠壓機電流、膠體分散時間、細粉量、殘存單體、保持力 與表面張力值，如表一所示。 比較例一： 1) 重覆實施例一步驟1)〜8)，但1%聚乙二醇二硬酯酸酯水溶 劑，改成70%聚乙二醇二硬酯酸酯水溶劑。 2) 其擠壓機電流、膠體分散時間、細粉量、殘存單體、保持力 與表面張力值，如表一所示。 比較例二： 1)重覆實施例一步驟1)〜8)，但將1%聚乙二醇二硬酯酸酯水溶 劑，於步驟3)絞碎時、步驟4)膠體製粒時之添加量由20%改成 40%。 2)其擠壓機電流、膠體分散時間、細粉量、殘存單體、保持力 與表面張力值，如表一所示。 比較例三： 24 200918581 覆實施例-步驟υ〜8)，但1%聚乙二醇二硬輯酸醋水溶 劑，改成帶有高價金屬離子之1%硬&旨酸錤水溶劑（中日合成 化學股份有限公司提供）。 2)其擠壓機電流、膠體分 與表面張力值，如表―所示。私里、殘存早體、保持力 比較例四： 1)重覆實施例一步驟1)〜8)，作。 劑，改成、純水溶劑。 1%聚乙二醇二硬醋酸酯水溶 辦擠壓機電流、膠體分散叫 與表面張力值，如表一所示、、、‘置、殘存早體、保持力 比較例五： 1)重覆實施例一步驟丨） ^ iB l〇/Mx _ 劑，改成不添加任何溶南丨 °也乙二醇二硬酯酸酯水溶 細粉量、殘存單體、保持力 2)其擠顯電流、膠體分散 與表面張力值，如表一所示。3 26200918581 表一 擠壓機 電流(A) 膠體分 散時間 (秒） 保持力 (g/g) 表面 張力 (dyne/ cm2) 細粉 量⑻ 殘存單 體 (ppm) 實施例 39 18.4 41.2 65.6 2. 02 340 實施例 38 15.6 40.6 59.4 1.68 306 實施例 39 19.2 41.4 66.7 2.12 356 實施例 40 15.7 42.0 63.3 1.89 412 實施例 39 13.4 41.4 57.6 1.54 387 實施例 41 16.9 42.3 65.4 2.03 442 實施例 38 19.7 41.8 62.3 2. 32 387 實施例 38 17.4 41.1 56.3 1.88 334 實施例 39 20.4 40.9 64.1 2.98 398 比較例 37 13.6 41.6 44.3 1.44 344 比較例 48 20.3 39.4 49.3 3. 54 367 比較例 39 18.6 36.8 63.1 1.87 382 比較例 73 38.9 41.6 70.2 5.12 612 比較例 58 33.2 40.9 70.7 4.67 563 26 27 200918581 【圖式簡單說明】 【主要元件符號說明】 27The polymerization starts by the decomposition of the radical polymerization initiator to generate a radical. The free radical initiator can be selected from a thermal decomposition type initiator, and the suitable thermal decomposition initiator is a peroxide such as hydrogen peroxide, dibutyl peroxide, peroxidic amine or persulfate. Salt (recording salt, metal salt), etc., and azo compounds such as: 2.2, _ azobis(2-mercaptopropenyl) dihydrochloride, 2 2, azo(bis), Ν Dimethylisobutane dihydrochloride; can also be used as a protoporative agent to form a domain-reducing reducing initiator such as acid sulfite, thiosulfuron, anti-bad or sub-entangled; or caged The reducing type initiator and the thermal decomposition type initiator are used in combination. First, the oxygen tilting initiator starts to react to generate a radical, and when the radical is transferred to the monomer, the polymerization reaction is initiated, because the polymerization is anti-money. The temperature is raised when the temperature reaches the decomposition temperature of the thermal decomposition type initiator, and the decomposition of the second stage thermal decomposition type initiator is also caused, so that the entire polymerization reaction is more completely treated. - The radical polymerization starts _ phasor is _wt% to chest% (based on the weight of the mouth = acid salt), more appropriate 0 between her and 5 sides, when the percentage is below, the reaction is too slow, which is unfavorable economic benefit. When using heavy weights hh to lGwtm, the reaction is too fast and the reaction heat is difficult to control. The polymerization reaction can be carried out in a traditional batch reaction vessel, or In order to carry out the drilling, the gel system 12 200918581 must be placed on the drying track by the mincer to dry, according to the knife of the invention, the resistance encountered during the process, and the addition of colloid == The concentration of the aqueous solution of the knife, the water, and the surface dispersant is preferably 001 to 440. The amount of the aqueous solution added is preferably about 5% by weight of the water-absorbing tree-turned body; The dispersing agent is also limited to the aqueous solution of the water-absorbing resin glue obtained by polymerization in other ways. When the water-absorbent resin glue is dispersed to the core resin, the fluidity can be turned over. ^ ^Cut the absorbent cloth is not red, the pure water The resin is scattered to reduce the efficiency of the whole process. In order to increase the dry efficiency, it is necessary to increase the temperature, and the amount of fine powder of the second is not good for the county, and the production capacity is reduced. It is advisable to play chess to 18 , In the early tenderness of the celestial body, 1 == 峨 峨 姆 糊 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : , 槪 dryer, _ chemical bed dryer, air flow dryer, infrared dryer, etc. The same water-absorbent resin is an insoluble hydrophilic polymer, the resin has a bridge structure of 14 14200918581, generally in order to change Folding, improving anti-caking property, such as =:== strong step bridge. This surface cross-linking treatment (4) has many patents with t: '(4); such as dispersion =; = surface interaction in organic (four) Cooking (jp.a_5=;^: Directly use crosslinker and crosslinker' to use inorganic powder (JP-A60-163956 ^ ;; f ^ ^ ^ #ί ^ ^ 11 (JP-A-M13406),? 5 (purchase -292004, US patent 6 = 9 $ polyol for surface treatment Mm / seek J 6346569), using organic solution, water, this, ^ / _ each 2_1539 () 3), etc.; these surface treatment methods Although it can increase the suction rate and increase the water absorption rate under pressure, it will cause the retention force to drop too much and reduce the performance of the actual application. The cross-linking agent capable of simultaneously reacting at the time of surface treatment may be a polyhydric alcohol such as: propylene tri-, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, and a three-cavity base. Methyl, sorbitol, etc.; or polyamines such as acetamide, amine, triethylenediamine, polyethylenediamine; or compounds having _ or more than two emulsifiers such as sorbitol Shrinkage _, polyglycerol polyglycidol 纩 一 一 & & 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 ; ; ; ; ; ; ; ; ; ; ; ; ; ; E-g; carbon, 4-methyl], 3-dioxacyclononyl dioxole m 4,4-dimercaptodioxanthene, 4-ethyl- _ Monooxol-2-one, 1,3-dioxane-2-ketone, 4,6-dimethyl-anthracene ring, 2, and 1; dioxane, 2, and K. The usage of the exchange can be used alone or in combination of two or more. The appropriate additive amount of the crosslinking agent is between 0.001wt〇/o and i〇wt〇/0 by weight of the weight of 14 200918581 (the amount of total solids of the reactant is reduced to _(10), and less than 0.001% by weight. When the cross-linking lion and New Zealand is more than 100% l〇wt%, the water absorption is too low, and the resin performance is lowered. When the knife surface cross-linking agent is applied, the way of adding the surface crosslinking agent is The righteousness, tenderness (4) fine-grained σ, _ braided cross-linking liquid added, or the surface of the cross-linking ugly water machine dissolves _ soluble organic solvents such as methanol, ethanol, propanol, isobutanol, acetone,曱 ether, B special restrictions, can form a solution, which is better with methanol, ethanol (United States: two surface cross-linking agent added in the high-powed fat can be added in the inert inorganic uncle to help the solution dispersion, inert inorganic The salt powder may be aluminum sulfate, or sulphur dioxide or oxidized or oxygenated, or a mixture thereof, wherein sulphuric acid is used, and oxygen is preferred. The use of the inert inorganic salt powder may be separately combined (4). The above mixed. Use. Inert inorganic salt powder is added in the range of 0005wt% to l〇. Between wt%, where 〇〇lwt% to 4 〇wt% is preferred. After surface cross-linking agent coating treatment, heat treatment is carried out at 9 (TC to 230 ° C) to make the surface cross-linked uniformly. Moreover, the cross-linking reaction is carried out rapidly, and the internal cross-linking reaction is carried out at the same time to achieve the effect of the present invention. The treatment temperature is 'C = the parental reaction time is too long, and the economical temperature is not economical. It is easy to degrade and affect the quality. The heat treatment time is from 3 〇 to 15 〇 minutes. The surface treatment effect obtained by the bather is adjusted by heat treatment. The heat treatment temperature is short, and the heat treatment temperature is short, and the temperature is reduced. The temperature is long. The heat treatment step can be completed by using a common dryer or heating furnace. It is suitable for the treatment of the heat treatment. It includes: tunnel mixing dryer 'drum drying 15 200918581 ^ tabletop dryer, fluidization After the bed is dry, air-drying and infrared drying, after heat treatment, 'water-insoluble micropowder is added to the superabsorbent resin, and the water is added to the water and the surface of the tree is high. The water is not mixed. Micropowder The addition method is straight 'two potentials, the pin will adhere the water to the superabsorbent resin surface; Shishan ^ί ^ sulfur _, magnesium sulfate, oxygen brain, oxidation town, zinc oxide, Yao + Wei Wei, Wei Tu, Soft soil, clay, talcum powder, stagnation stone, soil, activated carbon, silica dioxide, inorganic salt powder of titanium dioxide, and !s''^ 〇a 7 not / Qin qingzheng powder, adding inorganic salt powder _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Preferably, it is not more than 10 faces, and a more appropriate size is 0.6 mm or less. The adhesive may be a polyhydric alcohol such as glycerin, polyethylene glycol, sorbitan, etc.; or polyethyleneimine may be used. The m_ usage can be used alone or in combination of two or more. The appropriate amount of the additive of the adhesive is between 100% by weight and 0.01% by weight (based on the total solids of the reactants), more suitably between _5% and 5% by weight, the adhesive additive The amount is in the weight ratio of O.OOlwt. /. In the following, the inert inorganic salt powder cannot be completely adhered to the surface of the superabsorbent resin. When the amount of the adhesive additive is 1% by weight or more, the water absorption is too low, and the resin property is lowered. ^ The object of the present invention is to increase the production efficiency and enhance the physical properties of the product by adding a dispersing agent to the colloidal particles to produce a powdery type, insoluble in water, and can absorb 16 17 17200918581 sputum or urine and money, having High-resistance, low-resistance unreacted monomer, and high-performance superabsorbent resin having higher absorption rate characteristics under a lower pressure, the method of manufacturing at least includes: (a) a neutralization ratio of 45 to 85 The concentration of the aqueous solution of the unsaturated monomer is in the range of 20 to 55 parts by weight; (6) the high-yield resin hydrogel formed by polymerization after neutralization, first transferring the large hydrogel block through the cutter A small particle condensate is prepared, and an aqueous solution of a surface dispersing agent can be added in the process; (c) the surface of the spray is divided into water to dissolve the small condensate, so that it is mixed and thickened (d) dried, pulverized, and screened; e) surface crosslinker coating; and (1) temperature 90. 〇 to 23 (TC heating surface modification treatment. In addition to reverse phase suspension polymerization, the superabsorbent resin produced after polymerization is required to pass through a knife machine, a health machine or a granulator, etc. Water absorption (four) fat colloidal powder ¥ into!, granule resin' and in the process of squeezing and granulating (four), the water-absorbing tree swivel has = change:: hinder the operation of the extruded auger ' Once the resistance is too large, it may even jump = positive The operation of the process, before drying, evenly distributed resin = 2 belt shortage - important matters, if the distribution is uneven, check the high water absorption tree _ t to make the county's effect is not good, causing some of the difficulties are still dry Question: The process of the subsequent process is to increase the drying temperature to solve this problem. (4) The amount of fine powder after drying and pulverization is increased. When the superabsorbent resin is dried at high temperature and speed (4) Ignore the micro-escape, and 17 200918581 in the internal expansion of the formation of bubbles, the more bubbles, the more easily the bubble in the 18::: super-absorbent resin: and the production of organisms - the degree of influence, especially County in the air == Water absorption tree η / Outer generation fine 4 size suitable for commercial use Gori Reduces the more the amount of fine powder recovered, which will reduce the production efficiency and increase. [Embodiment] In order to despise the effect of the present invention on fine powder, it can be tested by the following steps. The catalyst is polymerized to obtain a highly water-absorbent resin hydrogel, and the hydrogel and the dispersing agent are added to a & machine (a product of the company, model No. T_SCN_2S), which comprises an array of tools and a porous machine. The plate and the hole are pinched for a range of m to 3, and a current sense is provided. The body resistance of the leaking screw can be monitored. After the left machine is connected, a roller granulator is connected to generate the dust. Small particle resin, directly guide the roller towel, and add the sub-division device to increase the dispersibility of the colloid, and at the exit, the colloid colloid is used as the colloidal dispersion test. The track is transported to the dry position (the mouth of the company like Qianrui, the type 5 tiger is DVTO type; or the product of Meridian Company, model 200918581 type), and it is completely dried by the dryer with 130~boots. After drying, the super absorbent resin granules are ground and pulverized by standard __ And calculate the distribution ratio of each particle (four), detect the difference of the drying temperature of the _ generation amount (four), and compare and influence the material. The method of testing the dispersion time in the present invention is to take the superabsorbent resin before drying. 2 'Put it into people's length, width and height for 5αη, 5αη, transparent gram of coffee, in the cylinder (the upper and lower ends of the tube are open), with the method of pressure, in the high suction After adding 1 psi to the pressure of 1 〇 psi for 1 〇 psi, pick up the acrylic tube and pressurize the code and then 'observe the high water absorption tree after pressing, and the square swells and scatters to The time required to mix the ground on the ground. The main work uses the JIS standard screen to check the amount of fine powder produced. According to the method described in the EDANA Procurement Method, wsp22().Liao); The disk_net is placed in the vibrator. The screen is arranged in the order of the smaller mesh, and the starter (the actuator has a shock amplitude of the kneading surface. After 10 minutes, the vibrator is stopped, and the surface water absorption of different grain control is classified and classified. The resin was weighed and the distribution ratio of each particle # was calculated by the following equation. Particle size distribution ratio = weight of superabsorbent resin in each layer of sieves. Total weight of superabsorbent resin in all screens *100% This month is the evaluation of easy screening performance, and the particle size of superabsorbent resin Less than, 06_qing standard screen is 14Gmesh) as a fine powder, the proportion of the paste is increased to determine the effect of drying temperature on the fine powder. 19 20 200918581 The surface tension will affect the urine_seepage; see, in order to highlight the high surface tension value of the superabsorbent resin of the present invention, the surface tension meter is used to determine the surface tension value by the surface tension meter; The initial weight of the 〇5g superabsorbent resin was placed in a beaker, 4 〇 ml 〇 9% saline was added, the magnet rotor was accommodated for 3 minutes, and then 9% liquid was passed through the crepe paper. The surface tension meter detects the surface tension of the filtrate. This concentrating force (CRC) is determined by the side tea bag test method, and the average value of the five-time system is removed, and the average value is taken, and the average value is taken; the G 2g super absorbent resin is placed in a tea bag and soaked in 〇 9% aqueous solution of NaC1 for 2 minutes, then centrifuge the soaked tea bag in a centrifuge (diameter 23 coffee, speed 14 〇〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The blank group tea bag weight (operating in the same step) is divided by the polymer weight to obtain the retention value. The measurement of the low residual body is determined by liquid chromatography (muscle c). 〇〇g super absorbent resin in 150cc Erlenmeyer flask, add 524.524% NaC1 aqueous solution ί 10, and a 2cm stirrer, stir at 5 rpm for one hour, add 20^2 (8〇 4) 3g aqueous solution 5g, and then use 2μιη filter paper to pass through, the filtrate is put into the liquid phase decanter for analysis, and the obtained signal is compared with the calibration curve to obtain the residual monomer amount. The invention is not limited by these embodiments. [Examples] Implementation A: 2,021,212,009,185,811) taking 48 ° /. 8〇2g of aqueous sodium hydroxide solution and 69.2g of water were placed in a 4000c.c conical flask, 330g of acrylic acid was slowly added and the water content of the bottle and the reaction system was kept below 40°C. The pH of the unsaturated monomer is 12 6 . After standing for 5 minutes, 660 g of acrylic acid was further added to the partially neutralized water-soluble unsaturated monomer, and the water-soluble unsaturated monomer after the complete neutralization had a value of 5). At this time, the water-soluble unsaturated monomer concentration was 42 wt%/. An aqueous solution in which 7 〇m〇l% (mole ratio) of acrylic acid is partially neutralized is sodium acrylate. 2) Further add 1.518 g of N,N'-methine bis acrylamide to the water-soluble unsaturated monomer solution and maintain the temperature at about 20 °C. 3) The reaction was initiated by adding 0.528 g of hydrogen peroxide, 6.62 g of sodium hydrogen sulfite and 6 62 g of persulfate. 4) The gel produced by the reaction is chopped by a chopping mill, and a non-ionic surface-dispersion 胄-polyethylene glycol di-hard acetic acid vinegar (provided by the Sino-Japanese Synthetic Chemicals Co., Ltd.) is added at this time. Its concentration is 1%, 1 〇 /. The dispersant is used for 20% of the crushed body and the extruder current is observed (see Table 1). Li Feng 5) Pour the pulverized colloid into the granulating drum, and add 1% mellow dihydro-acid cold water solvent at this time. The amount of pulverized colloid used in 1% dispersing surface = one mixing in the cylinder for about 5 minutes. After the removal, observe the change of the colloidal dispersion time (see Table 1). , ° month 6) and then 130. (:The temperature is dried for 2 hours. 7) After grinding, use JIS standard sieve (the mesh is (10) vibrator shock «the amount of fine powder obtained by riding in 1G minutes: _), 2. 02% (please refer to Table 1) . The ratio is 8) The superabsorbent resin obtained by the mill is larger than the super absorbent resin, and the residual monomer test, 21 22 200918581 retention force (CRC) test and surface tension test (see Table 1) are performed. Example 2: 1) Repeat Example - Step υ~8), but the concentration of polyethylene glycol hexazone was changed to 10% ‘1G% dispersant and the amount of pulverized colloid was reduced to 5%. 2) The current of the machine, the dispersion time of the colloid, the amount of fine powder, the residual monomer, the retention force and the surface tension value are shown in Table--. Example 3: 1) Repeat Example - Step υ~8), but add 1% ethanol to a 丨% polyethylene glycol diacetate aqueous solution. 2) The extruder current, the waist, the common volume, the amount of fine powder, the residual monomer, the retention force and the surface tension value are shown in the table. Example 4: 垔 贯 施 施 一步 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇And surface tension values, as shown in Table 1, 细, fine powder, residual monomer, retention Example 5: 1) Repeat the fourth step of the example 丨) 'Spot ionic surface dispersant _ polyethylene glycol 23 200918581 The alkyl ether sulfate ammonium salt concentration was changed to 10%, and the use amount of the 1% by weight dispersant to the pulverized colloid was reduced to 5%. 2) The current of the machine, the dispersion time of the colloid, the amount of fine powder, the residual monomer, the retention force and the surface tension value are shown in Table 1. Example 6: 1) Example 4, steps 1) to 2) were repeated, but 1% ethanol was added to a solution of % polyethylene glycol ether sulfate ammonium salt. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Example 7: υRepeat Example - Step υ~8) 'But the non-ionic surface-dispersed final polyethylene glycol is hard; the acid is intended to be changed to the ionic surface dispersant-succinic acid dioctyl Sodium vinegar sodium (provided by Sino-Japanese Synthetic Chemical Co., Ltd. 2) its extruder current, cross-distribution time, fine powder amount, residual monomer, retention and surface tension values, as shown in Table 1. Example 8: 1) Repeat Example 7 step υ~2), but the ionic surface dispersant-succinic acid dioctyl (tetra) sodium sulphate concentration was changed to 10%, 10% dispersant for pulverizing colloid _ Reduced to 5%. 2) The extruder current, dispersion time, fine powder amount, residual monomer, retention force 23 24 24200918581 and surface tension values, as shown in Table 1. Example 9: 1) Example 7, steps 1) to 2) were repeated, but 1% ethanol was added to 1% aqueous sodium dioctyl succinate sulfonate solution. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Comparative Example 1: 1) Example 1) Steps 1) to 8) were repeated, but a 1% polyethylene glycol distearate aqueous solvent was changed to a 70% polyethylene glycol distearate aqueous solvent. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Comparative Example 2: 1) Repeat Example 1 Steps 1) to 8), but when 1% polyethylene glycol distearate aqueous solvent is slurried in step 3), step 4) The amount added was changed from 20% to 40%. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Comparative Example 3: 24 200918581 Cover Example - Step υ ~ 8), but 1% polyethylene glycol di-hard acid vinegar water solvent, changed to 1% hard & acid hydrating solvent with high valence metal ions ( Provided by Sino-Japanese Synthetic Chemical Co., Ltd.) 2) The extruder current, colloid fraction and surface tension values are shown in the table. Private, residual, and retention. Comparative Example 4: 1) Repeat steps 1) to 8) of Example 1. The agent is changed into a pure water solvent. 1% polyethylene glycol di-hard acetate aqueous solution extruder current, colloidal dispersion and surface tension values, as shown in Table 1, , 'set, residual early body, retention force comparison example 5: 1) repeated Example 1 step 丨) ^ iB l〇 / Mx _ agent, changed to not add any dissolved 丨 ° ° also ethylene glycol distearate water soluble fine powder amount, residual monomer, retention 2) its extrusion current , colloidal dispersion and surface tension values, as shown in Table 1. 3 26200918581 Table 1 Extruder Current (A) Colloid Dispersion Time (sec) Retention (g/g) Surface Tension (dyne/cm2) Fine Powder (8) Residual Monomer (ppm) Example 39 18.4 41.2 65.6 2. 02 340 Example 38 15.6 40.6 59.4 1.68 306 Example 39 19.2 41.4 66.7 2.12 356 Example 40 15.7 42.0 63.3 1.89 412 Example 39 13.4 41.4 57.6 1.54 387 Example 41 16.9 42.3 65.4 2.03 442 Example 38 19.7 41.8 62.3 2. 32 387 Example 38 17.4 41.1 56.3 1.88 334 Example 39 20.4 40.9 64.1 2.98 398 Comparative Example 37 13.6 41.6 44.3 1.44 344 Comparative Example 48 20.3 39.4 49.3 3. 54 367 Comparative Example 39 18.6 36.8 63.1 1.87 382 Comparative Example 73 38.9 41.6 70.2 5.12 612 Comparative Example 58 33.2 40.9 70.7 4.67 563 26 27 200918581 [Simple description of the diagram] [Explanation of main component symbols] 27