201141918 六、發明說明： 【發明所屬之技術領域】 本發明是關於乾燥纖維素凝膠，尤其是關於吸水性優 異的乾燥纖維素凝膠及其製造方法。 【先前技術】 以往有提出一種利用放射線照射的自交聯型烷基纖維 素衍生物的製造方法（專利文獻1〜2)。 專利文獻1記載的方法’是朝相對於烷基纖維素衍生 物100重量部包含水5〜2000重量部的混合物，照射r線換 算0.1 kGy的放射線然後使其乾燥。利用在烷基纖維素衍生 物單體雖然會因放射線照射而分解，而在水的存在下，會 產生羥基而產生自交聯反應。 在專利文獻2記載的方法，是本發明者們對專利文獻】 記載的方法的改良，提出了爲了解決利用放射線照射而自 交聯後的乾燥步驟〜成型步驟的繁雜，使放射線照射後的 凝膠粒子化而使其乾燥的方法。在專利文獻2記載的方法 ，在將纖維素粉末與水以擠壓機混練之後，照射來自鈷60 的r線、X線、電子束使其進行交聯而成爲纖維素凝膠， 然後將其裁切、粒子化然後使其乾燥。可是’本發明者們 在反覆實驗後’ 了解所得到的纖維素凝膠的吸水率並不相 同，而無法量產。 [先前專利文獻] 201141918 [專利文獻] [專利文獻1 ] 曰本特開2001-2703號公報 [專利文獻2 ] 日本特開2009-179706號公報 【發明內容】 [發明欲解決的課題] 在專利文獻1及2記載的方法所得到的乾燥纖維素凝膠 ，會有吸水力較低，且吸水力不平均，而無法量產化的問 題。因此，本發明的目的，是要提供吸水性優異的乾燥纖 維素凝膠、以及將該乾燥纖維素凝膠量產化的製造方法。 [用以解決課題的手段] 本發明者們，爲了解決課題而硏究的結果，査明了吸 水性的降低以及不平均的原因，是放射線照射時的烷基纖 維素衍生物一水混合物的不均勻性以及氣泡的存在，而完 成了本發明。 也就是說，藉由本發明，提供一種乾燥纖維素凝膠的 製造方法，是包含有：在有加入水的混練機，一邊將霧狀 的水進行噴霧，一邊添加15〜25wt %的纖維素粉末之後， 在真空環境下將水與纖維素粉末進行混練，而得到糊狀的 纖維素混練物的步驟、對該纖維素混練物照射電子束來獲 得交聯纖維素凝膠的步驟、以及使該交聯纖維素凝膠乾燥201141918 VI. Description of the Invention: [Technical Field] The present invention relates to a dry cellulose gel, and more particularly to a dry cellulose gel excellent in water absorption and a method for producing the same. [Prior Art] A method for producing a self-crosslinking type alkyl cellulose derivative by radiation irradiation has been proposed (Patent Documents 1 to 2). The method described in Patent Document 1 is a mixture containing 5 to 2000 parts by weight of water with respect to 100 parts by weight of the alkylcellulose derivative, and irradiated with an x-ray to convert 0.1 kGy of radiation and then dried. The alkyl cellulose derivative monomer is decomposed by radiation irradiation, and in the presence of water, a hydroxyl group is generated to generate a self-crosslinking reaction. In the method described in the patent document 2, the inventors of the present invention have improved the method described in the patent document, and have proposed to solve the problem of the drying step to the molding step after self-crosslinking by radiation irradiation, and to condense after radiation irradiation. A method in which the gel is particleized to dry it. In the method described in Patent Document 2, after the cellulose powder and water are kneaded in an extruder, the r-ray, the X-ray, and the electron beam from the cobalt 60 are irradiated to be crosslinked to form a cellulose gel, and then the cellulose gel is used. Cut, particleize and then dry. However, the present inventors have learned that after the repeated experiments, the water absorption rate of the obtained cellulose gel is not the same, and it is impossible to mass-produce. [PATENT DOCUMENT] [Patent Document 1] [Patent Document 1] JP-A-2001-2703 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2009-179706 [Summary of the Invention] [Problems to be Solved by the Invention] The dried cellulose gel obtained by the methods described in Documents 1 and 2 has a problem that the water absorption is low and the water absorption is uneven, and mass production cannot be achieved. Accordingly, an object of the present invention is to provide a dried cellulose gel having excellent water absorbability and a method for producing the dried cellulose gel. [Means for Solving the Problem] The inventors of the present invention have found that the decrease in water absorbability and the cause of unevenness are the result of the investigation of the problem, and it is not the mixture of the alkyl cellulose derivative and the water at the time of radiation irradiation. The present invention has been completed by uniformity and the presence of bubbles. That is, the present invention provides a method for producing a dried cellulose gel comprising: adding 15 to 25 wt% of cellulose powder while spraying a mist of water in a kneader to which water is added Thereafter, the step of kneading the water with the cellulose powder in a vacuum environment to obtain a paste-like cellulose kneaded product, irradiating the cellulose kneaded material with an electron beam to obtain a crosslinked cellulose gel, and Crosslinked cellulose gel drying
-6 - 201141918 ，而得到乾燥纖維素凝膠的步驟。 在本發明，藉由在真空環境下進行水與纖維素粉末的 混練，從混練過的糊狀的纖維素混練物中將氣泡趕出，則 能解決：當電子束照射時因爲氣泡的存在導致交聯程度的 不均勻。 先將水加入混練機，當導入纖維素粉末時，纖維素粉 末揚起，不只是無法導入預定量的纖維素粉末，且當在真 空環境下進行混練時，會真空吸引纖維素粉末。本發明， 爲了可進行在真空環境下的混練，當將纖維素粉末朝混練 機導入時，將霧狀的水噴霧到纖維素粉末上，而能防止纖 維素粉末揚起，而且能使水與纖維素粉末的潤濕性提升。 粉末纖維素，是羧基烷基纖維素較佳，而羧基甲基纖 維素鈉最佳。 羧基烷基纖維素會與氯產生反應，所以直接導入到混 練機的水以及噴霧的水，是不含有氯或醇的水較佳，最好 是經脫氯及脫氣處理的水。 真空混練時的水與粉末纖維素，調整成粉末纖維素爲 1 5〜25 wt %的含有量。粉末纖維素的含有量太多的話，則 不能進行電子束照射所進行的交聯反應，會優先進行纖維 素的分解反應。相反的，如果粉末纖維素的含有量太少的 話，爲了產生電子束照射所進行的交聯反應，變得需要大 量的電子束照射而成本會變高。 在本發明，藉由對纖維素混練物使用電子束，則能緊 急以短時間的照射使其交聯。上述電子束的照射量雖然是 201141918 因應粉末纖維素的含有量而不同，而在粉末纖維素15〜 25wt%的範圍是9〜16 kGy較佳。電子束照射量較多的話， 則交聯構造的網目會變小，電子束照射量較少的話，交聯 構造的網目會變大。在上述範圍內的話則可以提高乾燥纖 維素凝膠的吸水率。 本發明的製造方法，又包含有：在真空環境下將上述 纖維素混練物成型的步驟。藉由在真空環境下成型，則能 避免：在含有水的纖維素混練物產生多餘的氣泡。 藉由上述本發明的製造方法，可得到：24小時吸水的 凝膠除以吸水前的初期重量所求出的吸水倍率爲1 50以上 的乾燥纖維素凝膠。 藉由本發明，是用來實施本發明的乾燥纖維素凝膠的 製造方法的裝置，提供乾燥纖維素凝膠的製造裝置，具備 有： 真空混練裝置，具備有：具備攪拌葉片的混練鍋、具 備沿著內周部設置的流水管以及在該流水管等間隔設置的 水噴霧部的蓋子、以及真空吸引單元； 電子束照射裝置，具備有：將從該真空混練裝置取出 的纖維素混練物予以搬運的輸送帶、電子束照射部、及電 子束源： 乾燥裝置，具備有：將從該電子束照射裝置取出的纖 維素凝膠予以搬運的通氣性的輸送帶、從該輸送帶上方輸 送熱風的循環風扇。 201141918 [發明效果] 藉由使用本發明的製造方法以及用來實施該製造方法 的製造裝置，能避免吸水率不平均，可讓吸水性優異的乾 燥纖維素凝膠量產化。 【實施方式】 參考圖面，來說明本發明的製造方法及裝置。 首先’參考第2圖〜第5圖來說明本發明的製造裝置。 如第2圖所示，本發明的製造裝置，是具備有：真空 混練裝置10、電子束照射裝置100、乾燥裝置200。 真空混練裝置10，如第3圖所示，是具備有：混練鍋 20、蓋子30、使蓋子30升降的升降缸40、油壓真空單元50 、混練用馬達60。蓋子30，是具備有：攪拌葉片31、原料 投入口 32、在較原料投入口 32更上方而設置於蓋內周部的 流水管34、以及等間隔設置於流水管34的水噴霧部33。當 使用時，藉由升降缸40讓蓋子30下降至混練鍋20的位置。 在使蓋子30與混練鍋20接合成密封狀態之後，藉由油壓真 空單元50將混練鍋20內部進行真空吸引，藉由混練用馬達 60來驅動攪拌葉片31。 電子束照射裝置100，如第4圖所示，具備有：將真空 混練裝置10所調製的纖維素混練物進行搬運的輸送帶110 、將電子束照射於纖維素混練物的電子束照射部1 20、及 電子束源130。電子束照射部120及電子束源130，收容於 用來防止電子束洩漏到外部的遮蔽包圍體140。在遮蔽包 -9 - 201141918 圍體140內部，配設有：用來給予所需要的電子束照射量 的充分長度的輸送帶110。例如，也可將輸送帶11〇作爲直 線路線、彎曲路線、折返路線、或複數段的立體路線。 本發明的製造裝置，也可具備有：用來將以電子束照 射裝置1 00經過交聯處理的交聯纖維素凝膠成形爲容易乾 燥處理的形狀的擠壓裝置150。擠壓裝置15〇，如第5圖所 示，具備有：用來接受交聯纖維素凝膠的料斗152、設置 於料斗152下部用來裁切交聯纖維素凝膠的切片機154、將 所裁切的交聯纖維素凝膠成形爲球狀而擠壓出的擠壓部 156及排出口 158。擠壓部156，具備有：圓筒狀主體156a 、以及可旋轉地設置於圓筒狀主體的內部的擠壓用螺旋部 15 6b。在排出口 158，設置有板狀構件158a，該板狀構件 158a具有用來將交聯纖維素凝膠擠壓成球狀的圓形的孔部 。擠壓用的螺旋部15 6b的前半部分的進料間距P1，爲後半 部分的進料間距P2的大約一半，是爲了讓前端部側的擠壓 壓力增加。在螺旋部156b的前端部與模具156c之間，形成 有：後側較寬狀的空間部156d。在模具l56c形成有用來粒 子化的多數個成形孔156e，各成形孔156e雖然沒有圖示， 而是成爲從螺旋部156b側的後面到成形孔156e的厚度方向 的中間位置，爲稍微前端較細狀的錐狀孔’從其中間位置 起到模具156c的前面爲止的直徑爲一定的直孔。成形孔 156e的直徑是因應乾燥凝膠的用途而有所不同’具有所需 要的直徑的模具156c爲可交換地安裝於擠壓裝置。 乾燥裝置200，如第6圖所示’具備有：接受被擠壓裝-6 - 201141918 , and the step of obtaining a dry cellulose gel. In the present invention, by performing the kneading of the water and the cellulose powder in a vacuum environment, the bubbles are ejected from the kneaded paste-like cellulose kneaded material, and the solution can be solved: when the electron beam is irradiated, the bubble is present. The degree of cross-linking is not uniform. Water is first added to the kneading machine. When the cellulose powder is introduced, the cellulose powder is raised, not only because a predetermined amount of cellulose powder cannot be introduced, but also when the kneading is carried out in a vacuum environment, the cellulose powder is vacuum-attracted. In the present invention, in order to carry out kneading in a vacuum environment, when the cellulose powder is introduced into the kneading machine, the misty water is sprayed onto the cellulose powder, thereby preventing the cellulose powder from rising and enabling the water to be The wettability of the cellulose powder is improved. The powdered cellulose is preferably a carboxyalkyl cellulose, and the carboxymethyl cellulose sodium is most preferred. Since the carboxyalkyl cellulose reacts with chlorine, the water directly introduced into the mixer and the water sprayed are preferably water containing no chlorine or alcohol, and preferably dechlorination and degassing. The water and powdered cellulose during vacuum mixing were adjusted to a powdered cellulose content of 15 to 25 wt%. When the content of the powdered cellulose is too large, the crosslinking reaction by the electron beam irradiation cannot be performed, and the decomposition reaction of the cellulose is preferentially carried out. On the other hand, if the content of the powdered cellulose is too small, a large amount of electron beam irradiation is required in order to generate a cross-linking reaction by electron beam irradiation, and the cost becomes high. In the present invention, by using an electron beam for a cellulose kneaded product, it is possible to crosslink it in a short time by irradiation. The irradiation amount of the above electron beam differs depending on the content of the powdered cellulose in 201141918, and is preferably in the range of 15 to 25 wt% of the powdered cellulose in the range of 9 to 16 kGy. When the amount of electron beam irradiation is large, the mesh of the crosslinked structure becomes small, and if the amount of electron beam irradiation is small, the mesh of the crosslinked structure becomes large. Within the above range, the water absorption of the dried cellulose gel can be improved. The production method of the present invention further comprises the step of molding the above-mentioned cellulose kneaded material in a vacuum environment. By molding in a vacuum environment, it is possible to avoid excessive bubbles in the cellulose kneaded material containing water. According to the production method of the present invention, a dry cellulose gel having a water absorption ratio of 150 or more obtained by dividing the gel which absorbs water for 24 hours by the initial weight before water absorption can be obtained. According to the present invention, there is provided an apparatus for producing a method for producing a dried cellulose gel of the present invention, comprising: a vacuum kneading device comprising: a kneading pot having a stirring blade; a water flow pipe provided along the inner peripheral portion, a cover of the water spray portion provided at equal intervals in the water flow pipe, and a vacuum suction unit; and the electron beam irradiation device includes: the cellulose kneaded material taken out from the vacuum kneading device Conveyor belt, electron beam irradiation unit, and electron beam source: The drying apparatus includes a ventilated conveyor belt that transports the cellulose gel taken out from the electron beam irradiation apparatus, and conveys hot air from above the conveyor belt Circulating fan. [Effect of the Invention] By using the production method of the present invention and the production apparatus for carrying out the production method, it is possible to prevent the water absorption rate from being uneven, and to mass-produce the dried cellulose gel having excellent water absorbability. [Embodiment] The manufacturing method and apparatus of the present invention will be described with reference to the drawings. First, the manufacturing apparatus of the present invention will be described with reference to Figs. 2 to 5. As shown in Fig. 2, the manufacturing apparatus of the present invention includes a vacuum kneading device 10, an electron beam irradiation device 100, and a drying device 200. As shown in Fig. 3, the vacuum kneading device 10 includes a kneading pot 20, a lid 30, a lift cylinder 40 for lifting and lowering the lid 30, a hydraulic vacuum unit 50, and a kneading motor 60. The lid 30 includes a stirring blade 31, a raw material inlet 32, a water conduit 34 provided on the inner peripheral portion of the lid above the material inlet port 32, and a water spray portion 33 which is provided at equal intervals in the water conduit 34. When in use, the lid 30 is lowered by the lift cylinder 40 to the position of the kneading pot 20. After the lid 30 and the kneading pot 20 are joined to each other in a sealed state, the inside of the kneading pot 20 is vacuum-sucked by the hydraulic pressure unit 50, and the stirring blade 31 is driven by the kneading motor 60. As shown in FIG. 4, the electron beam irradiation apparatus 100 includes a conveyor belt 110 that conveys the cellulose kneaded material prepared by the vacuum kneading device 10, and an electron beam irradiation unit that irradiates the electron beam to the cellulose kneaded material. 20. And an electron beam source 130. The electron beam irradiation unit 120 and the electron beam source 130 are housed in the shielding enclosure 140 for preventing the electron beam from leaking to the outside. Inside the enclosure -9 - 201141918, a wide length of conveyor belt 110 for imparting the desired amount of electron beam exposure is provided. For example, the conveyor belt 11 can also be used as a straight line, a curved route, a return route, or a plurality of three-dimensional routes. The manufacturing apparatus of the present invention may be provided with a pressing device 150 for forming a crosslinked cellulose gel subjected to cross-linking treatment by the electron beam irradiation device 100 to a shape which is easy to dry. The squeezing device 15A, as shown in Fig. 5, is provided with a hopper 152 for receiving the crosslinked cellulose gel, a dicing machine 154 disposed at the lower portion of the hopper 152 for cutting the crosslinked cellulose gel, and The cut crosslinked cellulose gel is formed into a spherical shape and extruded extruded portion 156 and discharge port 158. The pressing portion 156 includes a cylindrical body 156a and a pressing spiral portion 156b rotatably provided inside the cylindrical body. At the discharge port 158, a plate-like member 158a having a circular hole portion for extruding the crosslinked cellulose gel into a spherical shape is provided. The feed pitch P1 of the first half of the spiral portion 15b for extrusion is about half of the feed pitch P2 of the second half in order to increase the pressing pressure on the tip end side. Between the front end portion of the spiral portion 156b and the mold 156c, a space portion 156d having a wide rear side is formed. A plurality of molding holes 156e for particle formation are formed in the mold l56c, and each of the molding holes 156e is an intermediate position in the thickness direction from the rear side of the spiral portion 156b side to the longitudinal direction of the molding hole 156e, although not shown. The tapered hole of the shape is a straight hole having a constant diameter from the intermediate position to the front surface of the mold 156c. The diameter of the shaped hole 156e is different depending on the use of the dried gel. The mold 156c having the desired diameter is exchangeably mounted to the extrusion device. The drying device 200, as shown in Fig. 6, has: accepts the squeezed device
S -10- 201141918 置150成形爲粒子狀的交聯纖維素凝膠而將其進行搬運的 通氣性的輸送帶210、將熱風從輸送帶210上方進行送風的 循環風扇220 '排氣管道23 0、以及將乾燥後的交聯纖維素 凝膠取出的出口 2 40。通氣性的輸送帶210，用衝孔金屬製 或篩網金屬製都可以，只要是能讓來自循環風扇220的熱 風通氣的構造即可。排氣管道230，設置在較循環風扇220 更上方處，當熱風接觸交聯纖維素凝膠時，從乾燥裝置 2〇〇將包含從交聯纖維素凝膠去除的水分的排氣予以去除 。設置有複數個循環風扇，因應交聯纖維素凝膠的乾燥程 度來個別調節溫度較佳。 接著，參考第1圖，來說明本發明的製造步驟。S1， 是將纖維素粉末與水在真空環境下進行混練的真空混練步 驟，如第3圖所示在真空混練裝置10內進行較佳。S2，是 對纖維素混練物照射電子束的電子束照射步驟，如第4圖 所示在電子束照射裝置1〇〇內進行較佳。S3是使交聯纖維 素凝膠乾燥的乾燥步驟，如第5圖所示在乾燥裝置200內進 行較佳。 < S 1 > 預先將水導入真空混練裝置10的混練鍋20，接著，將 粉末纖維素從原料導入口 32導入。當將粉末纖維素導入到 混練鍋20時，從設置於蓋子30的水噴霧部33噴霧出霧狀的 水，避免粉末纖維素揚起，使粉末纖維素濕潤化’提升混 練鍋20內與水的潤濕性。 在將水及粉末纖維素導入混練鍋2〇之後’使蓋子30下 -11 - 201141918 降，藉由油壓真空單元50將混練鍋20內部進行真空吸引， 藉由混練用馬達6 0來驅動攪拌葉片3 1。本發明的真空狀態 ，是藉由真空泵浦施加5 00Pa〜0.13Pa的範圍，更好是130 Pa〜IPa的範圍的壓力而能達成，混練時間爲30〜60分鐘 之間，較佳爲40〜50分鐘之間。 接著，將已真空混練的纖維素混練物成形爲適合電子 束照射的尺寸及形狀。成形步驟用真空加壓機、真空擠壓 機等進行都可以，而也可以將真空狀態的混練鍋20加壓， 而從下部的擠壓口將纖維素混練物擠壓出而予以裁切。 < S2 > 成形後的纖維素混練物，放置於輸送帶1 1 0，搬運到 電子束照射裝置100內，在電子束照射部120接受來自電子 束源130的電子束的照射。 < S3 > 將藉由電子束照射所得到的交聯纖維素凝膠放置於輸 送帶110而搬運到擠壓裝置150的料斗152，然後將其投入 料斗152»投入於料斗152的交聯纖維素凝膠，被料斗152 下部的切片機154裁切，而供給到擠壓裝置150主體內。供 給到擠壓裝置150主體的擠壓部156的交聯纖維素凝膠，被 擠壓用螺旋部15 6b於圓筒狀主體156a朝向排出口 158擠壓 出，從排出口 158的板狀構件l58a的圓形的孔部擠壓出而 成爲球狀排出。此時，交聯纖維素凝膠，被旋轉的螺旋部 156b弄碎，一邊進行混練一邊將其朝圓筒狀主體156a的前 方推擠。由於螺旋部156b的前半部分的進料間距P1爲後半S -10- 201141918 An air-permeable conveyor belt 210 that is formed into a particulate cross-linked cellulose gel and conveyed 150, and a circulation fan 220 that exhausts hot air from above the conveyor belt 210, an exhaust pipe 23 0 And an outlet 2 40 from which the dried crosslinked cellulosic gel is removed. The air-permeable conveyor belt 210 may be made of a punched metal or a mesh metal, and may be any structure that allows the air from the circulation fan 220 to be ventilated. The exhaust duct 230 is disposed above the circulation fan 220, and when the hot air contacts the crosslinked cellulose gel, the exhaust gas containing the moisture removed from the crosslinked cellulose gel is removed from the drying device. A plurality of circulating fans are provided, and the temperature is individually adjusted in accordance with the degree of drying of the crosslinked cellulose gel. Next, the manufacturing steps of the present invention will be described with reference to Fig. 1. S1 is a vacuum kneading step in which the cellulose powder and water are kneaded in a vacuum environment, and is preferably carried out in the vacuum kneading device 10 as shown in Fig. 3. S2 is an electron beam irradiation step of irradiating an electron beam to the cellulose kneaded material, and is preferably carried out in the electron beam irradiation apparatus 1 as shown in Fig. 4. S3 is a drying step for drying the crosslinked cellulosic gel, and is preferably carried out in the drying apparatus 200 as shown in Fig. 5. <S 1 > Water is introduced into the kneading pot 20 of the vacuum kneading device 10 in advance, and then the powdered cellulose is introduced from the raw material introduction port 32. When the powdered cellulose is introduced into the kneading pot 20, the misty water is sprayed from the water spray portion 33 provided in the lid 30 to prevent the powdered cellulose from rising and the powdered cellulose to be humidified. Wettability. After the water and the powdered cellulose are introduced into the kneading pot 2', the lid 30 is lowered -11 - 201141918, and the inside of the kneading pot 20 is vacuum-sucked by the hydraulic vacuum unit 50, and the mixing is driven by the kneading motor 60. Blade 3 1. The vacuum state of the present invention can be achieved by applying a vacuum pumping range of 500 Pa to 0.13 Pa, more preferably 130 Pa to IPa, and the kneading time is between 30 and 60 minutes, preferably 40 to 40. Between 50 minutes. Next, the vacuum kneaded cellulose kneaded material is formed into a size and shape suitable for electron beam irradiation. The molding step may be carried out by a vacuum press, a vacuum extruder or the like, and the kneading pot 20 in a vacuum state may be pressurized, and the cellulose kneaded material may be extruded from the lower extrusion port and cut. < S2 > The formed cellulose kneaded product is placed on the conveyor belt 110 and transported to the electron beam irradiation apparatus 100, and the electron beam irradiation unit 120 receives the electron beam from the electron beam source 130. <S3 > The crosslinked cellulose gel obtained by electron beam irradiation is placed on the conveyor belt 110 and transported to the hopper 152 of the extrusion device 150, and then introduced into the hopper 152» into the cross-link of the hopper 152. The cellulose gel is cut by the slicer 154 at the lower portion of the hopper 152 and supplied to the body of the extrusion device 150. The crosslinked cellulose gel supplied to the pressing portion 156 of the main body of the pressing device 150 is extruded toward the discharge port 158 by the pressing screw portion 16 6b from the cylindrical body 156a, and the plate member from the discharge port 158 The circular hole portion of l58a is extruded and becomes a spherical discharge. At this time, the crosslinked cellulose gel is crushed by the rotating spiral portion 156b, and is pushed toward the front of the cylindrical body 156a while being kneaded. Since the feed pitch P1 of the front half of the spiral portion 156b is the second half
-12- 201141918 部分的進料間距P 2的大約一半’所以對於交聯纖維素凝膠 的混練物的推擠壓力會漸漸變高，以預定的擠壓力，從模 具156c的各成形孔156e將交聯纖維素凝膠擠壓出。當該擠 壓時’在交聯纖維素凝膠的水分含有率或黏彈強度等的關 係，交聯纖維素凝膠不是細長地連續，而是將其短短地裁 切而擠壓出成爲粒子狀凝膠。 成爲球狀而排出的交聯纖維素凝膠，以乾燥裝置2 00 的通氣性的輸送帶210接受，搬運到乾燥裝置200內。球狀 的交聯纖維素凝膠，在乾燥裝置200內的各乾燥室暴露於 60〜90°C的預定溫度的溫風，成爲乾燥交聯纖維素凝膠， 從出口 240取出。此時，熱風從通氣性輸送帶210的上方朝 向下方，以及從下方朝上方反覆流通，所以粒子狀交聯纖 維素凝膠，一邊低速移動一邊乾燥至剩餘水分率10 wt%程 度。 [實施例] 以下，參考實施例及比較例來更詳細說明本發明。 [實施例1] 作爲纖維素粉末，使用羧基烷基纖維素鈉，使含有量 變化成1 5wt%〜30wt%，使電子束照射量變化成7kGy〜 16kGy，使用第2圖所示的製造裝匱，製造出乾燥交聯纖維 素凝膠。也就是說，將10.5L〜12.75L的水注入到混練鍋 ’一邊將霧狀的水噴霧於羧基烷基纖維素鈉粉末2.25〜 -13- 201141918 4.5 kg—邊進行添加，然後關閉混練鍋的蓋子進行真空吸 引40分鐘期間，進行真空混練。接著，將已真空混練的纖 維素混練物移到電子束照射裝置，照射預定的電子束而使 其交聯，而獲得交聯纖維素凝膠。接著，將交聯纖維素凝 膠移到擠壓裝置而成形爲球狀之後，將其搬運到乾燥裝置 使其乾燥，而作成乾燥纖維素凝膠。 <吸水倍率> 針對各試料，24小時吸水的凝膠除以其吸水前的初期 重量來求出吸水倍率。在表1顯示製造條件及測定結果。 在第7圖（a)〜（c)，將表1的粉末纖維素含有量與電子 束照射量的關係以粉末纖維素的種類區別而作成長條圖。 根據第7圖，雖然原料的纖維素粉未的種類不同，而 纖維素粉末的含有量越增加則電子束的照射量越減少，爲 了達成高吸水倍率而組合最適當的纖維素粉末的含有量與 電子束照射量。 表1中「2200」是表示「Daicel Finechem公司（日本 )製羧基甲基纖維素鈉CMC2200」’ 「1 3 50」是表示「-12- 201141918 Part of the feed pitch P 2 is about half' so the pushing force for the kneaded material of the crosslinked cellulose gel will gradually become higher, with the predetermined pressing force, from the forming holes of the mold 156c 156e extrudes the crosslinked cellulose gel. When the extrusion is carried out, 'the relationship between the moisture content of the crosslinked cellulose gel or the viscoelasticity, etc., the crosslinked cellulose gel is not slenderly continuous, but is cut shortly and extruded into particles. Gel. The crosslinked cellulose gel discharged in a spherical shape is received by the air-permeable conveyor belt 210 of the drying device 200 and transported into the drying device 200. The spherical crosslinked cellulose gel is exposed to a predetermined temperature of 60 to 90 ° C in each drying chamber in the drying apparatus 200 to form a dry crosslinked cellulose gel, which is taken out from the outlet 240. At this time, the hot air flows downward from the upper side of the air-permeable conveyor belt 210 and upwards from the lower side. Therefore, the particulate cross-linked cellulose gel is dried while moving at a low speed to a residual moisture content of 10 wt%. [Examples] Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. [Example 1] As the cellulose powder, carboxyalkyl cellulose sodium was used, and the content was changed to 15 wt% to 30 wt%, and the electron beam irradiation amount was changed to 7 kGy to 16 kGy, and the manufacturing apparatus shown in Fig. 2 was used.匮, a dry crosslinked cellulose gel was produced. That is, 10.5L~12.75L of water is injected into the kneading pot' while spraying the misty water on the carboxyalkyl cellulose sodium powder 2.25~13-201141918 4.5 kg-, and then the kneading pot is closed. The vacuum was kneaded during the vacuum suction for 40 minutes. Next, the vacuum kneaded cellulose kneaded material is transferred to an electron beam irradiation apparatus, and a predetermined electron beam is irradiated to crosslink it to obtain a crosslinked cellulose gel. Next, the crosslinked cellulose gel was transferred to a pressing device to be formed into a spherical shape, and then transferred to a drying device to be dried to prepare a dried cellulose gel. <Water Absorption Ratio> For each sample, the water absorption ratio was determined by dividing the gel which absorbed water for 24 hours by the initial weight before water absorption. Table 1 shows the manufacturing conditions and measurement results. In Fig. 7 (a) to (c), the relationship between the content of the powdered cellulose in Table 1 and the amount of electron beam irradiation is differentiated by the type of powdered cellulose to form a growth bar graph. According to the seventh aspect, the amount of the cellulose powder of the raw material is different, and the amount of the cellulose powder is increased, the amount of irradiation of the electron beam is decreased, and the optimum amount of the cellulose powder is combined in order to achieve a high water absorption ratio. With the amount of electron beam exposure. "2200" in Table 1 means "Daicel Finechem (Japan) carboxymethylcellulose sodium CMC2200"' "1 3 50" means "
Daicel Finechem公司（日本）製羧基甲基纖維素鈉 CMC1350」，「350」是表示「日本製紙公司製（日本） 製羧基甲基纖維素鈉F350HC-4」。 表1中，評價項目「◎」是具有3 5 0倍以上的吸水倍率 ，是表示適合特別需要吸水能力的用途，「〇」是具有 150〜35 0倍的吸水倍率，是表示適合平常的乾燥凝膠的用 -14- 201141918 途，「△」是表示具有90〜150倍的吸水倍率。 m η 測試資料 公司 室 究 硏 S m 業曰曰 作射定 練照測 混束水 子吸 電 曰 定 11 11 11 ο ο ο 0 材料編號 材料比(％) 照射量(kGy) 吸水倍率g/lg 吸水時間 評價 備註 2200 30 7 76.91 24 2200 30 8 68.76 24 2200 25 8 110.33 24 Δ 保水性良好 2200 25 9 93.52 24 Δ 保水性良好 2200 20 9 164.99 24 〇 凝膠強度：高 2200 20 10 185.50 24 〇 凝膠強度：高 2200 20 11 186.44 24 〇 凝膠強度：高 350 25 13 102.12 24 Δ 保水性良好 350 25 14 95.30 24 Δ 保水性良好 350 20 14 205.95 24 〇 凝膠強度：高 350 20 15 209.93 24 〇 凝膠強度：高 350 15 15 363.77 24 ◎ 吸水速度：快 350 15 16 447.87 24 ◎ 吸水速度：快 350 10 16 不能測定 24 350 10 16 不能測定 1350 30 11 83.95 24 1350 30 12 73.61 24 1350 25 12 116.15 24 Δ 保水性良好 1350 25 13 107.24 24 △ 保水性良好 1350 20 13 286.61 24 〇 凝膠強度：高 1350 20 14 238.71 24 〇 凝膠強度：高 1350 15 14 327.77 24 〇 凝膠強度：高 1350 15 15 399.25 24 ◎ 吸水速度：快 1350 15 16 293.06 24 〇 凝膠強度：高 -15- 201141918 <乾燥凝膠的評價> 材料編號2200，照射後的未加工狀態的凝膠雖然較堅 固，而作爲乾燥凝膠的吸水力在三種材料中較差。 材料編號1 350，照射後的未加工狀態的凝膠，與2200 號比較起來較柔軟。三種材料之中，乾燥凝膠的吸水力容 易有不平均的情形。 材料編號3 50，照射後的未加工狀態的凝膠及乾燥凝 膠，都顯示穩定的高吸水倍率。 <乾燥凝膠的用途> 表1中得到「©j評價的乾燥凝膠，適合用於：需要 特別高的吸液性能的用途，例如，紙尿布或生理用品、用 於水災措施的土袋的代替品、沙漠綠化用保水材等。 表1中得到「△」的評價的乾燥凝膠，兼具柔軟性及 強度，分解較慢，適合作爲植物的保水材。 <膨潤度> 將本發明的乾燥纖維素凝膠1 g浸漬1 8小時於井水 1 600g，測定膨潤前後的質量，計算出膨潤度（=浸漬後 質量/浸漬前質量）。在表2顯示代表例的測定結果。 [表 2 ] , 表2 材料編號-試料 NO. 2200-175 1350—15 350- 15 膨潤度 290 360 430 -16- 201141918 [比較例1 ] 在大氣環境中進行混練以外，與實施例1同樣得到乾 燥纖維素凝膠，測定吸水倍率及膨潤度。在表3及表4顯示 結果。雖然吸水倍率的評價爲^ △」，而缺乏保水性，在 夏天晚上等等超過30 °C的高溫及高濕度下，也會在一個晚 上分解。 [表3] 材料編號 材料比(％) 照射量(kGy) 吸水倍率g/lg 供水時間 評價 CMC1380 20 10 136.2 24 Δ CMC2200 20 10 145.6 24 Δ CMC2260 20 10 140.6 24 Δ [表4] 材料編號 材料比(％) 照射量(kGy) 膨潤度 CMC1380 20 10 75.8 CMC1380 20 15 63.9 CMC2200 20 10 60.7 CMC2200 20 15 89.2 CMC2260 20 10 85.9 CMC2260 20 15 78.2 如表3及表4所示，可看出在大氣環境中混練的情況的 乾燥纖維素凝膠，與本發明的乾燥纖維素凝膠比較起來， 在吸水倍率及膨潤度方面都較差。 【圖式簡單說明】 第1圖是顯示本發明的製造步驟的槪略流程圖。 -17- 201141918 第2圖是槪略圖示在本發明使用的製造裝置全體的說 明圖。 第3圖（A)是顯示在本發明使用的真空混練裝置的槪 略正視圖，第3圖（B )是槪略側視圖，第3圖（C )是第3 圖（B)的A-A線的剖面圖。 第4圖（a)是顯示在本發明使用的電子束照射裝置的 槪略剖面圖。 第4圖（b)是槪略俯視圖。 第5圖是顯示在本發明使用的擠壓裝置的槪略剖面圖 〇 第6圖是顯示在本發明使用的乾燥裝置的槪略剖面圖 〇 第7圖（a )是顯示實施例1的吸水倍率的測定結果的 長條圖。 第7圖（b )是顯示實施例1的吸水倍率的測定結果的 長條圖。 第7圖（c )是顯示實施例1的吸水倍率的測定結果的 長條圖。 【主要元件符號說明】 1 〇 :真空混練裝置 2〇 :混練鍋 30 :蓋子 31 :攪拌葉片 -18 - 201141918 3 2 :原料投入口 3 3 :水噴霧部 3 4 :流水管 40 :升降缸 5 0 :油壓真空單元 6 0 ·混練用馬達 100 :電子束照射裝置 1 10 :輸送帶 1 2 0 :電子束照射部 1 3 0 :電子束源 140 :遮蔽包圍體 150 :擠壓裝置 1 52 :料斗 154 :切片機 1 5 6 :擠壓部 1 5 8 :排出口 2 0 0 :乾燥裝置 210 :輸送帶 2 2 0 :循環風扇 23 0 :排氣管道 240 :出口Daicel Finechem Co., Ltd. (Japan) carboxymethylcellulose sodium CMC1350", "350" means "Carboxymethylcellulose sodium F350HC-4 manufactured by Nippon Paper Industries Co., Ltd.". In Table 1, the evaluation item "◎" is a water absorption ratio of 350 times or more, and is suitable for applications in which water absorption capacity is particularly required. "〇" is a water absorption ratio of 150 to 35 times, which means that it is suitable for usual drying. For the gel, from -14 to 201141918, "△" means that the water absorption ratio is 90 to 150 times. m η Test data company room research 硏S m industry 射 定 练 练 11 11 11 11 11 11 ο ο ο 0 Material number material ratio (%) Irradiation (kGy) Absorption capacity g / Lg water absorption time evaluation remarks 2200 30 7 76.91 24 2200 30 8 68.76 24 2200 25 8 110.33 24 Δ good water retention 2200 25 9 93.52 24 Δ good water retention 2200 20 9 164.99 24 〇 gel strength: high 2200 20 10 185.50 24 〇 Gel strength: high 2200 20 11 186.44 24 〇 Gel strength: high 350 25 13 102.12 24 Δ good water retention 350 25 14 95.30 24 Δ good water retention 350 20 14 205.95 24 〇 gel strength: high 350 20 15 209.93 24 〇 Gel strength: high 350 15 15 363.77 24 ◎ Water absorption speed: fast 350 15 16 447.87 24 ◎ Water absorption speed: fast 350 10 16 Can not be measured 24 350 10 16 Can not be measured 1350 30 11 83.95 24 1350 30 12 73.61 24 1350 25 12 116.15 24 Δ good water retention 1350 25 13 107.24 24 △ good water retention 1350 20 13 286.61 24 〇 gel strength: high 1350 20 14 238.71 24 〇 gel strength: high 1350 15 14 327.77 24 〇 Gel strength: high 1350 15 15 399.25 24 ◎ Water absorption speed: fast 1350 15 16 293.06 24 〇 Gel strength: high -15- 201141918 <Evaluation of dry gel> Material No. 2200, after irradiation The gel in the processed state is relatively strong, and the water absorption as a dry gel is poor in the three materials. Material No. 1 350, the unprocessed gel after irradiation is softer than the 2200. Among the three materials, the water absorption of the dried gel is likely to be uneven. Material No. 3 50, the unprocessed gel and the dried gel after irradiation showed stable high water absorption ratio. <Use of Dry Gel> The dry gel evaluated in "j" is obtained in Table 1, and is suitable for use in applications requiring particularly high liquid absorption properties, for example, paper diapers or physiological products, soil for flooding measures. A substitute for a bag, a water retaining material for desert greening, etc. The dried gel obtained by the evaluation of "△" in Table 1 has both flexibility and strength, and is slowly decomposed, and is suitable as a water retaining material for plants. <Swelling degree> 1 g of the dried cellulose gel of the present invention was immersed in 1 600 g of well water for 1 hour, and the mass before and after swelling was measured, and the degree of swelling (= mass after immersion/mass before immersion) was calculated. The measurement results of the representative examples are shown in Table 2. [Table 2], Table 2 Material No. - Sample No. 2200-175 1350 - 15 350 - 15 Swelling degree 290 360 430 -16-201141918 [Comparative Example 1] The same procedure as in Example 1 was carried out except that kneading was carried out in an air atmosphere. The cellulose gel was dried to measure the water absorption ratio and the degree of swelling. The results are shown in Tables 3 and 4. Although the water absorption rate is evaluated as ^ △", and the water retention is lacking, it will decompose at a late night in the summer evening and other high temperatures and high humidity exceeding 30 °C. [Table 3] Material No. Material Ratio (%) Irradiation (kGy) Water Absorption Rate g/lg Water Supply Time Evaluation CMC1380 20 10 136.2 24 Δ CMC2200 20 10 145.6 24 Δ CMC2260 20 10 140.6 24 Δ [Table 4] Material No. Material Ratio (%) Irradiation (kGy) Swelling degree CMC1380 20 10 75.8 CMC1380 20 15 63.9 CMC2200 20 10 60.7 CMC2200 20 15 89.2 CMC2260 20 10 85.9 CMC2260 20 15 78.2 As shown in Tables 3 and 4, it can be seen in the atmosphere. The dry cellulose gel in the case of kneading is inferior in water absorption ratio and swelling degree as compared with the dried cellulose gel of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic flow chart showing the manufacturing steps of the present invention. -17-201141918 Fig. 2 is a schematic view showing the entire manufacturing apparatus used in the present invention. Fig. 3(A) is a schematic front elevational view showing the vacuum kneading apparatus used in the present invention, Fig. 3(B) is a schematic side view, and Fig. 3(C) is a line AA of Fig. 3(B). Sectional view. Fig. 4(a) is a schematic cross-sectional view showing the electron beam irradiation apparatus used in the present invention. Figure 4 (b) is a schematic plan view. 5 is a schematic cross-sectional view showing a pressing device used in the present invention. FIG. 6 is a schematic cross-sectional view showing a drying device used in the present invention. FIG. 7(a) is a view showing the water absorption of Example 1. A bar graph of the measurement result of the magnification. Fig. 7(b) is a bar graph showing the measurement results of the water absorption ratio of Example 1. Fig. 7(c) is a bar graph showing the measurement results of the water absorption ratio of Example 1. [Explanation of main component symbols] 1 〇: Vacuum kneading device 2〇: kneading pot 30: cover 31: mixing blade -18 - 201141918 3 2 : raw material input port 3 3 : water spray part 3 4 : water pipe 40 : lifting cylinder 5 0: hydraulic vacuum unit 60 • kneading motor 100: electron beam irradiation device 1 10: conveyor belt 1 2 0 : electron beam irradiation unit 1 3 0 : electron beam source 140: shielding enclosure 150: extrusion device 1 52 : hopper 154 : slicer 1 5 6 : pressing part 1 5 8 : discharge port 2 0 0 : drying device 210 : conveyor belt 2 2 0 : circulation fan 23 0 : exhaust duct 240 : outlet