200533810 九、發明說明： 【發明所屬之技術領域】 本發明係相關於兼具高吸放濕性及高外型安定性之吸放 濕紙及其製造方法。 【先前技術】 先前已有硏究開發有關吸放濕紙，亦即具吸放濕性的 紙，通常係使紙含有已知具吸放濕性的物質。具吸放濕性 的物質例如可採用具吸放濕性的纖維或具吸放濕性的微 粒。一般這類具吸放濕性的物質可分爲有機類和無機類， 前者的吸放濕性高，但會膨脹；後者不膨脹，但吸濕量少。 因此，不易製得兼具高吸放濕性及高外型安定性之吸放濕 紙。 使用具吸放濕性的纖維之吸放濕紙，例如由在丙烯酸系 纖維導入交聯鍵和羧基、並附加鈉離子而製得的吸放濕性 纖維、聚酯黏合劑纖維及針葉樹紙漿所組成之吸放濕紙（參 考專利文獻1 )。上述吸放濕性纖維，因可具有多量的羧 基，故吸放濕性優越，且因有交聯鍵，較一般吸放濕性纖 維更可抑制纖維的膨脹，只要使用少量即可維持吸放濕紙 的外型安定性。惟在高吸濕率的吸放濕紙使用量增加時， 其抑制膨脹效果仍不足，亦降低外型安定性。因此，此文 獻揭示的吸放濕紙中，企圖藉由使用大量的黏合劑纖維、 製成紙後進行熱加壓等提昇外型安定性。惟，使用多量的 黏合劑纖維後，因吸放濕性纖維被熔合的黏合劑纖維覆蓋 受限制，即使吸放濕性纖維具優異的吸放濕性，亦無法充 分發揮其性能，不易提昇吸放濕紙的吸放濕性。 200533810 在採用具吸放濕性的微粒之例子中，例如由矽膠或沸石 等無機顆粒、木材漿及熱熔合性纖維組成之已知吸放濕紙 等（參考專利文獻2 )。此吸放濕紙，因具吸放濕性的矽 膠或沸石等無機顆粒，即使吸濕亦不膨脹，故其外型安定 性優越。惟，如上所述，因無機顆粒的吸濕量少，故不易 製成具高吸放濕性的吸放濕紙，且因其吸濕速度緩慢，放 濕時需高溫，或重複吸放濕後易破碎而導致性能低落等缺 點，其應用領域亦受限。 專利文獻1 :特開平6-207398號公報 專利文獻2:特開平1 0-2 1 2692號公報 【發明內容】 需解決之問題 如上述般，先前的技術極不易製得兼具高吸放濕性及高 外型安定性之吸放濕紙。本發明的目的係提供一種克服相 關問題、且兼具高吸放濕性及高外型安定性之吸放濕紙、 及其製造方法。 解決問題之方法 本發明人爲達成上述目的而致力硏究的結果，發現採用 外型安定性優越的無機纖維可抑制黏合劑纖維的用量，此 外，採用具有交聯結構及酸性基的纖維作爲具吸放濕性的 物質，並變化造紙方法，在造紙後將此纖維的吸放濕性提 高至最佳狀態，藉此可製得兼具高吸放濕性及高外型安定 性之吸放濕紙而完成本發明。 亦即，藉著下面的方法可完成本發明。 (1 ) 一種吸放濕紙，其特徵爲由含有交聯結構及 200533810 1〜10mm〇l/g的酸性基、且該酸性基與大於immol/g之至少 1種選自鋰、鈉、鉀、鎂、鈣所組成組群之金屬的金屬離 子鍵結的纖維（以下亦稱爲具交聯結構及酸性基之纖維）、 無機纖維、及紙漿狀纖維組成之吸放濕紙，其使用除與上 述酸丨生基鍵結之金屬離子之外、其陽離子濃度小於1 p p m的 水’來調製含有具交聯結構及酸性基之纖維、無機纖維、 及紙漿狀纖維之水性漿再進行造紙。 (2 )如第（1 )項之吸放濕紙，其中含有交聯結構及酸 性基的纖維係在丙烯腈系纖維中，藉由肼化合物進行交聯 導入處理及藉由鹼金屬鹽進行水解處理，而形成丙烯酸吸 放濕性纖維。 (3 )如第（1 )或（2 )項之吸放濕紙，其中含有交聯結 構及酸性基的纖維係部分或全部原纖維化。 (4)如第（1 )〜（3 )項中任一項之吸放濕紙，其中紙 漿狀纖維係原纖維化之丙烯酸纖維。 (5 )如第（1 )〜（4 )項中任一項之吸放濕紙，其中在 2〇°C — 65%RH環境下的飽和吸濕率大於15% 。 (6 )如第（1 )〜（5 )項中任一項之吸放濕紙，其中熱 熔合性纖維的含量小於20重量％ 。 (7 )如第（1 )〜（6 )項中任一項之吸放濕紙，其中水 膨脹率小於5 0 % 。 (8 ) —種如第（1 )〜（7 )項中任一項的吸放濕紙之製 造方法，其特徵爲調製由含有交聯結構及1〜l〇mm〇l/g的酸 性基、且該酸性基至少大於lmmol/g之1種選自鋰、鈉、 # '鎂、鈣所組成組群之金屬的金屬離子鍵結的纖維、無200533810 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an absorbent and release wet paper having both high moisture absorption and release properties and high appearance stability, and a method for manufacturing the same. [Prior technology] Previously, research and development on absorbent and release paper, that is, absorbent and release paper, usually makes the paper contain a substance that is known to absorb and release moisture. As the substance having moisture absorption and desorption properties, for example, fibers having moisture absorption and desorption properties or fine particles having moisture absorption and desorption properties can be used. Generally, such substances with hygroscopicity can be divided into organic and inorganic types. The former has high hygroscopicity and dehydration, but it swells; the latter does not swell, but has a small amount of moisture. Therefore, it is not easy to produce a moisture absorption and release paper having both high moisture absorption and release properties and high appearance stability. Absorbent and release paper using absorbent and release fibers, for example, absorbent and release fibers produced by introducing cross-linking bonds and carboxyl groups to acrylic fibers and adding sodium ions, polyester binder fibers, and conifer pulp Composition of absorbent paper (refer to Patent Document 1). The above-mentioned moisture-absorbing and releasing fiber can have a large amount of carboxyl groups, so it has excellent moisture-absorbing and releasing properties, and because of the cross-linking bond, it can inhibit the expansion of the fiber more than ordinary moisture-absorbing and releasing fibers. The appearance stability of wet paper. However, when the amount of absorbent paper with high moisture absorption is increased, the effect of suppressing swelling is still insufficient, and the appearance stability is also reduced. Therefore, in the absorbent and release wet paper disclosed in this document, an attempt is made to improve the appearance stability by using a large amount of binder fibers and heat-pressing after making the paper. However, after using a large amount of the binder fiber, the coverage of the hygroscopic fiber by the fused binder fiber is limited. Even if the hygroscopic fiber has excellent hygroscopicity, the performance cannot be fully exerted, and it is not easy to improve the hygroscopicity. Hygroscopicity of the paper. 200533810 In the case of using microparticles with moisture absorption and release properties, for example, known moisture absorption papers composed of inorganic particles such as silica gel or zeolite, wood pulp, and heat-fusible fibers (refer to Patent Document 2). The absorbent and release paper is superior in stability due to inorganic particles such as silica gel or zeolite with absorbent and release properties, even if it absorbs moisture. However, as mentioned above, because the inorganic particles have a small amount of moisture absorption, it is not easy to make a moisture absorption and release paper with high moisture absorption and release properties, and because of its slow moisture absorption speed, high temperature is required during humidification, or repeated moisture absorption and release It is easy to be broken, resulting in low performance and other disadvantages, and its application field is also limited. Patent Document 1: Japanese Unexamined Patent Application Publication No. 6-207398 Patent Document 2: Japanese Unexamined Patent Application Publication No. 0-2 1 2692 [Summary of the Invention] Problems to be Solved As described above, the prior art is extremely difficult to produce both high moisture absorption and moisture release Absorbent and release paper with high stability and high appearance. An object of the present invention is to provide a moisture-absorbing and releasing paper which overcomes the related problems and has both high moisture absorption and release properties and high appearance stability, and a method for manufacturing the same. Solution to Problem As a result of intensive research in order to achieve the above-mentioned object, the inventors have found that the use of inorganic fibers with excellent appearance stability can suppress the amount of binder fibers. In addition, fibers with a crosslinked structure and acidic groups are used as A substance that absorbs and releases moisture, and changes the papermaking method. After papermaking, the fiber absorbs and releases moisture to an optimal state, thereby making it possible to obtain an absorbent and release that has both high moisture absorption and release and high external stability. The present invention was completed by wet paper. That is, the present invention can be completed by the following method. (1) A moisture absorption and release paper, which is characterized by containing a crosslinked structure and an acidic group of 200533810 1 to 10 mm / g, and the acidic group and at least one selected from immol / g are selected from lithium, sodium, and potassium Metal ion-bonded fibers (hereinafter also referred to as fibers with a cross-linked structure and acidic groups), inorganic fibers, and pulp-like fibers made of absorbent paper composed of magnesium, calcium, and metals. In addition to the metal ions bonded to the above-mentioned acid-based groups, water having a cation concentration of less than 1 ppm is used to prepare an aqueous pulp containing fibers having a cross-linked structure and an acidic group, inorganic fibers, and pulp-like fibers before papermaking. (2) The moisture-absorbing and releasing paper according to item (1), wherein the fiber containing the crosslinked structure and the acidic group is in acrylonitrile-based fiber, the cross-linking introduction treatment is performed by a hydrazine compound, and the hydrolysis is performed by an alkali metal salt. Treatment to form acrylic absorbent and dehumidifying fibers. (3) The absorbent paper according to item (1) or (2), wherein the fiber system containing the crosslinked structure and the acid group is partially or completely fibrillated. (4) The absorbent paper according to any one of items (1) to (3), wherein the pulp-like fibers are fibrillated acrylic fibers. (5) The moisture-absorbing and releasing paper according to any one of the items (1) to (4), wherein the saturated moisture absorption rate under the environment of 20 ° C-65% RH is greater than 15%. (6) The moisture-absorbing and releasing paper according to any one of items (1) to (5), wherein the content of the heat-fusible fiber is less than 20% by weight. (7) The absorbent paper according to any one of items (1) to (6), wherein the water expansion rate is less than 50%. (8) A method for producing a moisture-absorbing and releasing wet paper according to any one of the items (1) to (7), which is characterized by preparing an acidic group containing a crosslinked structure and 1 to 10 mm / g And the acidic group is at least 1 mmol / g of a metal ion-bonded fiber selected from the group consisting of lithium, sodium, # 'magnesium, and calcium,
200533810 機纖維、及紙漿狀纖維之水性漿，並名 式造紙法的造紙工程中，使用去除與」 屬離子後其陽離子濃度小於1 p p m的水 發明的效果 因本發明的吸放濕紙兼具高吸放濕 即使在不需抑制吸放濕性亦可維持外 供高吸放濕性。又，其因重複吸濕放 小，吸放濕紙的耐久性高，因此適用 濕元素。 實施發明之最佳型態 以下詳細說明本發明。本發明的吸® 有交聯結構及1〜10mmol/g的酸性基、 lmmol/g之至少1種選自錐、納、紳、| 金屬的金屬離子鍵結的纖維、無機纖雜 成之吸放濕紙，其使用除與上述酸性3 外、其陽離子濃度小於1 p p m的水，來言J 及酸性基之纖維、無機纖維、及紙漿形 行造紙。200533810 Aqueous pulp of machine fibers and pulp-like fibers, and in the papermaking process of the papermaking method, the use of water having a cation concentration of less than 1 ppm after the removal of ionic ions is advantageous because the absorbent paper of the present invention has both High moisture absorption and dehydration can maintain high moisture absorption and dehydration of external supply even without suppressing the moisture absorption and desorption. In addition, it is suitable for wet elements because it absorbs and wicks repeatedly and absorbs and releases paper with high durability. Best Mode for Carrying Out the Invention The present invention will be described in detail below. The adsorbent of the present invention has a crosslinked structure, an acidic group of 1 to 10 mmol / g, and at least one species of lmmol / g selected from the group consisting of cone, nano, gentle, and metal metal ion-bonded fibers and inorganic fibers. Moisture-releasing paper uses water other than the above-mentioned acidic 3 and having a cation concentration of less than 1 ppm, J and acid-based fibers, inorganic fibers, and pulp-shaped paper.
本發明中含有交聯結構及酸性基的纖 放濕紙中具有吸放濕功能的主成分。此 磺酸基。這些酸性基係在組成纖維的高 含這些酸性基的單體共聚合時導入，或 含腈基或羧酸酯的單體共聚合後進行水 又，含交聯結構和酸性基的纖維c 1〜10mm〇l/g，較理想爲3〜10mmol/g，又J 使用此水性漿之濕 述酸性基鍵結之金 〇 和高外型安定性， 之用途中，亦可提 所導致的外型變化 除濕空調機用的吸 濕紙之特徵爲由含 且該酸性基與大於 〖、鈣所組成組群之 、及紙漿狀纖維組 鍵結之金屬離子之 製含有具交聯結構 纖維之水性漿再進 維，係本發明的吸 酸性基例如羧基、 分子進行聚合時與 其爲羧基時，在與 解時導入。 3的酸性基含量爲 又 3~8mmol/g 更佳。 200533810 酸性基含量少於lmm〇l/g時，因只能與少量的後述金屬離 子鍵結，無法具有充分的吸放濕性，又超過l〇mmol/g時， 吸濕時劇烈膨脹使吸放濕紙的外型安定性不佳，或無法製 得實用上充分的纖維物性。 又，在含交聯結構和酸性基的纖維中的至少部分的酸性 基，必須與至少1種選自鋰、鈉、鉀、鎂、鈣等金屬的金 屬離子鍵結。藉著採用這些金屬離子，可具有高吸放濕性。 特別是使用鈉離子時，可具有優越的飽和吸濕量，使用鉀 φ 離子時，可具有優越的吸放濕速度。 爲使具有吸放濕性，上述金屬離子的鍵結量以總量大於 1 m m ο 1 / g較理想。亦即，若與鈉離子及紳離子鍵結時，鈉離 子及鉀離子的總量大於lmm〇l/g較理想。又，鍵結量的上 限，係可與含交聯結構和酸性基的纖維中的酸性基鍵結之 最大量。 含交聯結構和酸性基的纖維中，即使酸性基的含量大於 lmmol/g時，若上述金屬離子的鍵結量爲 1 m m ο 1 / g良P可具吸 •放濕性。惟，無法有效地利用多餘酸性基的潛在吸放濕性， 存在多量的酸性基對吸放濕性並無助益。爲要突顯其優 點，至少全部酸性基的5 0 m ο 1 %以上，最好7 0 m ο 1 %以上須 與金屬離子鍵結較理想。 與上述含交聯結構和酸性基的纖維中的酸性基鍵結的金 屬離子，因酸性基和離子鍵結，紙原料作成濃度1〜3重量 %的水性漿後，再稀釋成0.1〜1重量％如造紙工程般使用 大量的水時，此金屬離子會與存在於水中的其他陽離子進 行交換。因此，製作本發明的吸放濕紙時必須注意避免與 200533810 其他陽離子進行交換。 亦即，採用濕式造紙法時，水性漿的調製及之後的造紙 工程中，使用除與酸性基鍵結之金屬離子之外、其陽離子 濃度小於1 Ρ Ρ ΙΏ的水極重要。除與酸性基鍵結之金屬離子之 外、其陽離子濃度小於1 ppm的水’係指例如鈉離子鍵結於 酸性基時，去除鈉離子後其他陽離子的總計濃度小於丨ppm 的水。若使用這類的水，可將鍵結於酸性基的金屬離子與 其他陽離子交換抑制在最低限。相對於此，若使用含大量 φ 約50〜lOOppm陽離子的工業用水，因將發生與其他陽離子 的交換，依狀況將無法具有預期的吸放濕性。 除與酸性基鍵結之金屬離子之外、其陽離子濃度小於 1 ppm的水，較理想係使用蒸餾水或離子交換水。這類水對 吸放濕性的影響小且容易應用於工業上。又，本發明中的 離子交換水係指導電率小於3 // S/cm的水。通常，導電率 爲3 # S/cm時，全陽離子濃度爲0.6ppm。又，不限於蒸餾 水或離子交換水，亦可使用只含和鍵結於酸性基的金屬離 φ子相同的離子之水等。 本發明中含交聯結構及酸性基的纖維，因組成纖維的高 分子間係藉著交聯結構連結，故可抑制吸濕時的膨脹。此 交聯結構的種類無特別的限制，例如高分子聚合後再與 肼、乙二醇二縮水甘油醚等多官能化合物反應而形成交聯 結構。 含有交聯結構及酸性基的纖維，例如可使用在丙烯腈系 纖維中，藉由肼化合物進行交聯導入處理及藉由鹼金屬鹽 進行水解處理而形成丙烯酸吸放濕性纖維。此纖維較容易 -10- 200533810 調節交聯結構的量及竣基量，因亦可能含多量的羧基，可 符合吸放濕紙所需求的吸放濕性及外型安定性。以下，詳 細地說明此丙烯酸系吸放濕性纖維。 丙烯酸系吸放濕性纖維的原料纖維係丙烯腈系纖維，可 採用由丙烯腈單一聚合物或含大於40重量％的丙烯腈（較 理想爲大於50重量％ 、又以大於80重量％更佳）的丙烯腈 系共聚物形成之纖維。又，和丙烯腈共聚合的單體無特別 的限制，可適當地選擇。 p 丙烯腈系纖維係藉由肼化合物進行交聯導入，此處理係 由丙烯腈系纖維的腈基和肼化合物的胺基反應而形成交聯 結構，來增加纖維中的氮含量。增加的氮含量能符合交聯 的狀態，惟使用於本發明的吸放濕紙時，其量以1.0〜10重 量％較理想。 將增加的氮含量調整在1.0〜10重量％之方法，例如使上 述的丙烯腈系纖維在肼化合物濃度爲5〜60重量％的水溶 液中，於50〜120°C溫度下進行5小時之內的處理方法係較 φ理想的工業法。 其中使用的肼化合物無特別的限制，例如水合肼、和硫 酸肼、鹽酸肼、溴化氫酸肼、碳酸肼等肼衍生物、乙二胺、 硫酸脈、鹽酸脈、磷酸脈、三聚氰胺等含複數胺基之化合 物。The main component which has a moisture absorption and release function in the fiber release paper which contains a crosslinked structure and an acidic base in this invention. This sulfonic group. These acidic groups are introduced during the copolymerization of the monomers containing these acidic groups that make up the fiber, or the monomers containing nitrile groups or carboxylic acid esters are copolymerized and then water is added. The fibers containing crosslinked structures and acidic groups c 1 ~ 10mm〇l / g, more preferably 3 ~ 10mmol / g, and J uses the wet acidic bond of the water-based pulp and high appearance stability. In the application, the resulting external The characteristic of the absorbent paper used in the type-changing dehumidifying air conditioner is that it is made of water containing crosslinked structure fibers and containing acidic groups and metal ions bonded to groups larger than calcium, and pulp-like fiber groups. The re-feeding of the pulp is an acid-absorbing group of the present invention, for example, a carboxyl group, and when a molecule is polymerized with a carboxyl group, it is introduced at the time of reconciliation. The acid group content of 3 is more preferably 3 to 8 mmol / g. 200533810 When the content of acidic group is less than 1mmOl / g, it can only be bonded with a small amount of metal ions described later, and it cannot have sufficient moisture absorption and release properties. When it exceeds 10mmol / g, it will swell and make the absorption The appearance stability of the wet paper is not good, or it is impossible to obtain practically sufficient fiber physical properties. Further, at least a part of the acidic group in the fiber having a crosslinked structure and an acidic group must be bonded to at least one metal ion selected from the group consisting of lithium, sodium, potassium, magnesium, and calcium. By using these metal ions, high moisture absorption and desorption properties can be obtained. Especially when sodium ion is used, it can have superior saturated moisture absorption, and when potassium φ ion is used, it can have superior moisture absorption and release speed. In order to have moisture absorption and release properties, it is preferable that the total amount of bonding of the metal ions is greater than 1 m m ο 1 / g. That is, when it is bonded to sodium ions and gentle ions, the total amount of sodium ions and potassium ions is preferably greater than 1 mm / g. The upper limit of the bonding amount is the maximum amount that can be bonded to the acidic group in the fiber containing a crosslinked structure and an acidic group. In fibers containing a crosslinked structure and acidic groups, even if the content of acidic groups is greater than 1 mmol / g, if the bonding amount of the above metal ions is 1 m m ο 1 / g, good P can absorb moisture. However, the potential hygroscopicity of the excess acidic groups cannot be effectively utilized, and the presence of a large amount of acidic groups does not contribute to the hygroscopicity. In order to highlight its advantages, at least 50 m ο 1% of all the acidic groups, and preferably 70 m ο 1% or more, are ideally bonded to metal ions. The metal ions bonded to the acidic group in the fiber containing the cross-linked structure and the acidic group are bound by the acidic group and the ionic bond, and the paper material is made into an aqueous pulp having a concentration of 1 to 3% by weight, and then diluted to 0.1 to 1 weight % When a large amount of water is used as in papermaking engineering, this metal ion is exchanged with other cations present in the water. Therefore, when making the absorbent paper of the present invention, care must be taken to avoid exchange with 200533810 other cations. That is, when the wet papermaking method is used, it is extremely important to use water other than metal ions bonded to acidic groups and having a cation concentration of less than 1 ppm in the preparation of aqueous pulp and subsequent papermaking processes. Except for metal ions bonded to an acidic group, water having a cation concentration of less than 1 ppm means, for example, when sodium ions are bonded to an acidic group, the total concentration of other cations after removing sodium ions is less than 丨 ppm. With this type of water, the exchange of metal ions bonded to acidic groups with other cations can be minimized. On the other hand, if industrial water containing a large amount of cations with a diameter of about 50 to 100 ppm is used, exchange with other cations will occur, and depending on the situation, it will not have the expected moisture absorption and release properties. Except for metal ions bonded to acidic groups, water with a cation concentration of less than 1 ppm is preferably distilled or ion-exchanged water. This kind of water has a small influence on the moisture absorption and release properties and is easily applied to industry. In addition, the ion-exchanged water in the present invention refers to water having a specific electric capacity of less than 3 // S / cm. Generally, when the conductivity is 3 # S / cm, the total cation concentration is 0.6 ppm. Further, it is not limited to distilled water or ion-exchanged water, and water containing only the same ion as the metal bonded to the acidic group may be used. In the present invention, the fibers containing a cross-linked structure and an acidic group are connected by a cross-linked structure between the high molecular molecules constituting the fiber, so that swelling during moisture absorption can be suppressed. The type of the cross-linked structure is not particularly limited. For example, after the polymer is polymerized, it is reacted with a polyfunctional compound such as hydrazine or ethylene glycol diglycidyl ether to form a cross-linked structure. The fiber containing a crosslinked structure and an acidic group can be used, for example, in acrylonitrile-based fibers, to perform cross-linking introduction treatment with a hydrazine compound and hydrolysis treatment with an alkali metal salt to form acrylic hygroscopic fibers. This fiber is easier -10- 200533810 to adjust the amount of cross-linked structure and the amount of foundation, because it may also contain a large number of carboxyl groups, which can meet the moisture absorption and release properties and appearance stability required by absorbent paper. The acrylic hygroscopic fiber is described in detail below. Acrylonitrile fibers, which are raw materials of acrylic moisture-absorbing and releasing fibers, can be made of a single polymer of acrylonitrile or containing more than 40% by weight of acrylonitrile (more preferably, more than 50% by weight, and more preferably more than 80% by weight) ) Acrylonitrile-based copolymer fiber. The monomer copolymerized with acrylonitrile is not particularly limited and may be appropriately selected. p Acrylonitrile-based fibers are cross-linked and introduced by hydrazine compounds. This treatment is based on the reaction of the nitrile groups of acrylonitrile-based fibers with the amine groups of hydrazine compounds to form a cross-linked structure to increase the nitrogen content in the fibers. The increased nitrogen content can meet the state of cross-linking, but when used in the absorbent paper of the present invention, its amount is preferably 1.0 to 10% by weight. A method for adjusting the increased nitrogen content to 1.0 to 10% by weight. For example, the above-mentioned acrylonitrile-based fiber is subjected to a temperature of 50 to 120 ° C for 5 hours in an aqueous solution having a concentration of 5 to 60% by weight of a hydrazine compound. The treatment method is a more ideal industrial method. The hydrazine compounds used therein are not particularly limited, for example, hydrazine hydrate, and hydrazine derivatives such as hydrazine sulfate, hydrazine hydrochloride, hydrazine hydrobromide, hydrazine carbonate and the like, ethylenediamine, sulfate sulfate, hydrochloric acid vein, phosphate vein, melamine, etc. Compounds of multiple amine groups.
藉由肼化合物導入交聯處理的纖維，充分去除因處理而 殘留的肼化合物之後，再進行酸處理較理想。其中使用的 酸無特別的限制，例如硝酸、硫酸、鹽酸等無機酸或有機 酸等。而酸處理的條件亦無特別的限制，例如於50〜1 20°C 200533810 溫度下，使被處理纖維浸漬在酸濃度爲3〜2 0重量％ (較理 想爲7〜1 5重量％ )的水溶液中0.5〜1 0小時。 藉由肼化合物導入交聯處理的纖維或再經過酸處理的纖 維，接著進行藉由鹼金屬鹽的水解處理。與肼化合物導入 交聯處理不相關的殘留腈基、或交聯導入處理後進行酸處 理時殘留的腈基、和部份在酸處理時被水解生成的醯胺基 等，可藉著此水解處理轉換成羧基，此羧基與使用的鹼金 屬鹽的對應金屬離子鍵結係在結合之狀態。 ϋ 上述使用的鹼金屬鹽例如鹼金屬氫氧化物、鹼土類金屬 氫氧化物、鹼金屬碳酸鹽等，金屬種類例如鋰、鈉、鉀等 鹼金屬、鎂、鈣等鹼土類金屬。 經由水解處理生成的羧基量爲1〜10mmol/g，較理想爲 3〜l〇mmol/g，又以 3〜8mmol/g更佳。竣基量少於 lmmol/g 時，無法具有充分的吸放濕性；又超過iOmmol/g時，在吸 濕時會劇烈地膨脹，吸放濕紙的外型安定性不佳，或無法 製得實用上充分的纖維物性。 g 可依需要生成的羧基量適當地設定水解處理的條件，考 鼍工業、纖維物性等，較理想爲在0.5〜1 0重量％ (又以1〜5 遁量％更佳）的鹼金屬鹽水溶液中，於溫度5 0〜1 2 0 °C下處理 1〜1 0小時。又，經過水解處理的纖維，無論殘留或不殘留 腈基皆可。即使殘留腈基，可利用其反應性增加其功能。 進行水解處理的纖維，亦可依需求使用金屬鹽以調整與 羧基鍵結的金屬離子。使用於上述金屬離子來調整處理的 金屬鹽，其金屬種類可選自鋰、鈉、鉀、鈣、鎂，其中以 鈉、鉀、鈣特別理想。又，此處理中使用的鹽的種類爲這 -12- 200533810 些金屬的水溶性鹽即可，例如其氫氧化物、鹵化物、硝酸 鹽、硫酸鹽、碳酸鹽等。具體而言，各種金屬的代表爲： 鈉鹽例如氫氧化鈉、碳酸鈉，鉀鹽例如氫氧化鉀，鈣鹽例 如氫氧化鈣、硝酸鈣、氯化鈣等。 又，如上所述，若期望提昇飽和吸濕量，與丙烯酸系吸 放濕性纖維的羧基鍵結之金屬離子可選擇鈉離子；若期望 提高吸放濕速度，則可選擇鉀離子。 又，除了使丙烯酸系吸放濕性纖維進行上述藉由肼化合 物導入交聯的處理、酸處理、藉由鹼金屬鹽的水解處理、 ^ 金屬離子調整處理之外，亦可進行其他的處理，又，亦可 同時進行交聯導入處理和水解處理。 又，本發明含交聯結構及酸性基的纖維的部份或全部係 已被原纖維化者較理想。若本發明含交聯結構及酸性基的 纖維的部份或全部係已被原纖維化者，造紙時可在纖維間 形成更堅固的纏繞，而可製得外型安定性更優越的吸放濕 紙。且因纖維被細分化後表面積增加，亦可提升吸濕速度。 又，有關上述丙烯酸系吸放濕性纖維，製得被原纖維化之 I 物的方法除了使丙烯酸系吸放濕性纖維直接原纖維化的方 法之外，亦可採用使原料纖維丙烯腈系纖維原纖維化後再 進行上述處理之方法。 原纖維化的方法無特別的限制，可採用一般叩解的方 法。其代表例例如使用打漿機或精煉機等叩解機進行原纖 維化之方法。 以上，說明含交聯結構及酸性基的纖維，如上所述，即 使是含交聯結構及酸性基的纖維亦可能因吸放濕或加熱等 -13- 200533810 因素使外型發生一些變化。因此，若只使用含交聯結構及 酸性基的纖維，極不易使本發明的吸放濕紙具高外型安定 性。本發明中，爲了具有高外型安定性而使用的方法係倂 用無機纖維。無機纖維因吸放濕或加熱產生的外型變化極 小’對提高吸放濕紙的外型安定性極有幫助。這類無機纖 維無特別的限制，例如玻璃纖維、碳纖維、氧化鋁纖維、 金屬纖維等。 ’ 本發明中，除了含交聯結構及酸性基的纖維和無機纖 φ 維’亦使用紙漿狀纖維。若不使用紙漿狀纖維，纖維間的 纏繞不足，各纖維的牽引過輕，不易具有上述無機纖維的 外型安定之效果，有時不易作成紙。此紙漿狀纖維無特別 的限制，例如可採用原纖維化之針葉樹紙漿、闊葉樹紙漿 等木材紙漿、麻紙漿、棉紙漿、洋麻紙漿等非木材紙漿、 人造絲、維尼綸、丙烯酸等合成纖維。其中，與纖維素系 紙漿比較之下，使用丙烯酸纖維時，其耐水性增加，可製 得含水時具高強度的紙，故適用於重複吸濕放濕時需具備 Φ耐久性之用途。 又，上述經過原纖維化的含交聯結構及酸性基的纖維亦 可被使用作爲紙漿狀纖維。此時，因實際上組成吸放濕紙 含交聯結構及酸性基的纖維的量增多，可能具有高吸放濕 性。且，若採用含交聯結構及酸性基的纖維及紙漿狀纖維 兩者皆被原纖維化而含交聯結構及酸性基之纖維，除了可 提高吸放濕性，亦可提升外型安定性。 以上係本發明的吸放濕紙之組成成分，分別敘述含交聯 結構及酸性基的纖維、無機纖維、及紙漿狀纖維，通常各 • 14- 200533810 組成成分的使用比例，較理想爲5〜80重量％的含交聯結構 及酸性基的纖維、10〜40重量％的無機纖維、1〇〜55重量％ 的紙漿狀纖維。若不在此範圍內，不易兼具高吸放濕性和 高外型安定性。 又，需具備更佳的外型安定性時，除了上述組成外亦可 使用熱熔合性纖維。熱熔合性纖維無特別的限制，可使用 聚酯、聚乙烯、聚丙烯、聚醯胺、維尼綸等合成纖維。惟， 因熱熔合性纖維在熱熔合時會覆蓋、束縛含交聯結構及酸 φ 性基的纖維而多少降低吸放濕性，故使用時需特別注意， 其用量爲少於2 0重量％ ，以少於1 0重量％較理想，又以 少於5重量％更佳。 又，本發明的吸放濕紙中除了上述含交聯結構及酸性基 的纖維、無機纖維、紙漿狀纖維及熱熔合性纖維外，亦可 倂用其他天然纖維或合成纖維。 又，在20 °C — 65% RH的環境下，本發明的吸放濕紙的飽 和吸濕率大於1 5 % ，以大於2 0 %較理想。若飽和吸濕率小 φ於1 5 % ，此吸放濕紙不具功能。且本發明的吸放濕紙的水 膨脹率小於50% ，又以小於40%更佳。若水膨脹率超過50 %時，吸濕和放濕時外型發生過大的變化，其用途受到限 制。又’本發明中的飽和吸濕率及水膨脹率係依據後述的 測定方法求得。 其次，說明本發明的吸放濕紙之製造方法。通常可採用 下述的濕式造紙法。 首先，使含交聯結構及1〜1 〇 m m ο 1 / g的酸性基、且該酸性 基與大於1mmol/g之至少1種選自鋰、鈉、鉀、鎂、鈣所 -15- 200533810 組成組群之金屬的金屬離子鍵結的纖維、無機纖維、及紙 漿狀纖維均勻地混合分散於水中形成水性漿。其次，使用 圓網、短網、長網、或其複合式機器等造紙機進行造紙。 造紙後利用筒式乾燥器、洋基乾燥器、空氣乾燥器等常用 的乾燥機進行乾燥，藉此可製得本發明的吸放濕紙。水性 漿及造紙工程中使用的水，係使用如上所述除與酸性基鍵 結之金屬離子之外、其陽離子濃度小於1 p p m的水，其中使 用離子交換水或蒸餾水較理想。 又，上述製造方法中，亦可在水性漿中添加其他纖維或 通常濕式造紙使用的黏劑、膠料劑、染料、紙力增強劑等。 又，可依需求添加抑制塡料流失所需的固定劑。此固定劑 例如聚乙亞胺改良物、聚丙烯醯胺改良物、褐藻酸鈉、阿 拉伯膠、陽性澱粉、硫酸鋁、鉀礬等。 【實施方式】 實施例 以下，以實施例更具體地說明本發明，惟本發明不受限 於這些例子。又，實施例中的份及百分率係以重量基準來 表示。實施例中的離子交換水的陽離子濃度爲0.6ppm。以 下表示實施例中的測定方法、評估方法。 (1 )酸性基量（全羧基量） 精秤約lg充分乾燥的試驗品（Wl〔 g〕），加入200ml 的水後，於加溫至5(TC的同時，添加lmol/1鹽酸水溶液， 使之成爲PH2，其次依據常法，以0.1 mol/1氫氧化鈉水溶 液求出滴定曲線。從此滴定曲線，以羧基的消耗量求出的 氫氧化鈉水溶液消耗量（V 1〔 ml〕），根據下式算出全羧 -16 - 200533810 基量（A1〔 mmol/g〕）。 全竣基量〔mmol/g〕=0.1xVl/Wl (2 )金屬離子鍵結羧基量 在不需要藉著添加上述全羧基量測定操作中的lmQl/Ι鹽 酸水溶液來調整成pH2的情況下求出相同的滴定曲線，進 而求出含於試驗品中的 Η型羧基（COOH )的量（A2 〔mmol/g〕）。從此結果並根據下式算出金屬離子鍵結羧 基量。 金屬離子鍵結竣基量〔mmol/g〕zAl - A2 (3 )金屬離子量 精秤充分乾燥的試驗品，進行濕式分解，採用原子吸光 法求出金屬離子量。 (4 )飽和吸濕率 使0.5g的試驗品絕對乾燥，測定重量（W2〔 g〕）。其 次，將此試驗品置於溫度20°C、65% RH的恆濕槽24小時。 測定吸濕試驗品的重量（W3〔 g〕）。從以上的測定結果 並根據下式算出飽和吸濕率。After the cross-linked fiber is introduced into the hydrazine compound, the hydrazine compound remaining after the treatment is sufficiently removed, and then the acid treatment is preferably performed. The acid used therein is not particularly limited, and examples thereof include inorganic or organic acids such as nitric acid, sulfuric acid, and hydrochloric acid. The conditions of the acid treatment are also not particularly limited. For example, at a temperature of 50 to 120 ° C 200533810, the treated fiber is immersed in an acid concentration of 3 to 20% by weight (preferably 7 to 15% by weight). 0.5 ~ 10 hours in aqueous solution. Crosslinked fibers or acid-treated fibers are introduced by a hydrazine compound, followed by hydrolysis treatment by an alkali metal salt. Residual nitrile groups that are not related to the introduction of the hydrazine compound into the cross-linking treatment, or nitrile groups that remain when the acid treatment is performed after the cross-linking introduction treatment, and some amido groups that are hydrolyzed during the acid treatment can be used for hydrolysis. The treatment is converted into a carboxyl group, and this carboxyl group is bound to a corresponding metal ion bond of the alkali metal salt used. ϋ The alkali metal salts used above are, for example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, and the like, and the metal types are alkali metals such as lithium, sodium, and potassium, and alkaline earth metals such as magnesium and calcium. The amount of carboxyl groups generated by the hydrolysis treatment is 1 to 10 mmol / g, more preferably 3 to 10 mmol / g, and more preferably 3 to 8 mmol / g. When the basis amount is less than 1 mmol / g, it cannot have sufficient moisture absorption and release properties; when it exceeds iOmmol / g, it will swell violently during moisture absorption, and the appearance stability of the moisture absorption paper is not good, or it cannot be prepared. It has practically sufficient fiber physical properties. g The conditions of the hydrolysis treatment can be appropriately set according to the amount of carboxyl groups to be generated, and the alkali metal salt is more preferably 0.5 to 10% by weight (more preferably 1 to 5% by weight) based on industrial and fiber properties. In an aqueous solution, treat at a temperature of 50 to 120 ° C for 1 to 10 hours. In addition, the fibers subjected to the hydrolysis treatment may or may not have residual nitrile groups. Even if the nitrile group remains, its reactivity can be used to increase its function. Fibers subjected to hydrolysis treatment can also use metal salts to adjust the metal ions bonded to the carboxyl group as required. The metal salt used for the above-mentioned metal ion to adjust the treatment can be selected from lithium, sodium, potassium, calcium, and magnesium, and sodium, potassium, and calcium are particularly preferred. In addition, the kind of salt used in this treatment may be water-soluble salts of these metals, such as hydroxides, halides, nitrates, sulfates, carbonates, and the like. Specifically, various metals are represented by: sodium salts such as sodium hydroxide, sodium carbonate, potassium salts such as potassium hydroxide, calcium salts such as calcium hydroxide, calcium nitrate, calcium chloride and the like. Further, as described above, if it is desired to increase the saturated moisture absorption amount, sodium ion can be selected as the metal ion bonded to the carboxyl group of the acrylic hygroscopic fiber, and potassium ion can be selected if it is desired to increase the moisture absorption and release rate. Further, in addition to the acrylic absorbent and dehumidifying fiber, the above-mentioned treatment of introduction and cross-linking by a hydrazine compound, acid treatment, hydrolysis treatment by an alkali metal salt, and metal ion adjustment treatment may be performed. Moreover, a crosslinking introduction process and a hydrolysis process may be performed simultaneously. Further, it is preferred that the fiber containing a crosslinked structure and an acidic group of the present invention is partially or completely fibrillated. If some or all of the fibers containing the crosslinked structure and acidic base of the present invention have been fibrillated, a stronger entanglement between the fibers can be formed during papermaking, and a more stable absorption and release can be obtained. Wet paper. And because the surface area of the fibers is increased after being subdivided, the rate of moisture absorption can also be increased. In addition, as for the method for producing the fibrillated product I related to the above-mentioned acrylic moisture-absorbing and releasing fiber, in addition to the method of directly fibrillating the acrylic moisture-absorbing and releasing fiber, a raw fiber acrylonitrile-based fiber may also be used. After fibrillation, fibrillation is performed. The method of fibrillation is not particularly limited, and a general dissolution method can be used. A typical example thereof is a method of fibrillation using a disintegrator such as a beater or a refiner. As mentioned above, the fibers containing a crosslinked structure and an acidic group are described above. Even the fibers containing a crosslinked structure and an acidic group may have some changes in appearance due to moisture absorption, heat release, or heating. Therefore, if only fibers containing a crosslinked structure and an acidic group are used, it is extremely difficult to make the absorbent and release paper of the present invention highly stable. In the present invention, the method used in order to have high external stability is based on inorganic fibers. The change in the shape of the inorganic fiber due to moisture absorption and release or heating is extremely small ', which is extremely helpful to improve the appearance stability of the moisture absorption and release paper. Such inorganic fibers are not particularly limited, such as glass fibers, carbon fibers, alumina fibers, metal fibers, and the like. In the present invention, pulp-shaped fibers are used in addition to fibers having a cross-linked structure and acidic groups and inorganic fibers φ dimension. If pulp-like fibers are not used, the intertwining of the fibers is insufficient, and the traction of each fiber is too light, and it is difficult to have the effect of stabilizing the appearance of the inorganic fibers, and it is sometimes difficult to make paper. The pulp-like fibers are not particularly limited. For example, fibrillated coniferous pulp, hardwood pulp and other wood pulps, hemp pulp, cotton pulp, and kenaf pulp and other non-wood pulps, rayon, vinylon, acrylic and other synthetic fibers can be used. Among them, compared with cellulose pulp, when acrylic fiber is used, its water resistance is increased, and paper with high strength when water is obtained can be used. Therefore, it is suitable for applications that require Φdurability when repeated moisture absorption and release. The above-mentioned fibrillated fibers containing a crosslinked structure and an acidic group can also be used as pulp fibers. At this time, since the amount of fibers containing a cross-linked structure and acidic groups constituting the absorbent paper is actually increased, it may have high absorbent and release properties. In addition, if fibers containing a crosslinked structure and acidic groups and pulp-like fibers are both fibrillated and fibers containing a crosslinked structure and acidic groups are used, in addition to improving the moisture absorption and release properties, the appearance stability can also be improved. . The above are the constituents of the absorbent paper of the present invention. The fibers containing crosslinked structures and acidic groups, inorganic fibers, and pulp-like fibers are described respectively. Generally, the ratio of the use of the constituent components is 14 ~ 200533810, which is preferably 5 ~ 80% by weight of a fiber containing a crosslinked structure and an acidic group, 10 to 40% by weight of an inorganic fiber, and 10 to 55% by weight of a pulp-like fiber. If it is not within this range, it is difficult to have both high moisture absorption and desorption properties and high appearance stability. In addition, when better external stability is required, heat-fusible fibers may be used in addition to the above composition. The heat-fusible fiber is not particularly limited, and synthetic fibers such as polyester, polyethylene, polypropylene, polyamide, and vinylon can be used. However, since heat-fusible fibers will cover and bind fibers containing cross-linked structures and acid φ groups during heat fusion, the moisture absorption and release properties will be reduced to some extent. Therefore, special attention should be paid during use. The amount is less than 20% by weight. It is preferably less than 10% by weight, and more preferably less than 5% by weight. The absorbent and release paper of the present invention can use other natural fibers or synthetic fibers in addition to the above-mentioned crosslinked structure and acid group-containing fibers, inorganic fibers, pulp fibers, and heat-fusible fibers. In addition, in an environment of 20 ° C to 65% RH, the saturated moisture absorption rate of the absorbent paper of the present invention is more than 15%, and more preferably more than 20%. If the saturated moisture absorption rate is less than 15%, this moisture absorption and release paper is not functional. The water expansion rate of the absorbent paper of the present invention is less than 50%, and more preferably less than 40%. If the water expansion rate exceeds 50%, the appearance will change too much when absorbing and releasing moisture, and its use will be limited. In addition, the saturated moisture absorption rate and the water swelling rate in the present invention were obtained by a measuring method described later. Next, the manufacturing method of the absorbent paper of this invention is demonstrated. Generally, the following wet papermaking method can be used. First, a cross-linked structure and an acidic group of 1 to 10 mm ο 1 / g are selected, and at least one of the acidic group and more than 1 mmol / g is selected from the group consisting of lithium, sodium, potassium, magnesium, and calcium. 15- 200533810 Metal ion-bonded fibers, inorganic fibers, and pulp-like fibers of metals constituting the group are uniformly mixed and dispersed in water to form an aqueous slurry. Next, papermaking is performed using a paper machine such as a circular screen, a short screen, a long screen, or a composite machine thereof. After papermaking, drying is performed using a conventional dryer such as a drum dryer, a Yankee dryer, an air dryer, etc., whereby the absorbent paper of the present invention can be produced. The water used in the aqueous pulp and papermaking engineering is water having a cation concentration of less than 1 p pm, except for metal ions bonded to acidic groups, as described above, and ion exchanged water or distilled water is preferred. Further, in the above-mentioned production method, other fibers or a binder, a sizing agent, a dye, a paper strength enhancer, etc. which are usually used in wet papermaking may be added to the aqueous pulp. In addition, a fixing agent required for suppressing the loss of concrete can be added as required. Examples of the fixing agent include modified polyethyleneimine, modified polypropyleneimine, sodium alginate, Arabic gum, positive starch, aluminum sulfate, potassium alum, and the like. [Embodiments] Examples Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited to these examples. The parts and percentages in the examples are expressed on a weight basis. The cation concentration of the ion-exchanged water in the examples was 0.6 ppm. The measurement methods and evaluation methods in the examples are shown below. (1) The amount of acidic groups (amount of total carboxyl groups) is about 1 g of the test sample (Wl [g]) which is sufficiently dried. After adding 200 ml of water, the temperature is increased to 5 (TC, and 1 mol / 1 hydrochloric acid aqueous solution is added. Let it be PH2, and then calculate the titration curve with a 0.1 mol / 1 sodium hydroxide aqueous solution according to the ordinary method. From this titration curve, the consumption of sodium hydroxide aqueous solution (V 1 [ml]) was calculated from the consumption of carboxyl groups. Calculate the total amount of total carboxyl-16-200533810 (A1 [mmol / g]) according to the following formula. The total amount of basic group [mmol / g] = 0.1xVl / Wl (2) The amount of metal ion-bonded carboxyl groups need not be added The same titration curve was obtained when the lmQl / 1 hydrochloric acid aqueous solution was adjusted to pH 2 during the measurement of the total carboxyl group amount, and the amount of fluorene-type carboxyl group (COOH) contained in the test product (A2 [mmol / g ]]. From this result, the amount of metal ion bonded carboxyl groups was calculated according to the following formula. The amount of metal ion bonded radicals [mmol / g] zAl-A2 (3) The metal ion amount was fully dried and the test sample was subjected to wet decomposition. The atomic absorption method was used to determine the amount of metal ions. (4) The saturated moisture absorption rate was 0.5 g. The test article is absolutely dry and the weight is measured (W2 [g]). Next, this test article is placed in a constant humidity bath at a temperature of 20 ° C and 65% RH for 24 hours. The weight of the hygroscopic test article is measured (W3 [g]) From the above measurement results, the saturated moisture absorption rate was calculated according to the following formula.
飽和吸濕率〔％ 〕= ( ( W3 — W2 ) / W2 1 xlOO (5 )水膨脹率 使試驗品絕對乾燥，測定厚度（T 1 )。將此試驗料浸漬 於水中24小時後，使用離心脫水機（日本國產離心機（股） 公司製TYPEH-770A)在離心加速度160G(G表示爲重力 加速度）下脫水2分鐘，再度測定厚度（T2 )。從這些測 定値且根據下式算出水膨脹率。 水膨脹率〔％ 〕Saturated moisture absorption rate [%] = ((W3 — W2) / W2 1 x 100 (5) Water swelling rate makes the test product absolutely dry and measure the thickness (T 1). After immersing this test material in water for 24 hours, use centrifugation Dehydrator (TYPEH-770A, made by Japan-made centrifuge (stock) company) is dehydrated for 2 minutes at a centrifugal acceleration of 160G (G represents gravity acceleration), and the thickness (T2) is measured again. From these measurements, the water expansion is calculated according to the following formula Water expansion rate [%]
{ ( T2- T1 ) / T1 ) xlOO 200533810 又，實施例中的含交聯結構及酸性基的纖維及丙烯酸紙 漿之製法如下所示。 〔含交聯結構及酸性基的纖維A〕 將1 0份由9 0重量％丙烯腈和1 0重量％乙酸乙烯酯組成 之丙烯腈系聚合物溶解於9 0份的4 8 %硫氰酸鈉水溶液形 成紡絲原液，根據常法使此紡絲原液進行紡絲、展延（全 展延倍率：1〇倍）後，在乾球 /濕球=120°C / 6(TC的環 境下乾燥，之後經過溼熱處理、切斷，製得纖維長7mm、 卓纖維纖度0.9dtex的原料纖維a。在20重量％的讲水溶液 ® 中，使原料纖維a進行5小時9 8 °C的交聯導入處理並水洗。 之後’在3重量％的硝酸水溶液中，進行2小時90 °C的酸 處理。其次，在1重量％的氫氧化鈉水溶液中，進行2小 時90 C的水解處理並以離子交換水清洗，製得含交聯結構 及酸性基的纖維A的纖維。此纖維的酸性基量爲 1.2mmol/g、金屬離子鍵結羧基量爲i.lrnmol/g、鈉離子量 爲 1 · 1 mmol/g 〇 〔含交聯結構及酸性基的纖維B〕 ® 在原料纖維a的水解處理中，除了以3重量％的氫氧化 鉀水溶液進行處理之外，以和含交聯結構及酸性基的纖維 A相同之方法製得含交聯結構及酸性基的纖維b。此纖維 的酸性基量爲6.1 mmol/g、金屬離子鍵結羧基量爲 5.4mmol/g、鉀離子量爲 5.3mmol/g。 〔含交聯結構及酸性基的纖維C〕 在原料纖維a的水解處理中，除了以1 〇重量％的氫氧化 鈉水溶液進行處理之外，以和含交聯結構及酸性基的纖維 -18 - 200533810 A相同之方法製得含交聯結構及酸性基的纖維c °此纖維 的酸性基量爲 8 . 8 m m ο 1 / g、金屬離子鍵結殘基量爲 7.7mmol/g、鈉離子量爲 7.9mmol/g。 〔含交聯結構及酸性基的纖維D〕 將1 0份由9 8重量％丙烯腈和2重量％丙烯酸組成之丙 烯腈系聚合物溶解於9 0份的4 8 %硫氰酸蘇打水溶液形成 紡絲原液，根據常法使此紡絲原液進行濕式紡絲’得出單 纖維纖度0.9 dtex的原料纖維d。其次，將原料纖維d切成 5mm後使用熊谷理機工業（股）製的尼亞加拉式打漿機（型 ® 號B E — 1 0 )進行叩解，作成加拿大標準濾水度1 8 0 m 1的原 纖維化原料纖維d。在2 0重量％的肼水溶液中’使原料纖 維d進行5小時9 8 °C的交聯導入處理並水洗。之後，在3 重量％的硝酸水溶液中，進行2小時90 °C的酸處理。其次， 在3重量％的氫氧化鉀水溶液中，進行2小時90°C的水解 處理並以離子交換水清洗，製得含交聯結構及酸性基的纖 維D的纖維。此纖維的酸性基量爲5.8mmol/g、金屬離子鍵 結殘基量爲5.2mmol/g、鉀離子量爲5.3mmol/g。 β (實施例1〜5 ) 將含交聯結構及酸性基的纖維、無機纖維、紙漿狀纖維 及熱熔合性纖維依表1所示比例分散於離子交換水中，作 成濃度0.5%的水性漿。使用熊谷理機工業（股）製的方形 造紙機器使上述作成的水性漿進行造紙後夾於濾紙間，使 用熊谷理機工業（股）製的旋轉乾燥器，於1 45 °C進行乾燥 作成吸放濕紙。測定上述製得的吸放濕紙的水膨脹率作爲 外型安定性的指標，並測定飽和吸濕率作爲吸放濕性的指 -19- 200533810 標。其評估結果如表1所示。又，以下詳細說明表中的無 機纖維、紙漿狀纖維及熱熔合性纖維。 •玻璃纖維：纖維徑6 // m、纖維長6mm • Bi — PUL :日本益克斯隆工業（股）製的丙烯酸紙漿、 加拿大標準濾水度150ml •針葉樹工藝紙漿：加拿大標準濾水度600ml • VPB- 105 :可樂麗（股）製的維尼綸黏合劑纖維、纖 度1T、纖維長3mm (表1 ) 實施例1 實施例2 實施例3 實施例4 實施例 5 纖 維 組 成 含交聯結構及金屬離 子鍵結酸性基的纖維 % A 70 B 60 C 40 B 60 D 60 無機纖維 % 玻璃纖維 15 玻璃纖維 17 玻璃纖維 27 玻璃纖維 17 坡璃纖維 17 紙漿狀纖維 % Bi-PUL 15 Bi-PUL 20 Bi-PUL 30 針葉樹工藝紙漿 20 Bi-PUL 20 熱熔合性纖維 % — 0 VPB-105 3 VPB-105 3 VPB-105 3 VPB-105 3 評估 結果 水膨脹率（％ ) 20 29 32 40 23 飽和吸濕率（％ ) 15.5 26.6 29.2 28.1 26.3{(T2- T1) / T1) xlOO 200533810 In addition, the method for producing fibers and acrylic pulp containing a crosslinked structure and an acid group in the examples is shown below. [Fiber A containing a crosslinked structure and an acidic group] 10 parts of an acrylonitrile polymer consisting of 90% by weight of acrylonitrile and 10% by weight of vinyl acetate was dissolved in 90 parts of 48% thiocyanate The aqueous sodium solution is used to form a spinning dope, and the spinning dope is spun and stretched (full stretch ratio: 10 times) in accordance with a conventional method, and then in a dry / wet bulb = 120 ° C / 6 (TC environment) After drying, and after wet heat treatment and cutting, a raw fiber a having a fiber length of 7 mm and a fine fiber fineness of 0.9 dtex was prepared. The raw fiber a was crosslinked for 5 hours at 9 8 ° C in 20% by weight aqueous solution ®. Introduce and wash with water. Then, perform acid treatment for 2 hours at 90 ° C in a 3% by weight aqueous solution of nitric acid. Next, perform hydrolysis treatment at 90 C for 2 hours in a 1% by weight aqueous solution of sodium hydroxide and ionize The fiber was washed by exchanging water to obtain a fiber containing a crosslinked structure and an acidic fiber A. The fiber had an acidic amount of 1.2 mmol / g, a metal ion-bonded carboxyl amount of i.lrnmol / g, and a sodium ion amount of 1 · 1 mmol / g 〇 [Fiber B containing a crosslinked structure and an acidic group] ® at the hydrolysis position of the raw material fiber a In addition to the treatment with a 3% by weight potassium hydroxide aqueous solution, a fiber b containing a crosslinked structure and an acidic group was prepared in the same manner as the fiber A containing a crosslinked structure and an acidic group. The acidic group of this fiber The amount was 6.1 mmol / g, the amount of metal ion-bonded carboxyl groups was 5.4 mmol / g, and the amount of potassium ions was 5.3 mmol / g. [Fiber C containing a crosslinked structure and an acidic group] In the hydrolysis treatment of the raw material fiber a, A fiber with a crosslinked structure and an acidic group was prepared in the same way as a fiber containing a crosslinked structure and an acidic group, except that it was treated with a 10% by weight sodium hydroxide aqueous solution. The amount of acidic groups was 8.8 mm ο 1 / g, the amount of metal ion bond residues was 7.7 mmol / g, and the amount of sodium ions was 7.9 mmol / g. [Fiber D containing a crosslinked structure and acidic groups] 10 A part of an acrylonitrile polymer consisting of 98% by weight of acrylonitrile and 2% by weight of acrylic acid was dissolved in 90 parts of a 48% aqueous solution of thiocyanate soda to form a spinning dope, and the spinning dope was subjected to a wet method according to a conventional method. Spinning 'yields a raw fiber d with a single fiber fineness of 0.9 dtex. Second, The fiber d was cut into 5 mm and then mashed using a Niagara beater (type ® BE-10) manufactured by Kumagai Riki Kogyo Kogyo Co., Ltd. to produce a fibrillated raw fiber d with a Canadian standard water degree of 1 800 m 1 The raw fiber d was subjected to a cross-linking introduction treatment in a 20% by weight aqueous solution of hydrazine for 5 hours and 98 ° C and washed with water. After that, an acid treatment in a 3% by weight aqueous nitric acid solution was performed at 90 ° C for 2 hours. Next, a 3% by weight potassium hydroxide aqueous solution was subjected to a hydrolysis treatment at 90 ° C. for 2 hours and washed with ion-exchanged water to obtain fibers of a fiber D containing a crosslinked structure and an acidic group. The fiber had an acid group content of 5.8 mmol / g, a metal ion bond residue amount of 5.2 mmol / g, and a potassium ion amount of 5.3 mmol / g. β (Examples 1 to 5) Fibers containing a crosslinked structure and an acidic group, inorganic fibers, pulp-like fibers, and heat-fusible fibers were dispersed in ion-exchanged water in the proportion shown in Table 1 to prepare an aqueous slurry having a concentration of 0.5%. A square paper machine made by Kumagai Riki Kogyo Kogyo Co., Ltd. was used to make the aqueous pulp prepared above and sandwiched between filter papers. A rotary dryer made by Kumagaya Riki Kogyo Kogyo Co., Ltd. was used to dry at 1 45 ° C. Wet the paper. The water swelling ratio of the absorbent paper produced above was measured as an index of its external stability, and the saturated moisture absorption rate was measured as the index of -19-200533810. The evaluation results are shown in Table 1. In the following, the inorganic fibers, pulp-like fibers, and heat-fusible fibers in the table will be described in detail. • Glass fiber: Fiber diameter 6 // m, fiber length 6mm • Bi — PUL: Acrylic pulp made by Japan Exxon Industrial Co., Ltd., Canadian Standard Filtration 150ml • Conifer Craft Pulp: Canadian Standard Filtration 600ml • VPB-105: Vinylon adhesive fiber made by Kuraray (strand), fineness 1T, fiber length 3mm (Table 1) Example 1 Example 2 Example 3 Example 4 Example 5 The fiber composition contains a crosslinked structure and Metal ion-bonded acid-based fibers% A 70 B 60 C 40 B 60 D 60 Inorganic fibers% Glass fiber 15 Glass fiber 17 Glass fiber 27 Glass fiber 17 Slope glass fiber 17 Pulp fiber% Bi-PUL 15 Bi-PUL 20 Bi-PUL 30 Conifer Craft Pulp 20 Bi-PUL 20 Thermally fusible fiber% — 0 VPB-105 3 VPB-105 3 VPB-105 3 VPB-105 3 Evaluation results Water expansion rate (%) 20 29 32 40 23 Saturation absorption Wet rate (%) 15.5 26.6 29.2 28.1 26.3
實施例1〜5的吸放濕紙中任一者的水膨脹率均低，而飽 和吸濕率均高。特別是實施例5的吸放濕紙，其係使用原 纖維化纖維作爲含交聯結構及酸性基的纖維，因纖維間的 纏繞強，在和具有相同飽和吸濕率的實施例2的吸放濕紙 比較之下，其水膨脹率更低。 (比較例1〜3 ) 和實施例1〜5相同做法，將含交聯結構及酸性基的纖 維、無機纖維、紙漿狀纖維及熱熔合性纖維依表2所示比 例製成吸放濕紙。所製得的吸放濕紙，其評估結果如表2 -20- 200533810 所示。又，比較例3中使用工業用水取代離子交換水。 (表2) 比較例1 比較例2 比較例3 纖 維 組 成 含交聯結構及金 屬離子鍵結酸性 基的纖維 °/〇 B 60 A 70 A 70 無機纖維 % 一 0 一 0 玻璃纖維 15 紙漿狀纖維 % Bi-PUL 40 Bi-PUL 8 Bi-PUL 15 熱熔合性纖維 % — 0 VPB-105 22 一 0 評估 結果 水膨脹率（％ ) 56 12 18 飽和吸濕率（％ ) 27.0 8.8 11.2In any of the absorbent and release papers of Examples 1 to 5, the water expansion rate was low, and the saturated moisture absorption rate was high. In particular, the absorbent paper of Example 5 uses fibrillated fibers as fibers containing a cross-linked structure and acidic groups. Due to the strong intertwining between fibers, the absorbent paper of Example 2 has the same saturated moisture absorption rate. The water swelling rate is lower when compared to a wet paper. (Comparative Examples 1 to 3) In the same manner as in Examples 1 to 5, fibers having a crosslinked structure and an acidic group, inorganic fibers, pulp-like fibers, and heat-fusible fibers were made into absorbent paper according to the ratio shown in Table 2. . The evaluation results of the prepared absorbent and release paper are shown in Table 2-20-20200533810. In Comparative Example 3, industrial water was used instead of ion-exchanged water. (Table 2) Comparative example 1 Comparative example 2 Comparative example 3 Fiber composition Fibers containing a crosslinked structure and metal ion-bonded acidic groups ° / 〇B 60 A 70 A 70 Inorganic fibers% 10 0 Glass fibers 15 Pulp fibers % Bi-PUL 40 Bi-PUL 8 Bi-PUL 15 Thermally fusible fiber% — 0 VPB-105 22 — 0 Evaluation result Water expansion rate (%) 56 12 18 Saturated moisture absorption rate (%) 27.0 8.8 11.2
比較例1雖增加紙漿狀纖維，但因未使用無機纖維，故 無法充分抑制水膨脹。又，比較例2因增加熱熔合性纖維 的用量，故雖可抑制水膨脹率，惟由熱熔合性纖維所引發 之阻礙吸濕的可能性會增加，故飽和吸濕率大幅下降。比 較例3的吸放濕紙係由和實施例1完全相同的纖維組成， 惟因使用工業用水而製成，故工業用水中的陽離子和含交 聯結構及酸性基的纖維A的鈉離子發生離子交換，因而降 低其飽和吸濕率。 -21 -In Comparative Example 1, although pulp-like fibers were added, since inorganic fibers were not used, water swelling could not be sufficiently suppressed. In Comparative Example 2, the amount of thermally fusible fibers was increased, and although the water swelling rate was suppressed, the possibility of preventing moisture absorption caused by the thermally fusible fibers was increased, so that the saturated moisture absorption rate was greatly reduced. The absorbent paper of Comparative Example 3 is composed of exactly the same fibers as in Example 1, except that it is made of industrial water, so the cations in the industrial water and the sodium ions in the fiber A containing the crosslinked structure and the acid group are generated. Ion exchange, thus reducing its saturated moisture absorption. -twenty one -