200307721 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種吸水性樹脂及其製造方法。更詳細 的說，係關於一種吸水能力及生物分解性優異，且溶解成 分少的吸水性樹脂及其製造方法。 【先前技術】 近年來，吸水性樹脂不僅利用為紙尿布或生理用品等 衛生材料，亦利用在體液吸收材料等醫療領域；密封材料（ 防水材料）或防結露材料等土木、建築領域；鮮度保持材料 等食品領域；由溶劑中去除水分之脫水劑等工業領域；綠化 等農業、園藝領域等非常多樣化的領域中。且，因應該等 用途之吸水性樹脂也有許多種被提出。其中又以聚丙烯酸 (鹽）系之吸水性樹脂因具有良好吸水能力並且廉價，被廣 泛的使用。不過，聚丙稀酸（鹽）系之吸水系樹脂雖在吸水 狀態下具有若干光分解性，卻幾乎不具有生物分解性。因 此’在處理聚丙烯酸（鹽）系之吸水系樹脂廢棄物時，比如 ，若進行掩埋處理，不易為土中之細菌或微生物所分解， 因而會發生環境污染的問題。 另一方面，吸水能力優異且具有生物分解性之吸水性 樹脂已知有比如，將多糖類本身交聯之吸水性樹脂（日本 專利特開昭56-5137號公報、特開昭58—79〇〇6號公報、特 開昭60-58443號公報、特開平8-89796號公報）、使用纖 維素衍生物作為多糖類衍生物，並將該纖維素衍生物交聯 之吸水性樹脂（特開昭49-128987號公報、特開昭5〇-85689 200307721 唬公報、特開昭54-163981號公報、特開昭55-5〇〇785號 公報、特開昭54-28755號公報、特開昭57_1373〇1號公報 、特開昭58-1701號公報、特開昭61 —89364號公報、特開 平5-49925號公報、特開平5_123573號公報）等。 但是，將多糖類或多糖類衍生物予以交聯之吸水性樹 月曰，其生物分解性較做為原料之多糖類或者多糖類衍生物 之生物分解性為差。而且，為使吸水性樹脂之吸水能力增 加，理論上必需使交聯密度減小，但是若使交聯密度減小 則未交聯之多糖類或者多糖類衍生物會溶解於水，會有溶 解成分增加的問題。因此，期待能有吸水性良好且生物分 解性良好，並且對水之溶解成分少的吸水性樹脂及其製造 方法。 【發明内容】 本發明之目的為提供一種吸水性良好且生物分解性良 好、且對水之溶解成分少之吸水性樹脂及其製造方法。 本發明者等發現將多糖類與聚乙烯醇以交聯劑進行交 聯所得到之吸水性樹脂其吸水性良好且生物分解性良好， 並且對水之溶解成分少，因而完成了本發明。 亦即，本發明係關於將多糖類與聚乙烯醇以交聯劑進 仃交聯所得到之吸水性樹脂。 上述吸水性樹脂以對生理食鹽水之吸水能力為l〇g/g 以上’對生理食鹽水之溶解成分為30%以下，且生物分解 率為15%以上者為佳。 200307721 上述聚乙烯醇之比例相對於多糖類100重量份，以 0· 1〜200重量份為佳。 上述交聯劑之使用量相對於多糖類與聚乙烯醇合計量 1〇〇重量份’以〇· 05〜50重量份為佳。 上述交聯劑以二醛類或多元羧酸類為佳。 上述多糖類以羧基甲基纖維素為佳。 又’本發明係關於一種吸水性樹脂之製造方法，其特 欲為’將多糖類與聚乙烯醇與交聯劑進行混合再加熱。 (發明之詳細揭示） 用於本發明之多糖類不特別限定，比如有多糖類、多 糖類衍生物及該等之鈉鹽或鉀鹽等鹼金屬鹽等。 夕糖類比如有纖維素、甲基纖維素、乙基纖維素、甲 基乙基纖維素、半纖維素、澱粉、甲基澱粉、乙基澱粉、 甲基乙基澱粉、瓊脂、角叉菜膠、海藻酸、果酸、瓜爾膠 、羅望子（tamarind)膠、刺槐豆膠、筠篛甘露聚糖 (mannan)、葡聚糖、黃原膠、黏稠性多糖、格蘭膠、幾丁 貝、幾丁聚糖、軟骨質硫酸、肝素、透明質酸等。 多糖衍生物比如有將前述多糖類予以羧基烷化或羥基 烷化之羧基曱基纖維素、羥基乙基纖維素、澱粉二醇酸、 瓊脂衍生物、角叉菜膠衍生物等。 又，本說明書中之多糖類尚包含多糖類衍生物及該等 之金屬鹽。 該等多糖類、多糖類衍生物及該等之金屬鹽可單獨使 200307721 用或者亦可將2種以上適當混合。其中，以能夠得到具有 高吸水能力之吸水性樹脂的觀點，較適用的為羧基甲基纖 維素及其鈉鹽或卸鹽等之驗金屬鹽。 前述多糖類之鹼金屬鹽及多糖類衍生物之鹼金屬鹽中 鹽之取代度為0.2〜1.2，較佳為〇· 4〜0· 9。取代度未滿〇 2 時’所得到之吸水性樹脂之吸水性可能會下降。又，若取 代度超過1 · 2，所得到之吸水性樹脂其生物分解率可能會 下降。 日 用於本發明之聚乙烯醇之重量平均分子量不特別限定 ，較佳為100000以下，更佳為90000以下，以 8〇〇00〜1〇〇〇〇又更佳。重量平均分子量若是超過1〇〇〇〇〇時 所得到之吸水性樹脂之生物分解性可能會下降。 聚乙烯醇之皂化度不特別限定，以60〜99· 9%為較佳， 又以80〜99%更佳。皂化度未滿6〇%時，或者超過99•⑽時 所得到之吸水性樹脂其吸水能力可能會下降。 聚乙缚醇之較佳比例對於多糖類100重量份，為 〇·1 200重里份，以丨〜15〇重量份較佳，又以1〇〜12〇重量 h更k。又’聚乙稀醇之比例若未滿i重量份時，所得 到之吸水性樹脂其溶解成分可能會提高。聚乙烯醇之比例 若超過200 4量份日寺，所得到之吸水性樹脂其吸水能力可 能會下降。 用於本發明之交聯劑不特別限定，&如有二醛類、 多元羧酸類、環氣化人必 乳化口物專。其中又以二醛類、多元羧酸 類較佳。 200307721 一醛類比如有乙二醛、戊二醛、對苯二甲醛等。其中 ，以容易取得且廉價之觀點來看，適用者為乙二醛、戊二 醛。 多兀羧酸比如有草酸、順丁烯二酸、琥珀酸、天冬胺 酸、聚丙稀酸等。其+，由安全性高的觀點上，以破拍酸 為適用者。 裱氧化合物比如有乙二醇二縮水甘油醚、聚乙二醇二 縮水甘油醚、甘油聚縮水甘油醚、二甘油二縮水甘油醚、 聚甘油聚縮水甘油醚、丙二醇二縮水甘油醚、聚丙二醇二 縮水甘油鱗、ί辰氧丙醇、7 -縮水甘油醚基丙基三甲氧基 矽烷等。 交聯劑之較佳使用量相對於多糖類及聚乙烯醇合計量 100重置份為〇〇5〜5〇重量份，更佳為〇卜2〇重量份，又 以1〜10重量份更佳。交聯劑之用量未滿〇 〇5重量份時， 所得到之吸水性樹脂之溶解成分可能會增加。又，交聯劑 之用1超過50重量份時，不僅得不到符合使用量之效果， 而且所得到之吸水性樹脂之吸水能力可能會下降。 本發明之吸水性樹脂可利用將多糖類及聚乙烯醇及交 聯劑混合、加熱，進行交聯來製造。 將多糖類及聚乙烯醇以交聯劑進行交聯時，為使能夠 進行均一之交聯反應，以進行均一且充分之混合為佳◊比 如，有將粉體彼此混合之方法、以漿料狀態混合之方法、 以溶液狀態混合之方法等。其中，基於能夠更為均一且充 分混合之觀點，適用者為以溶液狀態混合之方法。 200307721 將多糖類及聚乙烯醇製成溶液時，該溶液之濃度以 0.1:20重量%為佳，又以。5，重量%更佳。濃度未滿 重量%時，溶液量會變多，且為除去溶劑需要長時間加熱 ’可月b會使製造效率下降。又’若濃度超過20重量%時， 水溶液之黏度會變高，將多糖類及聚乙烯醇均一且充分的 混合會變得困難。 ' 加熱並進行交聯時，加熱溫度以6〇〜18〇<>c為佳，又以 '15(TC：更佳。當加熱溫度未滿帆時，交聯反應可能會 篗付難以進行。又，若加熱溫度超過180°C時，多糖類可 月b會著色，或者交聯反應會過度進行而使吸水能力下降。 又，加熱方法不特別限定，比如，有以遠紅外線、微波照 射之方法、使用熱風乾燥機、減壓乾燥機等方法。 加熱時間不特別限定，只要配合多糖類、聚乙烯醇、 交聯劑及溶劑之種類或其組合、加熱溫度、所需吸水性樹 脂之物性來適當設定即可，通常為卜別小時左右。 " 本發明中，依需要為使交聯反應能順利進行，亦可添 加觸媒以進行交聯反應。觸媒之適用者有硫酸、鹽酸、矽 酸、硝酸等酸。 年 觸媒之使用量以對交聯劑100重量份，為b2〇〇重旦 份為佳。觸媒之使用量未滿i重量份時，反應可能會變二 很難進行。又，若觸媒之使用量超過200重量份時，無2 得到符合觸媒使用量的效果，是不經濟的做法。 … 本發明之吸水性樹脂製造方法中’比如，係將多糖類 、聚乙烯醇、交聯劑分別製為水溶液，並將多糖類與聚乙 11 200307721 烯醇之水溶液預先溫人 、 · σ後’添加交聯劑之水溶液並再度混 〇 °將所得到之水滚该 八/合液進仃加熱，使其一面進行交聯反應 一面由水溶液b ’、舌水而乾燥，藉此得到乾燥品。將所得 到之進行粉碎可以製造吸水性樹脂。 、以上述方式所得之吸水性樹脂對生理食鹽水之吸水能 力為 10g/g 以 1« 、 ’又以15〜80g/g較佳。吸水能力若未滿 l〇g/g ’ ϋ吸水性樹脂之使用量會增大故不佳。X，本發明 中之吸水忐力係指將吸水性樹脂lg放入〇. 9重量%之食鹽 水200ml中’使其充分膨潤，接著，以2〇〇篩目之金屬網 _ 將吸水性樹脂過遽，冑定所得到《口及水性樹脂i量A(运） ，再利用下式所算出之值。 吸水能力（g/g)=A/l 又’本發明之吸水性樹脂對生理食鹽水之溶解成分為 30%以下’以25%以下為較佳。溶解成分若超過3〇%時，因 為吸水能力會下降故不佳。又，本發明中之溶解成分係指 ’將吸水性樹脂lg放入〇· 9重量％之食鹽水25〇ml中，以 攪拌子進行3小時之攪拌，接著，以2〇〇篩目之金屬網過 _ 滤’再將回收之濾液50ml放入事先已乾燥之已知重量為 A(g)的燒杯内，正確測出其重量，再測定經過16小時以 140°C乾燥後之重量B(g)，並依下式所算出之值。 溶解成分（％M(B-A)/50 X 250-250 X 0· 〇〇9] X 100 再者，本發明之吸水性樹脂之生物分解率為15%以上 ，以20%以上較佳。生物分解率未滿15%時，生物分解性差 ，可能會發生環境污染等問題。又，本發明之生物分解率 12 200307721 ’係依據JIS K6951，將無水磷酸二氫鉀8 5g、無水鱗酸 氫二鉀21.75g、磷酸氫二鈉二水合物33.4g、氣化銨0.5g 溶解於蒸餾水使成為lOOOmL，於該標準試驗培養液4〇〇mL 中添加吸水性樹脂80mg，接著，將添加有標準活性污泥 3〇ppm的培養液以攪拌子攪拌下，於25〇c培養28天後，求 出所產生之二氧化碳總量A(mg)，另外，同樣的，也求出 未添加吸水性樹脂之培養液所產生之二氧化碳總量 ’並且’求出吸水性樹脂完全分解後所產生之二氧化碳量 之計算值C(mg)，再以下式算出生物分解率之值。 生物分解率（％) = (A-B)/Cx 100 本發明之吸水性樹脂為使加工性改善及品質性能提高 ，亦可依需要，添加二氧化矽微粒子等無機微粒子或由紙 漿纖維所構成之充填劑、活性碳或鐵鈦菁染料衍生物、以 吸附有植物性精油等之沸石為主體的除臭劑、芳香劑、以 銀或銅、辞等金屬為主體的抗菌劑、殺菌劑、防黴劑、防 腐劑、脫氧劑（抗氧化劑）、界面活性劑、發泡劑、香料等 添加劑。前述添加劑之添加量因添加劑種類不同無法一概 決疋’但對於吸水性樹脂1〇〇重量份，通常為〇· 〇1〜5 旦 份左右。 f 本發明之吸水性樹脂不僅可利用在紙尿布或生理用品 等之衛生材料等領域上，亦可利用在如外科手術時之體液 吸收材料、傷口保護材料等醫療領域；密封工程之密封材料 、混凝土熟化材料、凝膠水囊、結露防止材料等土木建築 領域；肉或魚等之滴液吸收材料或鮮度保持材料、蔬菜等之 13 200307721 ••羊度保持材料等食品領域；由溶劑巾除去水分賴水材料等 業邊或，進仃4化時之土壤保水材料或植物栽培用保水材 料、種子覆膜材料等農業、園藝領域等，還有，亦可利用 為油水分離材料、廢液吸收劑、防振材料、隔音材料、家 庭用雜貨品、玩具、人造雪等非常多樣化的領域上。 【實施方式】 (實施發明之最佳形態） 以下利用實施例及比較例詳細敘述本發明，但本發明 不限定於該等實施例。 (實施例1) 將羧基曱基纖維素（阿德利取公司製，取代度〇. 7)之5 重量％水溶液400g與聚乙烯醇（和光純藥工業股份有限公司 製，分子篁44000’息化度88%)之5重量％水溶液10〇g於 80°C下攪拌5小時進行混合。接著，加入40重量％之乙二 醛水溶液5g與濃硫酸0.25g，再度充分的攪拌混合。將所 得到之混合液放在設定在100°C之熱風乾燥機内靜置7小 時，一面進行交聯反應，一面從混合液除去水分使其乾燥 。將所得到之乾燥物用攪拌器粉碎，得到吸水性樹脂 24· 5g 〇 (實施例2) 除將實施例1中，於熱風乾燥機内之靜置時間由7小 時變更為10小時以外，與實施例1同樣進行’得到吸水性 樹脂23. 8g。 200307721 (實施例3) 除將實施例1中，熱風乾燥機内之啤金ώ200307721 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a water-absorbent resin and a manufacturing method thereof. More specifically, it relates to a water-absorbent resin which is excellent in water absorption capacity and biodegradability, and has a small amount of dissolved components, and a method for producing the same. [Prior technology] In recent years, water-absorbent resins have been used not only as sanitary materials such as paper diapers or physiological products, but also in medical fields such as body fluid absorbent materials; civil engineering and construction fields such as sealing materials (waterproof materials) or anti-condensation materials; freshness preservation Food fields such as materials; industrial fields such as dehydrating agents that remove water from solvents; agricultural and horticultural fields such as greening. In addition, many types of water-absorbent resins have been proposed for applications. Among them, polyacrylic acid (salt) -based water-absorbent resins are widely used because they have good water-absorbing ability and are inexpensive. However, although the polyacrylic acid (salt) -based water-absorbing resin has some photodegradability under water absorption, it has almost no biodegradability. Therefore, when processing polyacrylic acid (salt) -based water-absorbing resin waste, for example, if it is buried, it will not be easily decomposed by bacteria or microorganisms in the soil, which will cause environmental pollution. On the other hand, water-absorbent resins having excellent water-absorbing ability and biodegradability are known, for example, water-absorbent resins in which polysaccharides are crosslinked (Japanese Patent Laid-Open No. 56-5137, Japanese Patent Laid-Open No. 58-79). 〇6, JP-A-60-58443, JP-A-8-89796), a water-absorbent resin that uses a cellulose derivative as a polysaccharide derivative and cross-links the cellulose derivative (Japanese Patent Application Laid-Open) Sho 49-128987, JP Sho 50-85689 200307721 Blind Gazette, JP Sho 54-163981, JP Sho 55-50 00785, Sho 54-28755, JP Sho 54-28755 Sho 57_1373〇1, JP Sho 58-1701, JP Sho 61-89364, JP 5-49925, JP 5_123573, etc.). However, a water-absorbent tree in which a polysaccharide or a polysaccharide derivative is crosslinked is said to have a lower biodegradability than a polysaccharide or a polysaccharide derivative used as a raw material. In addition, in order to increase the water absorption capacity of the water-absorbent resin, it is theoretically necessary to reduce the cross-linking density. However, if the cross-linking density is reduced, uncrosslinked polysaccharides or polysaccharide derivatives will dissolve in water and will dissolve. The problem of increased ingredients. Therefore, a water-absorbent resin having good water absorption, good biodegradability, and low water-soluble components and a method for producing the same are expected. SUMMARY OF THE INVENTION An object of the present invention is to provide a water-absorbent resin having good water absorption, good biodegradability, and low water-soluble components, and a method for producing the same. The present inventors have found that the water-absorbent resin obtained by cross-linking polysaccharides and polyvinyl alcohol with a cross-linking agent has good water absorption and good biodegradability, and has few soluble components in water, and has completed the present invention. That is, the present invention relates to a water-absorbent resin obtained by cross-linking polysaccharides and polyvinyl alcohol with a crosslinking agent. The water-absorbent resin preferably has a water-absorbing capacity of physiological saline of 10 g / g or more, and a soluble component of physiological saline of 30% or less, and a biodegradability of 15% or more is preferred. 200307721 The proportion of the polyvinyl alcohol is preferably 0.1 to 200 parts by weight based on 100 parts by weight of the polysaccharide. The amount of the cross-linking agent used is preferably 0.05 to 50 parts by weight based on 100 parts by weight of the total amount of the polysaccharide and the polyvinyl alcohol. The cross-linking agent is preferably a dialdehyde or a polycarboxylic acid. The polysaccharide is preferably carboxymethyl cellulose. The present invention also relates to a method for producing a water-absorbent resin, and specifically, the polysaccharide is mixed with polyvinyl alcohol and a crosslinking agent and then heated. (Detailed disclosure of the invention) The polysaccharides used in the present invention are not particularly limited, and examples thereof include polysaccharides, polysaccharide derivatives, and alkali metal salts such as sodium or potassium salts thereof. Sugars such as cellulose, methyl cellulose, ethyl cellulose, methyl ethyl cellulose, hemicellulose, starch, methyl starch, ethyl starch, methyl ethyl starch, agar, carrageenan , Alginic acid, fruit acid, guar gum, tamarind gum, locust bean gum, mannan, dextran, xanthan gum, viscous polysaccharides, granules, chitin , Chitosan, cartilage sulfate, heparin, hyaluronic acid, etc. Examples of the polysaccharide derivative include carboxyalkylated cellulose, hydroxyethyl cellulose, starch glycolic acid, agar derivatives, and carrageenan derivatives in which the polysaccharides are carboxy-alkylated or hydroxy-alkylated. The polysaccharides in this specification also include polysaccharide derivatives and metal salts thereof. These polysaccharides, polysaccharide derivatives, and these metal salts may be used alone or in combination of two or more types. Among these, from the viewpoint of obtaining a water-absorbent resin having a high water-absorbing capacity, carboxymethylcellulose and its metal salt such as sodium salt or unsalted salt are more suitable. The degree of substitution of the salt in the alkali metal salt of the polysaccharide and the alkali metal salt of the polysaccharide derivative is 0.2 to 1.2, and preferably 0.4 to 0.9. When the degree of substitution is less than 02, the water absorbency of the water-absorbent resin obtained may decrease. If the substitution degree exceeds 1.2, the biodegradability of the obtained water-absorbent resin may decrease. The weight average molecular weight of the polyvinyl alcohol used in the present invention is not particularly limited, but is preferably 100,000 or less, more preferably 90,000 or less, and more preferably 8,000 to 10,000. If the weight average molecular weight exceeds 10,000, the biodegradability of the water-absorbent resin obtained may decrease. The saponification degree of polyvinyl alcohol is not particularly limited, but 60 to 99.9% is more preferable, and 80 to 99% is more preferable. When the saponification degree is less than 60%, or when it exceeds 99 • ⑽, the water-absorbing resin obtained may have a reduced water absorption capacity. The preferred ratio of polyethylene glycol is 0.12 parts by weight to 100 parts by weight of the polysaccharide, more preferably from 1 to 15 parts by weight, and 10 to 12 parts by weight. When the proportion of 'polyvinyl alcohol is less than i parts by weight, the dissolved component of the water-absorbent resin obtained may increase. If the proportion of polyvinyl alcohol exceeds 200 4 parts by weight of Risi, the water-absorbent resin obtained may have a reduced water absorption capacity. The cross-linking agent used in the present invention is not particularly limited, and if there are dialdehydes, polycarboxylic acids, ring gasification, etc. Among them, dialdehydes and polycarboxylic acids are preferred. 200307721 Monoaldehydes such as glyoxal, glutaraldehyde, terephthalaldehyde, etc. Among them, glyoxal and glutaraldehyde are applicable from the viewpoint of easy availability and low cost. Examples of polycarboxylic acids include oxalic acid, maleic acid, succinic acid, aspartic acid, and polyacrylic acid. From the viewpoint of high safety, it is suitable to use breaking acid. Examples of mounting oxygen compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol diglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl scale, hexanopropanol, 7-glycidyl ether propyltrimethoxysilane, etc. The preferred amount of the cross-linking agent is 0.05 to 50 parts by weight, more preferably 20 to 20 parts by weight, and 1 to 10 parts by weight relative to 100 reset parts of polysaccharides and polyvinyl alcohol. good. When the amount of the crosslinking agent is less than 0.05 parts by weight, the dissolved component of the obtained water-absorbent resin may increase. In addition, when the use amount of the crosslinking agent is more than 50 parts by weight, not only the effect according to the amount used cannot be obtained, but also the water-absorbing ability of the obtained water-absorbent resin may decrease. The water-absorbent resin of the present invention can be produced by mixing, heating, and crosslinking a polysaccharide, polyvinyl alcohol, and a crosslinking agent. When polysaccharides and polyvinyl alcohol are cross-linked with a cross-linking agent, in order to enable a uniform cross-linking reaction and uniform and sufficient mixing is preferred, for example, there is a method of mixing powders with each other and using a slurry A method of mixing in a state, a method of mixing in a solution state, and the like. Among them, from the viewpoint of more uniform and sufficient mixing, a method of mixing in a solution state is applicable. 200307721 When polysaccharides and polyvinyl alcohol are made into a solution, the concentration of the solution is preferably 0.1: 20% by weight, and more preferably. 5, weight% is better. When the concentration is less than% by weight, the amount of solution will increase, and it will take a long time to heat the solvent to remove the solvent, and the manufacturing efficiency will decrease. When the concentration exceeds 20% by weight, the viscosity of the aqueous solution becomes high, and it becomes difficult to uniformly and sufficiently mix the polysaccharides and the polyvinyl alcohol. 'When heating and cross-linking, the heating temperature is preferably 60 ° to 18 ° < > c, and '15 (TC: more preferably.) When the heating temperature is not full, the crosslinking reaction may be difficult to overcome. If the heating temperature exceeds 180 ° C, the polysaccharides may be colored, or the cross-linking reaction may proceed excessively to reduce the water absorption capacity. In addition, the heating method is not particularly limited, for example, irradiation with far infrared rays or microwaves Method, using hot air dryer, reduced pressure dryer, etc. The heating time is not particularly limited, as long as the type or combination of polysaccharides, polyvinyl alcohol, cross-linking agent, and solvent, heating temperature, required water-absorbing resin The physical properties can be appropriately set, usually about one hour. &Quot; In the present invention, in order to enable the cross-linking reaction to proceed smoothly, a catalyst can also be added to perform the cross-linking reaction. Suitable catalysts include sulfuric acid, Acids such as hydrochloric acid, silicic acid, nitric acid, etc. The amount of catalyst used per year is preferably 100 parts by weight of the cross-linking agent, which is preferably 200 parts by weight. When the amount of catalyst used is less than i parts by weight, the reaction may change. The second is very difficult. And, if When the amount of the catalyst used exceeds 200 parts by weight, it is not economical to obtain an effect in accordance with the amount of the catalyst without using 2.… In the manufacturing method of the water-absorbent resin of the present invention, for example, polysaccharides, polyvinyl alcohol, The cross-linking agent is separately made into an aqueous solution, and the polysaccharide and the aqueous solution of polyethylene 11 200307721 enol are warmed in advance. After adding σ, the aqueous solution of the cross-linking agent is added and mixed again by 0 °. The liquid is heated and dried while being subjected to a cross-linking reaction with an aqueous solution b 'and tongue water to obtain a dried product. The obtained product is pulverized to produce a water-absorbent resin. The water-absorbent resin obtained in the above manner The water absorption capacity of physiological saline is 10g / g, 1 «, and 15 ~ 80g / g is better. If the water absorption capacity is less than 10g / g ', the amount of water-absorbent resin will increase, so it is not good. X. The water absorption force in the present invention means that the water-absorbent resin lg is put into 200 ml of 0.9% by weight saline solution to make it fully swelled, and then a 200-mesh metal mesh _ will absorb water Resin was overwhelmed, and I got the "mouth and water The amount A (transport) of the resin I is calculated using the following formula: Water absorption capacity (g / g) = A / l Also, the water-soluble resin of the present invention has a dissolved component of physiological saline of 30% or less. 25% or less is preferred. If the dissolved component exceeds 30%, the water absorption capacity will decrease, which is not good. In addition, the soluble component in the present invention means' put the water-absorbing resin lg into 0.9% by weight of common salt Water was stirred for 3 hours with a stirrer in 25 ml of water, and then filtered through a 200-mesh metal mesh. Then, 50 ml of the recovered filtrate was put into a previously-known dried weight of A (g). In the beaker, the weight was accurately measured, and then the weight B (g) after drying at 140 ° C for 16 hours was measured, and the value was calculated according to the following formula. Dissolved component (% M (BA) / 50 X 250-250 X 0 · 〇〇09] X 100 Furthermore, the biodegradation rate of the water-absorbent resin of the present invention is 15% or more, preferably 20% or more. Biodegradation When the ratio is less than 15%, the biodegradability is poor, and problems such as environmental pollution may occur. In addition, the biodegradability of the present invention 12 200307721 is based on JIS K6951, which is an anhydrous potassium dihydrogen phosphate 8 5 g, anhydrous dipotassium hydrogen phosphate 21.75 g, 33.4 g of disodium hydrogen phosphate dihydrate, and 0.5 g of ammonium gaseous solution were dissolved in distilled water to make 1,000 mL, and 80 mg of a water-absorbent resin was added to 400 mL of the standard test culture solution. Next, a standard active soil was added. 30 ppm of the culture solution was stirred with a stirrer, and after 28 days of incubation at 25 ° C, the total amount of carbon dioxide A (mg) was obtained. In addition, the culture without adding a water-absorbent resin was also calculated in the same manner. The total amount of carbon dioxide produced by the liquid 'and' calculate the calculated value C (mg) of the amount of carbon dioxide produced after the water-absorbent resin is completely decomposed, and then calculate the value of the biodegradation rate by the following formula. Biodegradation rate (%) = (AB ) / Cx 100 The water-absorbent resin of the present invention It can improve the quality and performance, and can also add inorganic fine particles such as silicon dioxide fine particles or fillers composed of pulp fibers, activated carbon or iron titanium cyanine dye derivatives, and zeolites with plant essential oils as the main component. Deodorants, fragrances, antibacterial agents based on silver, copper, or other metals, bactericides, fungicides, preservatives, deoxidants (antioxidants), surfactants, foaming agents, perfumes and other additives The amount of the aforementioned additives cannot be determined altogether depending on the type of the additive. However, for 100 parts by weight of the water-absorbent resin, it is usually about 0.001 to 5 deniers. F The water-absorbent resin of the present invention can be used not only in paper In the fields of sanitary materials such as diapers and physiological products, it can also be used in medical fields such as body fluid absorption materials and wound protection materials during surgical operations; sealing materials for sealing engineering, concrete curing materials, gel water sacs, and condensation prevention materials Civil engineering construction fields; drip absorption materials for meat or fish, freshness retention materials, vegetables, etc. 13 200307721 •• Sheep retention materials, etc. In the food field, it can be used to remove water and water from solvent towels, and can also be used as a soil water-retaining material or a water-retaining material for plant cultivation, seed coating materials, and other agricultural and horticultural fields. Oil-water separation materials, waste liquid absorbents, vibration-proof materials, sound-proof materials, household groceries, toys, artificial snow, and other fields are very diverse. [Embodiment] (The best form of implementing the invention) The following uses examples and Comparative examples describe the present invention in detail, but the present invention is not limited to these examples. (Example 1) 400 g of a 5% by weight aqueous solution of carboxyfluorenyl cellulose (manufactured by Adele Corporation, degree of substitution 0.7) and 100 g of a 5% by weight aqueous solution of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 44000 '88%) was stirred at 80 ° C for 5 hours to mix. Next, 5 g of a 40% by weight aqueous solution of glyoxal and 0.25 g of concentrated sulfuric acid were added, and they were sufficiently stirred and mixed again. The obtained mixed liquid was left to stand in a hot-air dryer set at 100 ° C for 7 hours, while the cross-linking reaction proceeded, and water was removed from the mixed liquid and dried. The obtained dried product was pulverized with a stirrer to obtain 24.5 g of a water-absorbent resin. (Example 2) Except that the standing time in the hot air dryer in Example 1 was changed from 7 hours to 10 hours, the same procedure was performed. 8g。 Example 1 was also performed 'to obtain a water-absorbent resin 23. 8g. 200307721 (Example 3) Except that in Example 1, the beer gold in the hot air dryer
又》又疋/皿度由1 〇 〇 〇C 變更為14(TC以外’與實施例1同樣進行，得到吸水性 脂 2 3 · 4 g。 (實施例4) 除將實施例1中，乙二酸變更為戊二醛以外，與實施 例1同樣進行，得到吸水性樹脂24. 4g。 (實施例5) 除將實施例1中，乙二醛變更為琥珀酸以外，與實施 隹 例1同樣進行，得到吸水性樹脂24.4g。 (實施例6) 除將實施例1中羧基曱基纖維素之5重量％水溶液與聚 乙烯醇之5重量％水溶液之量分別變更為25〇g以外與實 施例1同樣進行，得到吸水性樹脂24. 2g。 (比較例1) 將羧基甲基纖維素（阿德利取公司製，取代度〇· 7)之5 重水溶液500g、40重量％之乙二醛水溶液5g、濃硫酸 鲁 〇.25g攪拌混合。將所得到之混合液放在設定在ι〇〇τ之熱 風乾燥機内靜置7小時，一面進行交聯反應，一面從浪合 液除去水勿使其乾燥。將所得到之乾燥物用攪拌器粉碎， 得到吸水性樹脂24. 3g。 (比較例2) 將χκ乙烯醇（和光純藥工業股份有限公司製，分子量 44000 ’皂化度88%)之5重量％水溶液5〇〇g、4〇重量％之乙 15 200307721 二醛水溶液5g、濃硫酸〇.25g攪拌混合。將所得到之混合 液放在設定在i〇〇°c之熱風乾燥機内靜置7小時，一面進 打交聯反應，一面從混合液除去水分使其乾燥。將所得到 之乾燥物用攪拌器粉碎，得到吸水性樹脂24. 1 g。 將各實施例及比較例中所得到之吸水性樹脂之物性值 依以下所示之方法測定。結果表示於表1。 (1) 吸水能力 將吸水性樹脂lg放入〇· 9重量％之食鹽水2〇〇ml中， 使其充分膨潤，接著，以200篩目之金屬網將吸水性樹脂 過濾，測定所得到之吸水性樹脂重量A(g)，再利用下式算 出吸水能力（g/g)。 吸水能力（g/g)=A/l (2) 溶解成分 將吸水性樹脂lg放入〇· 9重量％之食鹽水25〇mi中， 以攪拌子進行3小時之攪拌，接著，以200篩目之金屬網 過濾，回收濾液。將回收之濾液50ml放入事先已乾燥之已 知重量為A(g)的燒杯内，正確測出其重量，再測定以14〇 °C乾燥16小時後之重量B(g)，並依下式所算出之值。 溶解成分（％) = [(B-A)/50 X 250-250 X 0. 〇〇9] X 1〇〇 (3) 生物分解率 係依據JIS K6951，將無水磷酸二氫鉀8 5g、無水構 酸氫二鉀21· 75g、磷酸氫二鈉二水合物33· 4g、氣化錄 〇.5g溶解於蒸餾水使為10〇〇mi之標準試驗培養液，於該 培養液400ml中添加吸水性樹脂80mg，接著，添加濃产 30ppm標準活性污泥（（財團法人）化學物質評價研究機構製 200307721 )。將該培養液以攪拌子攪拌下，於25t下培養28天。在 前述期間中定期測定所產生之二氧化碳量，並求出所產生 之二氧化碳總量A(mg)。另外，同樣的，也求出未添加吸 水性樹脂之培養液所產生之二氧化碳總量B(mg)，並且， 求出吸水性樹脂完全分解後所產生之二氧化碳量之計算值 C(mg)後’以下式算出生物分解率（％)。 生物分解率（％) = (A-B)/CX 100 表1 吸水能力（g/g) 溶解成分00 生物分解率(%) 實施例1 25 17 45 ---—---- 27 "Sr施例2 ~"~~19 -—__ 18 實施例3 16 16 22 實施例4 23 24 33 實施例5 22 25 35 Ϊ施例6 20 18 50 比較例1 16 33 20 比較例2 j 7 10 12 由表1可知實施例1〜實施例6之吸水性樹脂之吸水能 力及生物分解性良好。相對於此，僅由多糖類交聯之比較 例1吸水性樹脂之吸水能力及生物分解性雖然良好，但溶 解成分多。又，僅由聚乙烯醇交聯之比較例2吸水性樹脂 之溶解成分雖然少，但吸水能力及生物分解性低。 (產業上可利用性） 若依本發明’可提供一種吸水能力及生物分解性良好 、並且溶解成分少的吸水性樹脂及其製造方法。 17Also, the temperature was changed from 1000 ° C to 14 (other than TC '). The same procedure was performed as in Example 1 to obtain a water-absorbent lipid 2 3 · 4 g. (Example 4) In addition to Example 1, Except changing the diacid to glutaraldehyde, it was carried out in the same manner as in Example 1 to obtain 24.4 g of a water-absorbent resin. (Example 5) Except that the glyoxal was changed to succinic acid in Example 1, Example 1 was performed. The same procedure was performed to obtain 24.4 g of a water-absorbent resin. (Example 6) Except that the amounts of a 5% by weight aqueous solution of carboxyfluorenyl cellulose and a 5% by weight aqueous solution of polyvinyl alcohol in Example 1 were changed to 25 g, respectively. Example 1 was performed in the same manner to obtain 24.2 g of a water-absorbent resin. (Comparative Example 1) Carboxymethylcellulose (manufactured by Adele Corporation, degree of substitution: 0.7), 500 g of 5 weight aqueous solution, 40% by weight of ethyl acetate 5 g of dialdehyde aqueous solution and 0.25 g of concentrated sulfuric acid were stirred and mixed. The obtained mixed liquid was left to stand in a hot air dryer set at 〇〇〇τ for 7 hours, while the cross-linking reaction was carried out, and water was removed from the Langhe liquid. The obtained dried product was pulverized with a stirrer to obtain a water-absorbent resin 24. 3g. (Comparative Example 2) 5000 g of 5% kappa vinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 44000 'saponification degree 88%), 5,000 g, 40% by weight, 15 200307721 dialdehyde 5 g of aqueous solution and 0.25 g of concentrated sulfuric acid were stirred and mixed. The obtained mixed liquid was left to stand in a hot air dryer set at 100 ° C for 7 hours, and a cross-linking reaction was carried out while removing water from the mixed liquid to make it Dry. The obtained dried product was pulverized with a stirrer to obtain 24.1 g of a water-absorbent resin. The physical properties of the water-absorbent resin obtained in each of the Examples and Comparative Examples were measured by the following methods. The results are shown in Table 1. (1) Water absorption capacity The water-absorbent resin lg was put into 200 ml of 0.9% by weight saline solution to make it fully swelled. Then, the water-absorbent resin was filtered through a 200-mesh metal mesh and measured. The obtained water-absorbent resin weighs A (g), and the water absorption capacity (g / g) is calculated using the following formula: Water absorption capacity (g / g) = A / l (2) Dissolving component Put water-absorbent resin lg into the 0 · Stir with 9% by weight of sodium chloride for 2 hours with a stir bar. Next, it was filtered through a 200-mesh metal mesh to recover the filtrate. 50 ml of the recovered filtrate was placed in a beaker of a known weight A (g) that had been dried beforehand, and its weight was accurately measured, and then measured at 14 ° C. The weight B (g) after 16 hours of drying was calculated according to the following formula: Dissolved component (%) = [(BA) / 50 X 250-250 X 0. 〇〇9] X 1〇〇 (3) The biodegradation rate is based on JIS K6951. 8.5 g of anhydrous potassium dihydrogen phosphate, 21.75 g of anhydrous dibasic acid hydrogen phosphate, 33.4 g of disodium hydrogen phosphate dihydrate, and 0.5 g of gasification record are dissolved in distilled water to 10 A standard test culture solution of 〇〇mi was added to 400 ml of the culture solution to 80 mg of a water-absorbent resin, and then 30 ppm of standard activated sludge (200307721, manufactured by the Chemical Substance Evaluation Research Institute) was added. This culture liquid was stirred at 25 t for 28 days under stirring with a stirrer. During the aforementioned period, the amount of carbon dioxide produced was periodically measured, and the total amount of carbon dioxide produced (mg) was obtained. In the same manner, the total amount of carbon dioxide B (mg) generated from the culture solution to which the water-absorbent resin was not added was also calculated, and the calculated value C (mg) of the amount of carbon dioxide generated after the water-absorbent resin was completely decomposed was calculated. 'The biodegradation rate (%) is calculated by the following formula. Biodegradability (%) = (AB) / CX 100 Table 1 Water absorption capacity (g / g) Dissolved component 00 Biodegradability (%) Example 1 25 17 45 ----------- 27 " Sr Example 2 ~ " ~~ 19 -----__ 18 Example 3 16 16 22 Example 4 23 24 33 Example 5 22 25 35 Ϊ Example 6 20 18 50 Comparative Example 1 16 33 20 Comparative Example 2 j 7 10 12 It can be seen from Table 1 that the water-absorbing resins and biodegradability of the water-absorbing resins of Examples 1 to 6 are good. On the other hand, although the water-absorbent resin and the biodegradability of Comparative Example 1 which was crosslinked only with polysaccharides were good, there were many dissolved components. In addition, although the water-absorbing resin of Comparative Example 2 which was crosslinked only with polyvinyl alcohol had a small amount of dissolved components, its water-absorbing ability and biodegradability were low. (Industrial Applicability) According to the present invention, it is possible to provide a water-absorbent resin having good water absorption capacity and biodegradability, and having few dissolved components, and a method for producing the same. 17