1331900 玖、發明說明： 【發明所屬之技術領域】 本發明相關於一種水溶性曱殼素’尤指一種包含水溶 性甲殼素的抗微生物組成物、除臭及防臭組成物、農藥組 成物及一種農業上抗微生物的方法。 【先前技術】_ 甲殼素是地球上蘊藏量第二豐富的天然高分子，主要 取自瑕蟹水產的殼廢棄物，曱殼素的化學結構為多醣體 (polysaccharide)，一 般包括幾丁質（chitin)、幾 丁胺醣 (chitosan)以及這兩者的衍生物，幾丁質是由蝦蟹殼經過除 去辦質和除去蛋白質後的產物，化學式為乙醯胺葡萄醣{ poly[P-(l_>4)-2-acetamido-2-deoxy-D-glucopyranose] }， 表丁胺st是由幾丁質經過脫乙醯反應（deaeetylation)所得到 的產物，化學式為胺基葡萄醣丨h de〇xy-D-glueopyranose]丨’一般幾丁胺醣是指脫乙醯度 (degree 〇f deacetyUti〇n)介於 7〇1〇〇%的產物，而幾 丁質和 幾丁胺醣都無法單獨且直接溶於水令，必須使用有機酸或 其他溶媒才能將幾丁質和幾丁胺醣溶於水中。 經由實驗證明曱殼素具有抑制微生物生長的特性，在 目前的應用上，現行技術皆為將幾丁質或幾丁質衍生物如 幾丁胺醋溶解於酸中，或製作成幾丁胺_生物，由於必 須溶解於酸中’故現行技術都存在有pH值不安定、效果 不佳以及與其他化合物不相容的問題。 1331900 【發明内容】 本發明相關於一種抗微生物組成物，包含抗微生物有 效量之水溶性甲殼素及一種以上的金屬鹽，該金眉鹽對該 水溶性甲殼素之重量比介於1:1 0至1:5〇〇。 本發明所述之抗微生物組成物係形成水溶液、凝膠或 固體形式，或上述一種以上組合的形式。 本發明所述之抗微生物組成物中，該水溶性曱殼素可 為脫乙醯化幾丁質，該脫乙醯化幾丁質之脫乙醯度介於 40-60%，而分子量介於5,000至500,000，較佳地，該水 溶性曱殼素係可為幾丁募酷（Oligo-chitin)或幾丁胺寡醣 (Oligo-chitosan) ’或上述之組合’該幾丁寡醣和幾丁胺寡 醣係為單醣、雙醣、三醣、四醣、五醣、六醣、七醣、八 餹、九或十酷’或上述一種以上之組合。 本發明所述之抗微生物組成物中，該金屬鹽中金屬離 子可為汞（Hg)離子、錫（Sn)離子、鉛（Pb)離子、銅（Cu)離子 、銀（Ag)離子或鋅（Zn)離子，本發明之抗微生物組成物可 含有以上一種或一種以上的金屬離子。 本發明所述之抗微生物組成物中，該金屬鹽之鹽基可 為醋酸（acetate)鹽、蝴酸（borate)鹽、漠（bromide)鹽、碳酸 (carbonate)鹽、氣酸（chlorate)鹽、氯（chloride)鹽、鉻酸 (chromate)鹽、重鉻酸（dichromaie)鹽、檸檬酸（citrate)鹽、 曱酸（formate)鹽、葡萄酸（giuc〇nate)鹽、硝酸（nitrate)鹽、 過氯酸（perchlorate)鹽、填酸（phosphate)鹽、水揚酸 1331900 (salicylate)鹽、硫酸（sulfate)鹽或酒石酸（tartrate)鹽，由上 述一種或一種以上之組合所構成。 本發明所述之抗微生物組成物除了抗細菌成分以外， 可進而包括有機醇類化合物’其係選自甲醇（methanol)、 乙醇（ethanol)、正丙醇（n-propanol)、異丙醇（i_pr〇pan〇i)、 乙二醇（ethylene glycol)和丙三醇（glycohol)所組成的族群 〇 本發明所述之抗微生物組成物中，為達到各種應用上 的需要，可進而包括增稍劑、界面活性劑、香料或色料， 或上述一種以上之組合，增加的成分佔該組成物的〇. 5 -50%，該增稠劑可為水溶性高分子，其係選自澱粉衍生物 (modified starch)、纖維素衍生物（cellulose derivatives)、 蛋白質（proteins)、藻酸膠（alginate)、聚乙烯醇（polyvinyl alcohol)、聚丙稀醯酸聚合物（polyacrylics)、聚醋 (polyester)和聚胺基甲酸醋—(polyurethane)所組成之族群， 而該界面活性劑包括陰離子型界面活性劑、陽離子型界面 活性劑、非離子型界面活性劑或兩性界面活性劑，或上述 一種以上之組合’且該界面活性劑的HLB值界於1 -1 5。 本發明亦相關於一種除臭及防臭組成物，包含除臭及 防臭有效量之水溶性曱殼素及一種以上的金屬鹽，該金屬 鹽對該水溶性曱殼素之重量比介於1:丨〇至1 ·5〇〇。 本發明所述之除臭及防臭組成物中，其係形成水溶液 、凝勝或固體形式，或上述一種以上組合的形式。 本發明所述之除臭及防臭組成物中，該水溶性曱殼素 叫9〇〇 :〇為脫乙4匕幾丁質，該脫乙醯化幾丁質之脫乙醯度介於 A 6〇/。，而分子量介於5,〇〇〇至500,000，較佳地，該水 冷性曱殼素可為幾丁寡醣或幾丁胺寡醣，《上述之組合， 且该幾丁寡醣和幾丁胺寡醣可為單醣、雙醣、三醣、四醣 五醣、六醣、七醣、八醣、九醣或十醣，或上述一種以 上之組合。 本發明所述之除臭及防臭組成物中，該金屬鹽中金屬 離子可為汞（Hg)離子、錫（sn)離子、鉛（pb)離子、銅（Cu)離 子、銀（Ag)離子或鋅（Zn)離子，本發明之除臭及防臭組成 物可含有以上一種或一種以上的金屬離子。 本發明所述之除臭及防臭組成物中，該金屬鹽之鹽基 可為醋酸（acetate)鹽、硼酸（borate)鹽、溴（bromide)鹽、碳 酸（carbonate)鹽、氣酸（chlorate)鹽、氣（chloride)鹽、鉻酸 (chromate)鹽、重鉻酸（dichromate)鹽、檸檬酸（citrate)鹽、 曱酸（formate)鹽、葡萄酸（gluconate)鹽、硝酸（nitrate)鹽、 過氯酸（perchlorate)鹽、磷酸（phosphate)鹽、水楊酸 (salicylate)鹽、硫酸（sulfate)鹽或酒石酸（tartrate)鹽，由上 述一種或一種以上之組合所構成。 本發明所述之除臭及防臭組成物除了抗細菌成分以外 ，可進而包括有機醇類化合物，其係選自曱醇（methanol) 、乙醇（ethanol)、正丙醇（n-propanol)、異丙醇（i-propan〇i) 、乙二醇（ethylene glycol)和丙三醇（glycohol)所組成的族 群。 本發明所述之除臭及防臭組成物中，為達到各種應用 1331900 上的需要，可進而包括增稠劑、界面活性劑、香料或色料 ，或上述一種以上之組合，增加的成分佔該組成物的0 5 -50%，該增稠劑為水溶性高分子，其係選自澱粉衍生物 (modified starch)、纖維素衍生物（cellulose derivatives)、 蛋白質（proteins)、藻酸膠（alginate)、聚乙烯醇（p〇iyv丨nyl alcohol)、聚丙稀酿酸聚合物（polyacrylics)、聚醋 (polyester)和聚胺基曱酸酯（polyurethane)所組成之族群， 而該界面活性劑包括陰離子型界面活性劑、陽離子型界面 活性劑、非離子型界面活性劑或兩性界面活性劑，或上述 一種以上之組合，且該界面活性劑的HLB值界於1 -丨5。 本發明另亦相關於一種農藥組成物，包含抗微生物有 效量之水溶性甲殼素、一種以上農業化學可接受金屬鹽且 至少一種佐劑，該金屬鹽對該水溶性甲殼素之重量比介於 1:10 至 1:500 。 本發明所述之農藥組成物中，該水溶性曱殼素為脫乙 酿化幾丁質，該脫乙醯化幾丁質之脫乙醯度介於40_6〇%， 而分子量介於5,000至500,000。 本發明所述之農藥組成物中’該水溶性甲殼素係可為 幾丁寡骑或幾丁胺寡醣’或上述之組合，而該幾丁募聽和 幾丁胺募醣係可為單骑，、雙酷、三醣、四醣、五醣、六聽 、七醣、八醣、九醣或十醣，或上述—種以上之組合。 本發明所述之農藥組成物中’該金屬鹽中金屬離子可 為汞（Hg)離子、錫（Sn)離子、鉛（Pb)離子、銅（Cu)離子銀 (八幻離子或鋅（Zn)離子，本發明之農藥組成物可含有以上 1331900 一種或一種以上的金屬離子。 本發明所述之農藥組成物中，該金屬鹽之鹽基可為醋 酸（acetate)鹽、硼酸（borate)鹽、溴（bromide)鹽、碳酸 (carbonate)鹽、氯酸（chlorate)鹽、氣（chi〇ride)鹽、絡酸 (chromate)鹽、重鉻酸（dichromate)鹽、檸檬酸（Citrate)鹽、 曱酸（formate)鹽' 葡萄酸（giuc〇nate)鹽、硝酸（nitrate)鹽、 過氯酸（perchlorate)鹽、磷酸（phosphate)鹽、水揚酸 (salicylate)鹽、硫酸（sulfate)鹽或酒石酸（tartrate)鹽，由上 述一種或一種以上之組合所構成。 本發明另亦相關於一種農業上抗微生物的方法，其係 括C用本發明所述之農藥組成物於植物、植物的一部份 有吾物或地面上。 【實施方式】 ，由於一般幾丁胺醣之脫乙醯度為介力7〇-1〇〇%的產物 不易冷於水然而當乙醯胺葡萄醣和胺基葡萄醣的 =構分子之脫乙喊介於45_55%之間，也就是乙醯胺葡萄 骑和胺基葡萄醣的結構中分早h圭 义 τ刀千比率相當時，則這種脫乙酿 化的幾丁質可以直接溶 、κ 柄為水溶性曱殼素，其化學 式4如下示： 1331900 除了 45-55%之脫乙酸產物以外，低分子量的幾丁質或 幾丁胺醣也是水溶性f殼素的規格，當幾丁質或幾丁胺黯 高分子經過降解（degradation)而生成寡醣，當聚人产 DP<丨0時，便出現水溶性，水溶性的甲殼素具有可以配成 中性溶液的特性，對於皮膚的刺激性小，且和其他化合物 的相容性佳，因此可使用的範圍比一般ρ殼素寬廣。 本發明使用之水溶性甲殼素可藉由其特性直接溶於水 中’因此能夠避免使用酸性溶液’故可解決pH值不安定 、效果不佳以及與其他化合物不相容的問題，並可運用銅 、銀、鋅等金屬離子與水溶性曱殼素結合，達到增強抗菌 防黴效果，藉由曱殼素與金屬離子形成的金屬鹽製作成水 溶液、凝膠、固體不同型態的產品，而適合不同的用途， 藉此達到抗微生物的功能。 由於本發明之水溶性曱殼素和水溶性金屬鹽混合可達 到抗微生物的功效，進而可除臭及防臭，亦可運用於農業 上作為農藥組成物’利用該農藥組成物施用於植物及栽培 空間’而於農業上作為抗微生物的方法。 本發明所述的組合物，由水溶性甲殼素和水溶性金屬 鹽兩者所構成，該水溶性甲殼素為脫乙醯化幾丁質，該脫 乙酿化幾丁質之脫乙醯度介於40-60%，而分子量介於 5,000至500,〇〇〇，該水溶性甲殼素可為幾丁寡醣或幾丁胺 寡畴’或上述之組合’該幾丁寡醣和幾丁胺寡醣係可為單 醣又醣、二醣、四醣、五醣、六醣、七醣、八醣、九醣 或十醣’或上述一種以上之組合。 10 1331900 邊金屬鹽中金屬離子可為汞（Hg)離子、錫（Sn)離子、 鉛（Pb)離子、銅（Cu)離子、銀（Ag)離子或鋅（Zn)離子，由上 述一種或一種以上的金屬離子組成，而該金屬鹽之鹽基可 為醋酸（acetate)鹽 '硼酸（borate)鹽、溴（br〇mide)鹽、碳酸 (carbonate)鹽、氣酸（chlorate)鹽、氣（chl〇ride)鹽、鉻酸 (chromate)鹽、重鉻酸（dichromate)鹽、檸檬酸（citrate)鹽、 曱酸（formate)鹽、葡萄酸（giuconate)鹽、硝酸（nitrate)鹽、 過氣酸（perchlorate)鹽、填酸（phosphate)鹽' 水楊酸 (salicylate)鹽、硫酸（suifate)鹽或酒石酸（Urtrate)鹽，由上 述一種或一種以上之組合所構成。。 將水溶性曱殼素先溶於水’再與金屬鹽混合，形成均 勻的溶液’該金屬鹽對該水溶性甲殼素之重量比介於丨：i 〇 至1:5〇〇，藉由水溶性曱殼素與金屬鹽的濃度和重量比， 控制產物的型態’當金屬鹽的比率提高時，水溶性曱殼素 由液體中漸漸形成凝膠，當金屬鹽的濃度（比率）再提高到 一個臨界值以後’水溶性曱殼素在溶液中形成固體沉澱物 ’這三種型態的產物’視使用需要進一步加工，擴大用途 〇 液體產物可以摻入界面活性劑、增稠劑、有機溶劑、 色料、香料等添加物，而凝膠產物可以作為抗菌劑或直接 壓鑄成膠膜與勝片’另固體產物可以過濾後作成分散液或 乾粉。 該有機醇類化合物係可選自甲醇（methan〇丨）、乙醇 (ethanol)、正丙醇（n_pr〇pan〇i)、異丙醇、乙二 1331900 醇（ethylene g丨yco丨）和丙三醇（glyc〇h〇i)所組成的族群，另 亦進而包括增稠劑、界面活性劑、香料或色料，或上述— 種以上之組。’其中增加的成分佔該組成物的， 而該增稍劑可為水溶性高分子，彡係選自澱粉衍生物 (m〇dified Starch)、纖維素衍生物（cellulose derivatives)、 蛋白質（proteins)、藻酸膠（alginate)、聚乙烯醇（p〇lyvinyi alcohol)、聚丙烯醯酸聚合物（p〇]yacryHcs)、聚酯 (polyester)和聚胺基甲酸酯（p〇Iyureihane)所組成之族群， 該界面活性劑包括陰離子型界面活性劑、陽離子型界面活 性劑、非離子型界面活性劑或兩性界面活性劑，或上述— 種以上之組合’其中該界面活性劑的HLB值界於1 _丨5。 本發明其他的特徵及優點將可明顯見於下列較佳具體事實 及申請專利範圍。 實例 下列實施例用於示範說明本發明。這些實施例不以任何方 式意欲限制本發明之範圍，但用於指示如何實施本發明的材料 及方法。 實.1例1 溶性甲殼音之組成物的配方及抗骷 菌試驗 1.1配方 取1 000毫升的純水，加入30公克脫乙醯度48%的脫 1331900 乙醯幾丁質，再加入2公克硫酸鋅，攪拌丨小時後形成黏 液，靜置48小時後，得到凝膠。將凝膠倒入培養皿中， 放在6〇°C下烘培12小時，得到膠片，此膠片以ASTm G21標準檢測其抗黴性。 L2試驗方法 4驗菌種：黑麴菌心尽er) ATcc 9642 剪裁6Cmx2Cm的長方形試片，將之平貼在植菌的培養 基上，經過36。<3七日培養後，觀察黴菌生長特性。 U試驗結果 由第圖及第二圖所示，第一圖係未貼試片的培養皿 4培養皿上長滿孢子，而第二圖係貼有試片的培養皿， 邊忒片上不長孢子，而於試片外長滿孢子，結果顯示，孢 子生長面積由95%減到20%。 素之组成物的配方方 2 · 1配方 取1000毫升的純水，加入3公克脫乙醯度48%的脫 士 i幾丁質、2公克幾丁寡醣及3毫克氣化錫，攪拌i小 時達到完全溶解，再加人5G公克酒精和2公克檜木精油 搜拌均勻後使用於冑霧，冑其抗微生物的效能進行驗證 〇 2 · 2喊驗方法 式驗菌種：金黃色葡萄球菌…即紗/ac〇ccw⑽aw) 13 1331900 ATCC 65381331900 玖Invention Description: [Technical Field] The present invention relates to a water-soluble chitin, especially an antimicrobial composition comprising a water-soluble chitin, a deodorizing and deodorizing composition, a pesticide composition and a Agricultural methods of antimicrobials. [Prior Art] _ Chitin is the second most abundant natural polymer on the earth. It is mainly taken from the shell waste of the crab crab. The chemical structure of chitin is polysaccharide, which usually includes chitin ( Chitin), chitosan (chitosan) and derivatives of the two, chitin is a product of the shrimp and crab shell after removing the medium and removing the protein. The chemical formula is acetaminophen glucose { poly[P-(l_>) ;4)-2-acetamido-2-deoxy-D-glucopyranose] }, epithylamine st is a product obtained by dedeeetylation of chitin, the chemical formula is aminoglucose h de〇xy -D-glueopyranose]丨 'General chitosan sugar refers to the product of 7〇1〇〇% of degree 〇f deacetyUti〇n, and chitin and chitosan cannot be separate and Directly soluble in water, organic acids or other solvents must be used to dissolve chitin and chitosan sugar in water. It has been proved through experiments that quercetin has the property of inhibiting the growth of microorganisms. In the current application, the current technology is to dissolve chitin or chitin derivatives such as chitosan vinegar in acid or make chitosan. Since organisms must be dissolved in acid, there are problems in the prior art that pH is unstable, the effect is poor, and it is incompatible with other compounds. 1331900 SUMMARY OF THE INVENTION The present invention relates to an antimicrobial composition comprising an antimicrobially effective amount of water-soluble chitin and one or more metal salts, the weight ratio of the golden eyebrow salt to the water-soluble chitin is 1:1 0 to 1:5〇〇. The antimicrobial composition of the present invention forms an aqueous solution, a gel or a solid form, or a combination of one or more of the above. In the antimicrobial composition of the present invention, the water-soluble chitin may be deacetylated chitin, and the deacetylated chitin has a deacetylation degree of 40-60%, and the molecular weight is Preferably, the water-soluble crustacean may be Oligo-chitin or Oligo-chitosan 'or a combination of the above-mentioned chitosan oligosaccharides and 3-5 to 500,000. The chitosan oligosaccharide is a monosaccharide, disaccharide, trisaccharide, tetrasaccharide, pentasaccharide, hexose, heptasaccharide, gossip, ninth or tenth cool or a combination of more than one of the above. In the antimicrobial composition of the present invention, the metal ion in the metal salt may be mercury (Hg) ion, tin (Sn) ion, lead (Pb) ion, copper (Cu) ion, silver (Ag) ion or zinc. The (Zn) ion, the antimicrobial composition of the present invention may contain one or more of the above metal ions. In the antimicrobial composition of the present invention, the base of the metal salt may be an acetate salt, a borate salt, a bromide salt, a carbonate salt, a chlorate salt. , chloride, chromate, dichromaie, citrate, forate, giuc〇nate, nitrate And a perchlorate salt, a phosphate salt, a salicylic acid 1331900 (salicylate) salt, a sulfuric acid salt or a tartrate salt, which is composed of one or a combination of the above. The antimicrobial composition of the present invention may further comprise, in addition to the antibacterial component, an organic alcohol compound selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol ( a group consisting of i_pr〇pan〇i), ethylene glycol, and glycerol. The antimicrobial composition of the present invention may further include an increase in the antimicrobial composition of the present invention. The agent, the surfactant, the fragrance or the colorant, or a combination of one or more of the above, the added component is 〇. 5 - 50% of the composition, the thickener may be a water-soluble polymer selected from the group consisting of starch. Modified starch, cellulose derivatives, proteins, alginate, polyvinyl alcohol, polyacrylics, polyester And a group of polyurethanes, and the surfactant includes an anionic surfactant, a cationic surfactant, a nonionic surfactant or an amphoteric surfactant. Or one or more of the above-described composition 'and the HLB value of the surfactant is bound to 1-15. The invention also relates to a deodorizing and deodorizing composition comprising a deodorizing and deodorizing effective amount of water-soluble chitin and one or more metal salts, wherein the weight ratio of the metal salt to the water-soluble chitin is 1:丨〇 to 1 · 5〇〇. In the deodorant and deodorant composition of the present invention, it is in the form of an aqueous solution, a condensed or solid form, or a combination of one or more of the above. In the deodorizing and deodorizing composition of the present invention, the water-soluble chitin is called 9: 〇 is deacetylated, and the deacetylation degree of the deacetylated chitin is between A. 6〇/. And the molecular weight is between 5 and 500,000. Preferably, the water-cooled chitin is a chitosan oligosaccharide or a chitosan oligosaccharide, the combination of the above, and the chitosan oligosaccharide and the chitin The amine oligosaccharide may be a monosaccharide, a disaccharide, a trisaccharide, a tetrasaccharide pentasaccharide, a hexose, a heptasaccharide, an octasaccharide, a pentose or a decasaccharide, or a combination of one or more of the foregoing. In the deodorant and deodorant composition of the present invention, the metal ions in the metal salt may be mercury (Hg) ions, tin (sn) ions, lead (pb) ions, copper (Cu) ions, silver (Ag) ions. Or zinc (Zn) ions, the deodorant and deodorant composition of the present invention may contain one or more of the above metal ions. In the deodorant and deodorant composition of the present invention, the base of the metal salt may be an acetate salt, a borate salt, a bromide salt, a carbonate salt, or a chlorate. Salt, chloride salt, chromate salt, dichromate salt, citrate salt, formate salt, gluconate salt, nitrate salt, A perchlorate salt, a phosphate salt, a salicylate salt, a sulfate salt or a tartrate salt is composed of one or a combination of the above. The deodorant and deodorant composition of the present invention may further comprise, in addition to the antibacterial component, an organic alcohol compound selected from the group consisting of methanol, ethanol, n-propanol, and iso-alcohol. A group of i-propan〇i, ethylene glycol, and glycerol. The deodorant and deodorant composition of the present invention may further comprise a thickener, a surfactant, a perfume or a colorant, or a combination of the above, in order to meet the needs of various applications 1331900, and the added component accounts for 0 5 - 50% of the composition, the thickener is a water-soluble polymer selected from the group consisting of modified starch, cellulose derivatives, proteins, and alginate a group consisting of polyvinyl alcohol (polyvinyl alcohol), polyacrylics, polyester, and polyurethane, and the surfactant includes An anionic surfactant, a cationic surfactant, a nonionic surfactant or an amphoteric surfactant, or a combination of one or more of the above, and the HLB value of the surfactant is between 1 and 丨5. The invention further relates to a pesticide composition comprising an antimicrobially effective amount of water-soluble chitin, one or more agrochemically acceptable metal salts and at least one adjuvant, the weight ratio of the metal salt to the water-soluble chitin 1:10 to 1:500. In the pesticide composition of the present invention, the water-soluble chitin is deacetylated chitin, the deacetylated chitin has a deacetylation degree of 40-6%, and the molecular weight is 5,000. 500,000. In the pesticide composition of the present invention, the water-soluble chitin system may be a chitosan or chitosan oligosaccharide or a combination thereof, and the chitin and chitosan glycosides may be single Ride, double cool, trisaccharide, tetrasaccharide, pentasaccharide, six listen, heptasaccharide, octaose, nine sugar or ten sugar, or a combination of the above. In the pesticide composition of the present invention, the metal ion in the metal salt may be mercury (Hg) ion, tin (Sn) ion, lead (Pb) ion, copper (Cu) ion silver (octal magic ion or zinc (Zn). Ion, the pesticide composition of the present invention may contain one or more of the above 1331900 metal ions. In the pesticide composition of the present invention, the base of the metal salt may be an acetate salt or a borate salt. , bromide salt, carbonate salt, chlorate salt, chi〇ride salt, chromate salt, dichromate salt, citrate salt, A valate salt, a giuc〇nate salt, a nitrate salt, a perchlorate salt, a phosphate salt, a salicylate salt, a sulfate salt or The tartrate salt is composed of one or more of the above combinations. The present invention is also related to an agricultural antimicrobial method, which comprises the use of the pesticide composition of the present invention in a plant or a plant. Some of them are on the ground or on the ground. Because the deacetylation degree of chitosan is generally 7介-1〇〇%, the product is not easy to be cold in water. However, when the deacetylation of acetaminophen and aminoglycoside is in the range of 45_55% Between the acetamide grape ride and the structure of the aminoglycol, the chitosan can be directly dissolved, and the κ stalk is water soluble. Chitin, its chemical formula 4 is as follows: 1331900 In addition to 45-55% of the deacetic acid product, low molecular weight chitin or chitosan sugar is also the specification of water-soluble f-shell, when chitin or chitosan The polymer is degraded to form oligosaccharides. When PP is produced, it is water-soluble. The water-soluble chitin has the property of being able to be formulated into a neutral solution, and has little irritation to the skin. It has good compatibility with other compounds, so it can be used in a wider range than general hull. The water-soluble chitin used in the present invention can be directly dissolved in water by its characteristics, so that the use of an acidic solution can be avoided, so that the pH can be solved. Unstable values, poor results, and The problem of compound incompatibility, and the use of copper, silver, zinc and other metal ions combined with water-soluble chitin, to enhance the antibacterial and anti-mildew effect, by the metal salt formed by the chitin and metal ions into an aqueous solution, condensation Different types of rubber and solid products, suitable for different purposes, thereby achieving anti-microbial function. Since the water-soluble chitin and the water-soluble metal salt of the present invention are mixed, the anti-microbial effect can be achieved, thereby deodorizing and Deodorant, it can also be used in agriculture as a pesticide composition 'application of the pesticide composition to plants and cultivation space' and agriculturally as an antimicrobial method. The composition of the present invention is composed of both water-soluble chitin and a water-soluble metal salt, and the water-soluble chitin is deacetylated chitin, and the deacetylation degree of the chitosanized chitin Between 40 and 60%, and the molecular weight is between 5,000 and 500, 水溶性, the water-soluble chitin can be chitosan oligosaccharide or chitosan oligodomain 'or a combination of the above' The amine oligosaccharide may be a monosaccharide, a sugar, a disaccharide, a tetrasaccharide, a pentasaccharide, a hexasaccharide, a heptasaccharide, an octasaccharide, a pentose or a decasaccharide, or a combination of at least one of the foregoing. 10 1331900 The metal ion in the side metal salt may be a mercury (Hg) ion, a tin (Sn) ion, a lead (Pb) ion, a copper (Cu) ion, a silver (Ag) ion or a zinc (Zn) ion, by the above one or More than one metal ion composition, and the salt base of the metal salt may be an acetic acid salt 'borate salt, br〇mide salt, carbonate salt, chlorate salt, gas. (chl〇ride) salt, chromate salt, dichromate salt, citrate salt, formate salt, giuconate salt, nitric acid salt, A perchlorate salt, a salt salt, a salicylate salt, a suifate salt or a tartaric acid salt, is composed of one or a combination of the above. . The water-soluble quercetin is first dissolved in water and then mixed with the metal salt to form a homogeneous solution. The weight ratio of the metal salt to the water-soluble chitin is between 丨:i 〇 to 1:5 〇〇, dissolved by water. The concentration and weight ratio of chitin and metal salt, control the type of product 'When the ratio of metal salt increases, the water-soluble chitin gradually forms a gel from the liquid, and the concentration (ratio) of the metal salt increases. After a critical value, the product of the three types of water-soluble chitin forming a solid precipitate in solution 'further processing is required for further use, and the liquid product can be incorporated into a surfactant, a thickener, or an organic solvent. Additives such as pigments, perfumes, etc., and the gel product can be used as an antibacterial agent or directly die-cast into a film and a tablet. Another solid product can be filtered to form a dispersion or a dry powder. The organic alcohol compound may be selected from the group consisting of methanol (methan), ethanol, n-propanol (n_pr〇pan〇i), isopropanol, ethylene 1331900 alcohol (ethylene g丨yco丨), and C3. A group of alcohols (glyc〇h〇i), which in turn further comprises a thickener, a surfactant, a perfume or a colorant, or a group of the above. 'The added component accounts for the composition, and the enhancer can be a water-soluble polymer. The lanthanide is selected from the group consisting of starch derivatives, cellulose derivatives, and proteins. , alginate (alginate), polyvinyl alcohol (p〇lyvinyi alcohol), polypropylene phthalic acid polymer (p〇] yacryHcs), polyester (polyester) and polyurethane (p〇Iyureihane) The surfactant, the anionic surfactant, the cationic surfactant, the nonionic surfactant or the amphoteric surfactant, or a combination of the above-mentioned combinations, wherein the HLB value of the surfactant is bounded by 1 _丨5. Other features and advantages of the present invention will be apparent from the following detailed description of the invention. EXAMPLES The following examples are intended to illustrate the invention. These examples are not intended to limit the scope of the invention in any way, but are intended to indicate how to practice the materials and methods of the invention. 1. 1 case 1 Formulation of soluble chitin sound and anti-fungal test 1.1 Formulation Take 1 000 ml of pure water, add 30 g of deacetylated 48% of 1331900 Ethylene, and add 2 g Zinc sulfate was formed into a mucus after stirring for a few hours, and after standing for 48 hours, a gel was obtained. The gel was poured into a Petri dish and baked at 6 ° C for 12 hours to obtain a film which was tested for its mold resistance by the ASTM G21 standard. L2 test method 4 test strain: black bacillus heart er) ATcc 9642 cut 6Cmx2Cm rectangular test piece, flatten it on the culture substrate of the bacteria, after 36. <3 After 7 days of culture, the mold growth characteristics were observed. The U test results are shown in the figure and the second figure. The first picture is a petri dish without a test piece. The culture dish is sprinkled with a test piece, and the second picture is a petri dish with a test piece. The spores were sprinkled outside the test piece and the results showed that the spore growth area was reduced from 95% to 20%. Formulation of the composition of the compound 2 · 1 formula Take 1000 ml of pure water, add 3 grams of deacetylated 48% of the diced chitin, 2 grams of chitosan oligosaccharide and 3 mg of gasification tin, stir i The hour is fully dissolved, and 5G grams of alcohol and 2 grams of eucalyptus essential oil are mixed and used evenly in the mist, and the antibacterial efficacy is verified. 2 2 Calling test method: Staphylococcus aureus... Yarn/ac〇ccw(10)aw) 13 1331900 ATCC 6538
”將試驗菌以平行劃線方式播種在 式片以垂直方向平貼其上經過37。C 37°C > 24 察細菌生長情形 平版培養基上，再將 24小時培養後，觀 2，3试驗結果 由第二圖及第四圖所示，"The test bacteria were sown in parallel lines on the sheet and placed in the vertical direction. After 37 ° C 37 ° C > 24 to observe the growth of the bacteria on the lithographic medium, and then 24 hours of cultivation, 2, 3 test The test results are shown in the second and fourth figures.
之效果，出現 mm的抑菌區間。 溶性甲殼素之_組成物的配方及抗菌和農作物栽培訧龄 3.丨配方 取50公克脫乙醯度48%的脫乙醯幾丁質，再加入1〇 毫克柳·檬酸銀及20公克的藻酸鈉’加到1 〇〇〇毫升的純水 中，攪拌1 小時後得到均勻的水溶液，對於上述水溶液進 行抗菌測試，並進而實施農作物栽培試驗。 3.2抗菌測試 3.2.1方法 °式驗囷種：金黃色葡萄球菌awrews) ATCC 6538 在12支50毫升的試管中分別注入ι〇毫升的上述曱 殼素溶液’再取1毫升不同濃度的菌液（l.〇x〗〇7- 1331900 1 ·〇χ 1 09cfu/ml)注入各個試管中，振盪作用1 0分鐘以後， 取出試管内的溶液，以平版技術法檢測菌數。 3,2.2結果 每10毫升溶液10分種内可以殺死2x 1 07cfu的金黃色 葡萄球菌。 表1:作用1 0分鐘後菌數檢測結果 植菌 1 .Ox 8.0 6.0 4.0 2.0 1.0 濃度 109 xlO8 xlO8 xlO8 xlO8 xlO8 (cfu/ml) 10分 + + + + + + + + + + + + 鐘後菌數 + + + + + 植菌 5.〇χ 3.3 2.5 2.0 1.0 濃度 107 xlO7 xlO7 xlO7 χΙΟ7 (cfu/ml) 10分 鐘後菌數 + + + + + - -The effect is that the inhibition zone of mm appears. Formulation of soluble chitin and composition of antibacterial and crop cultivation age 3. Formulation 50 grams of deacetylated chitin with 48% deacetylation, then 1 mg of silver citrate and 20 g The sodium alginate was added to 1 ml of pure water, and after stirring for 1 hour, a uniform aqueous solution was obtained, and the above aqueous solution was subjected to an antibacterial test, and then a crop cultivation test was carried out. 3.2 Antibacterial test 3.2.1 Method ° Test type: Staphylococcus aureus awrews) ATCC 6538 Into 12 50 ml tubes, respectively, inject ι ml of the above chitin solution 'take another 1 ml of different concentrations of bacteria liquid (l.〇x〗〇7- 1331900 1 ·〇χ 1 09cfu/ml) was injected into each tube, and after 10 minutes of shaking, the solution in the test tube was taken out, and the number of bacteria was detected by the lithographic technique. 3, 2.2 Results 2 x 1 07 cfu of Staphylococcus aureus can be killed in 10 minutes per 10 ml of solution. Table 1: After 1 minute, the number of bacteria is detected. 1Ox 8.0 6.0 4.0 2.0 1.0 Concentration 109 xlO8 xlO8 xlO8 xlO8 xlO8 (cfu/ml) 10 points + + + + + + + + + + + + Number of bacteria + + + + + Phytophthora 5. 〇χ 3.3 2.5 2.0 1.0 Concentration 107 xlO7 xlO7 xlO7 χΙΟ7 (cfu/ml) Number of bacteria after 10 minutes + + + + + - -
-:無菌落滋生 + :菌落少於30大於0 + +:菌落少於300大於30 + + + :菌落大於300 3.3農作物栽培試驗 3.3.1方法 以相鄰二塊4mx3m的栽培基地種植油菜，進行田野測 15 ^ ’將上述甲殼素溶液加水稀釋1_倍 令〜塊基地，每7曰喷灑〗·欠…更，運在其 ，除了 …去、 不喷灑甲殼素 別认貝/ "又*、以外，二塊基地以相同的條件栽培，分 广種植後28及35日從各基地隨機採取1〇個樣本，紀 錄平均重量及莖葉長度。 、 3.3 · 2結果 —___ 均重量（g) 莖葉長/? ('em) 栽種 28 35 28曰 35曰 ---— 方式 曰 曰 基 不噴甲 〇·5〇 土 1.40 土 27.04士 32.30土 殼素 0.11 0.10 1.25 2.21 基 噴甲殼 0.62+ 1.68 土 30.50土 36.0+1 地B 素 0.04 0.60 1.20 .82___-: Aseptic growth +: Colonies less than 30 greater than 0 + +: Colonies less than 300 greater than 30 + + + : Colonies greater than 300 3.3 Crop cultivation test 3.3.1 Method Planting rapeseed with two adjacent 4mx3m cultivation bases Field test 15 ^ 'Dilute the above chitin solution with water 1_ times ~ block base, spray every 7 〗 〗 〖 owe ... more, transported in it, except ... go, do not spray chitin not recognize the shell / " In addition, the two bases were cultivated under the same conditions, and one sample was randomly taken from each base on 28 and 35 days after the wide planting, and the average weight and stem and leaf length were recorded. , 3.3 · 2 Results - ___ Average weight (g) Stem and leaf length /? ('em) Planting 28 35 28曰35曰---- Way 曰曰基不喷甲〇·5〇土1.40 土27.04士32.30土Shell 0.11 0.10 1.25 2.21 base spray shell 0.62+ 1.68 soil 30.50 soil 36.0+1 ground B prime 0.04 0.60 1.20 .82___
[圖式簡單說明】 圖式部分 第一圖係未貼試片的培養皿進行抗黴性試驗結果ι照 片。 第一圖係貼有試片的培養皿進行抗徵性試驗結茱ι ”、' 片° 第三圖係貼有未噴甲殼素濾紙之空白對照組試片培養 皿進行抑菌試驗之結果的照片。 16 1331900 第四圖係貼有噴甲殼素濾紙之空白對照組試片培養m 進行抑菌試驗之結果的照片。[Simple description of the diagram] The first part of the drawing shows the results of the anti-fungal test of the petri dish without the test piece. The first figure is a petri dish with test strips for the test of resistance. 茱 茱 ”, '片° The third figure is the result of the bacteriostatic test of the blank control sample dish with the unsprayed chitin filter paper. Photographs 16 1331900 The fourth photograph is a photograph of the results of a bacteriostatic test in which a blank control sample of a sprayed chitin filter paper was incubated.
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