200946031 六、發明說明： 【發明所屬之技術領域】 本發明係關於可去除魚醬油中所含之重金屬類，製作 - 提高魚醬油之安全性且不損及魚醬油特徵（鮮味等之有效 . 成分）之食品之去除魚醬油中之重金屬的方法。 【先前技術】 « 〇 利用沙丁魚、烏賊等之魚類內臟等之魚醬油中，含有 大量的重金屬類。 然而，雖然至今生產地域居民的飲食習慣仍經常地攝 取如此之魚醬油者，但至今仍未有特定疾病（如痛痛病等 之公害）發生例之報告。 於如此理由下，傳統以來，魚醬油未曾施以去除重金 屬處理而商品化係現實情況。 然而，以活用魚醬油之有效成分、作爲調味料之全國 ® 推廣•輸出海外等之消費擴大爲目標時，就吃的安全、安 全之觀點上，含重金屬成爲問題，預測必須進行該去除處 理。 然而，未發現著眼自魚醬油等之水產加工品去除重金 屬類之傳統技術文獻。 不僅水產加工品本身，爲有效利用而不廢棄處理帆立 貝或烏賊等之內臟殘渣，揭示自內臟殘渣去除重金屬的方 '法如下述文獻。 〔專利文獻1〕特開2001-137810號公報 200946031 〔專利文獻2〕特開2000-2963 89號公報 〔專利文獻3〕特開2006-5 5 7 1 7號公報 〔專利文獻4〕特開2000-78959號公報 【發明內容】 . 發明所欲解決之課題 上述例如專利文獻1係記載使用甲酸、乳酸、醋酸等 之有機酸、或鹽酸、硫酸、磷酸等之無機酸，成爲PH3〜 & 3.5之弱酸性，進而由蛋白質分解酵素的作用，分解與重 金屬鍵結之蛋白質，使重金屬自蛋白質解離，使重金屬溶 出於酸處理液中，由螯合劑等分離已溶出於水溶液中之重 金屬類之方法。 但是，魚醬油等之水產加工品時，使含有重金屬類溶 出於酸處理液中之專利文獻1之方法，爲提高重金屬類之 去除效率，必須以pH3〜3.5之低pH處理，以低pH處理 時，魚醬油中之蛋白質可溶化而溶出，因味道改變，所以 © 不能直接作爲調味料。 亦即，對於即使未溶出而殘留的蛋白質，因酵素活性 降低，即使可作爲水產萃取物利用，若對如魚醬油之發酵 食品本身進行利用時，有招來商品品質降低之問題。 尤其如專利文獻1記載之方法，倂用低pH之酸處理 液及蛋白質分解酵素進行處理時，將更加擴大上述問題點 ，如此方法係侷限於用以安全廢棄魚醬油殘渣之前處理方 法，或利用魚醬油殘渣作爲飼料或肥料等時之處理方法， -6- 200946031 不適用作爲用以利用爲發酵食品魚醬油之處理方法者。 另外’專利文獻2係記載使接觸磷酸水溶液、有機酸 、鹽酸、硝酸、硼酸或硫酸之水溶液，使溶出重金屬之方 - 法。 • 專利文獻2或同樣的專利文獻3記載之方法，使用的 酸濃度高時，砷的去除率佳，但將混入食品添加物外的酸 於食品，就食品之安全性必須進行再評估。 φ 另外，有效成分酵素有失去活性之虞，或使用的酸濃 度低時，有砷的去除率低等之缺點，爲魚醬油不能採用之 方法。 接著，於專利文獻4記載之方法，使食品直接接觸食 品添加物之沸石以去除之方法，可預測連有效成分同時被 去除，另外，於使接觸沸石前，因爲使用荷性鈉等以進行 pH調整，所以作爲調味料之味覺改變，或因爲食品安全 性之問題，爲魚醬油不能採用之方法。 G 本發明係有鑑於上述傳統的課題者，提供不損及魚醬 油所含有蛋白質等之鮮味成分，有效地去除魚醬油中之重 金屬類，可達成有效地利用作爲調味料或以此爲原料之去 除魚醬油中之重金屬的方法爲目的。 課題之解決手段 申請專利範圍第1項之本發明之去除魚醬油中之重金 屬的方法係於魚醬油中添加食品添加物之單寧或含單寧之 食品添加物，進行固液分離，在不損及鮮味成分等之有效 200946031 成分下自魚醬油中去除固形物爲特徵者。 申請專利範圍第2項之發明，單寧的量係相對於丨份 之魚醬油’以重量比0.001〜0.5之比例進行添加爲特徵者 〇 申請專利範圍第3項之發明，於申請專利範圍第i項 或第2項中，以膜分離或離心分離或濾器過濾進行固液分 離爲特徵者。 發明之功效 依據本發明方法處理魚醬油時，可有效率地減低魚醬 油中之重金屬類至規定濃度以下，並同時去除重金屬類後 之魚醬油係在不損及顯示鮮味之胺基酸下維持品質，就安 全性更加提高之魚醬油，具有可商品化之效果。 另外，不僅作爲安全性更加提高之魚醬油之調味料， 亦具有可期待利用此於原料之食品補充品等之廣範圍的利 用效果。 接著，本發明方法係無須調整pH等之處理條件少之 簡易處理方法，因利用食品添加物，所以製品安全性亦無 問題，有達成利用促進本方法之效果。 用以實施發明之最佳型態 本發明方法係使如上述之魚醬油，混合單寧或含單寧 之食品添加物，進行處理後，分離、去除魚醬油中之沈澱 物之液體作爲調味料。 200946031 {旦胃’單寧的量係必須在不損及呈味性之程度，相對 於1份之魚醬油’以重量比0.001〜0.5之比例添加爲宜， 以0_05〜0.1倍尤佳。 - 含單寧之食品添加物係考慮例如柿澀。 • 使魚醬油與助濾劑接觸之時間爲數分鐘〜1天程度， 但以1 2小時〜24小時爲宜，處理溫度係在不失去有效成 分之溫度進行’只要於—1〇〜9(rc之溫度範圍內，任一種 0 溫度皆可。 -1 0°c w T時’因魚醬油冷凍而明顯地發生品質降低 ，90°c以上時發生風味降低。 另外’當然適當攪拌可加快凝聚反應。 自添加助濾、劑之魚醬油，用以去除沈澱物之具體方法 ’可列舉冷凍融解法、藉由濾布等之過濾法、藉由高速離 心分離機之方法等，但以藉由濾布過濾爲宜。 亦考量冷凍融解、離心分離時，有連魚醬油之必要成 Ο 分亦被去除之虞’濾布係具有可僅去除藉由添加助濾劑發 生的沈澱成分之確實性，另外，此等過濾的方法中，濾布 亦具有最廉價之優點。 最後係以處理魚醬油中之重金屬類成1 ppm以下爲宜 ’處理的重複次數雖依魚醬油中之重金屬類量，添加助濾 劑之使用量等而異，但以2〜5次爲宜。 另外，作爲分離處理後魚醬油及沈澱物之方法，只要 如前述之離心分離、傾析、過濾法等之一般可分離處理殘 渣及處理液之方法，使用任何方法皆可。 -9- 200946031 如上所述，自通常所生產之魚醬油去除重金屬後，作 爲安全調味料，可出貨於市場。 另外，亦可使經去除重金屬之魚醬油乾燥’作爲營養 補給品或粉末調味料等之食品加工原料利用。 使魚醬油乾燥時，若進行加熱乾燥，因爲有味道香味 之呈味性改變，或魚醬油中酵素活性消失之虞’所以以真 空乾燥或真空冷凍乾燥等之加熱以外之方法乾燥爲宜。 本發明方法係因爲成爲處理對象之魚醬油含重金屬含 量多，所以列舉必須注意安全性之沙丁魚內臟、烏賊內臟 、竹莢魚內臟、其他魚貝類內臟爲原料之魚醬油’即使油 脂含量多者仍可不進行脫脂處理利用。 【實施方式】 〔實施例1〕 於10mL之魚醬油，加入1ml之單寧水溶液（0.1、 1.0 ' 5.0% )、或蒸餾水、或 5%之葡萄糖酸內酯（ ◎200946031 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to the removal of heavy metals contained in fish soy sauce, which are produced to improve the safety of fish soy sauce without detracting from the characteristics of fish sauce (smell, etc.). A method of removing heavy metals from fish soy sauce in foods. [Prior Art] « 鱼 Fish soy sauce using sardines, squid and other fish viscera contains a large amount of heavy metals. However, although the eating habits of the local residents have been frequently taken to such fish soy sauce, there have been no reports of occurrences of specific diseases (such as public health diseases such as pain and pain). For this reason, in the past, fish soy sauce has not been applied to remove heavy metal treatment and commercialization is a reality. However, when it is aimed at expanding the consumption of the active ingredients of fish soy sauce and the national ® promotion and export of the seasonings, it is a problem that the heavy metal is a problem in terms of safety and safety of eating, and it is predicted that the removal must be performed. However, no conventional technical literature has been found to remove heavy metal species from aquatic products such as fish sauce. In addition to the processed products of the aquatic products, the visceral residue such as the scallops or the squid is discarded, and the method of removing heavy metals from the visceral residue is disclosed. [Patent Document 1] JP-A-2001-137810, JP-A No. 2000-46031 [PATENT DOCUMENT 2] JP-A-2000-199693 (Patent Document 3) JP-A-2006-5 5 7 1 7 (patent document 4) In the above-mentioned patent document 1, it is described that an organic acid such as formic acid, lactic acid or acetic acid or an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid is used, and it is PH 3 to & 3.5. The weak acidity, and in turn, by the action of proteolytic enzymes, decomposing proteins bound by heavy metals, dissociating heavy metals from proteins, dissolving heavy metals in acid treatment liquids, and separating heavy metals dissolved in aqueous solutions by chelating agents, etc. . However, in the case of a fish processed product such as fish sauce, the method of Patent Document 1 in which a heavy metal is dissolved in an acid treatment liquid is required to be treated at a low pH of pH 3 to 3.5 and to be treated at a low pH in order to improve the removal efficiency of heavy metals. When the protein in the fish sauce is dissolved and dissolved, the taste is changed, so © cannot be used directly as a seasoning. In other words, even if the protein remains in the protein which is not eluted, the enzyme activity is lowered, and even if it is used as an aquatic extract, when the fermented food itself such as fish sauce is used, there is a problem that the quality of the product is lowered. In particular, in the method described in Patent Document 1, when the treatment with a low-pH acid treatment solution and a proteolytic enzyme is carried out, the above problem is further expanded, and the method is limited to a method for safely disposing of the fish sauce residue before use, or utilization. When the fish sauce residue is used as a feed or fertilizer, -6- 200946031 is not applicable as a treatment method for using the fish sauce as a fermented food. Further, Patent Document 2 describes a method in which an aqueous solution of a phosphoric acid aqueous solution, an organic acid, hydrochloric acid, nitric acid, boric acid or sulfuric acid is contacted to dissolve a heavy metal. • In the method described in Patent Document 2 or the same Patent Document 3, when the acid concentration used is high, the removal rate of arsenic is good. However, when the acid other than the food additive is mixed into the food, the safety of the food must be re-evaluated. φ In addition, when the active ingredient enzyme has inactivity, or when the acid concentration used is low, the removal rate of arsenic is low, which is a method that cannot be used for fish sauce. Next, in the method described in Patent Document 4, the method in which the food is directly contacted with the zeolite of the food additive is removed, and it is predicted that the active ingredient is simultaneously removed, and the pH is adjusted by using sodium or the like before contacting the zeolite. Adjustment, so as the taste of the seasoning changes, or because of food safety issues, the method can not be used for fish sauce. In the present invention, it is possible to effectively remove heavy metals in fish soy sauce without damaging the umami ingredients such as protein contained in fish sauce, and to achieve effective use as a seasoning or as a raw material. The purpose of removing heavy metals from fish soy sauce is for the purpose. Solution to Problem The method for removing heavy metals in fish soy sauce according to the invention of claim 1 is to add a tannin of a food additive or a food additive containing tannin to a fish soy sauce for solid-liquid separation. Effective damage to umami ingredients, etc. 200946031 The composition is characterized by the removal of solids from fish sauce. In the invention of claim 2, the amount of tannin is added to the ratio of 0.001 to 0.5 by weight of the fish soy sauce of 丨 为 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 In item i or item 2, it is characterized by membrane separation or centrifugation or filter filtration for solid-liquid separation. Effect of the Invention According to the method of the present invention, when the fish sauce is treated, the heavy metal in the fish sauce can be efficiently reduced to a predetermined concentration or lower, and the fish sauce after removing the heavy metal is not damaged by the amino acid which shows the umami taste. The fish soy sauce, which maintains the quality and improves safety, has a commercial effect. In addition, it is not only a seasoning of fish sauce which is more safe, but also a wide range of effects that can be expected to utilize the food supplement of the raw material. Next, the method of the present invention does not require a simple treatment method for adjusting the pH and the like, and the use of the food additive is not problematic in terms of product safety, and the effect of promoting the method is achieved. BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention is a method for separating and removing a liquid in a fish soy sauce as a seasoning after the fish soy sauce, the mixed tannin or the tannin-containing food additive is treated as described above. . 200946031 The amount of tannin in the stomach should not be impaired to the extent of taste, and it is preferably added in a ratio of 0.001 to 0.5 by weight relative to 1 part of the soy sauce, preferably 0_05 to 0.1 times. - Food supplements containing tannins are considered, for example, persimmon. • The time for contacting the fish sauce with the filter aid is several minutes to one day, but it is preferably from 12 hours to 24 hours. The treatment temperature is carried out at a temperature that does not lose the active ingredient, as long as it is -1〇~9 ( Within the temperature range of rc, any temperature can be 0. -1 0°cw T When 'the fish sauce is frozen, the quality is obviously reduced, and the flavor is reduced when the temperature is above 90°C. In addition, of course, proper agitation can accelerate the coagulation reaction. The specific method for removing the sediment from the addition of the filter aid and the fish soy sauce can be exemplified by a freeze-thaw method, a filtration method using a filter cloth, a method by a high-speed centrifugal separator, etc., but by filtration. It is advisable to filter the cloth. It is also considered that when the freeze-thaw and the centrifugal separation are carried out, the necessary ingredients of the fish sauce are also removed. The filter cloth has the reliability of removing only the precipitation component which is caused by the addition of the filter aid. In addition, in the filtration method, the filter cloth also has the advantage of being the least expensive. Finally, it is preferable to treat the heavy metal in the fish sauce to be 1 ppm or less, and the number of repetitions of the treatment is increased according to the amount of heavy metals in the fish sauce. help The amount of the agent to be used may vary, but it is preferably 2 to 5 times. Further, as a method of separating the fish soy sauce and the precipitate after the treatment, the residue can be separated as described above by centrifugation, decantation, filtration, or the like. As for the method of treating the liquid, any method can be used. -9- 200946031 As described above, since the fish sauce which is usually produced is removed from heavy metals, it can be shipped as a safe seasoning, and can be removed from the heavy metal. The dried fish soy sauce is used as a food processing raw material such as a nutritional supplement or a powder seasoning. When the fish sauce is dried, if it is heated and dried, the taste of the flavor is changed, or the enzyme activity in the fish sauce disappears. Therefore, it is preferable to dry by vacuum drying or vacuum freeze-drying, etc. The method of the present invention is because the fish sauce to be treated has a large content of heavy metals, so the sardine viscera, squid viscera, and bamboo pods which must be taken care of for safety are listed. Fish squid, other fish and shellfish viscera as raw material of fish soy sauce 'even if the oil content is high, it can not be degreased . [Embodiment Example 1] in 10mL of fish sauce, was added 1ml of an aqueous solution of tannin (0.1, 1.0 '5.0%), or distilled water, or 5% gluconolactone (◎
Glucono-delta-lactone; GDL)，攪伴後，以離心分離（ 8000rpm，15分鐘）進行固液分離。 加入5mL之硝酸於lmL之各處理後之上清液及未處 理之魚醬油，進行加熱分解。 自已進行各處理之魚醬油去除Cd之結果如表1所示 〇 分解液之Cd濃度（ppm)係以ICP發光分析法測定 -10- 200946031Glucono-delta-lactone; GDL), after stirring, solid-liquid separation was carried out by centrifugation (8000 rpm, 15 minutes). 5 mL of nitric acid was added to 1 mL of each of the supernatant and the untreated fish sauce for heat decomposition. The results of removing Cd from the fish soy sauce of each treatment are shown in Table 1. C The Cd concentration (ppm) of the decomposition liquid is determined by ICP emission spectrometry -10- 200946031
Cd去除率係由處理前後之Cd濃度算出° 〔表1〕 添加劑 未處理 單寧水溶令 夜 蒸餾水 GDL 水溶液 5% 0.1% 1% 5% 魚醬油之Cd濃度 (ppm) 4.3 1.2 0.3 0.2 1.5 1.5 Cd之去除率 (%) — 72 93 95 65 65 認爲添加單寧水溶液之魚醬油之Cd去除結果係比添 加蒸餾水、或葡萄糖酸內酯（GDL )水溶液之魚醬油有明 顯的效果。 另外，測定處理後之魚醬油之總氮、游離胺基酸量、 乳酸量、抗氧化性之結果與未處理時比較，如表2所示。 由該結果確認依本發明相關處理，機能性無明顯變化 〇 〔表2〕 單寧水溶液濃度 (wt% ) 0.1 1 5 未處理 總氮 (g/lOOml) 2.17 2.16 2.21 2.20 總游離胺基 (mg/l〇〇ml) 8250 7890 8020 8270 乳酸量 (mg/ioomi) 2280 2500 2350 2100 抗氧化性 (β mol/ml) 1.40 1.23 1.90 1.08 -11 - 200946031 〔實施例2〕The Cd removal rate is calculated from the Cd concentration before and after treatment. [Table 1] Additive untreated tannin water soluble night distilled water GDL aqueous solution 5% 0.1% 1% 5% Cd concentration of fish soy sauce (ppm) 4.3 1.2 0.3 0.2 1.5 1.5 Cd Removal rate (%) — 72 93 95 65 65 It is considered that the Cd removal result of the fish sauce added with the aqueous tannin solution is more effective than the fish sauce added with distilled water or an aqueous solution of gluconolactone (GDL). Further, the results of measuring the total nitrogen, the amount of free amino acid, the amount of lactic acid, and the oxidation resistance of the fish soy sauce after the treatment were compared with those of the untreated, as shown in Table 2. From the results, it was confirmed that there was no significant change in the functional properties according to the treatment of the present invention [Table 2] Aqueous solution concentration of tannin (wt%) 0.1 1 5 Total untreated nitrogen (g/lOOml) 2.17 2.16 2.21 2.20 Total free amine group (mg /l〇〇ml) 8250 7890 8020 8270 Amount of lactic acid (mg/ioomi) 2280 2500 2350 2100 Oxidation resistance (β mol/ml) 1.40 1.23 1.90 1.08 -11 - 200946031 [Example 2]
於 10mL 之魚醬油，加入 O.lmL、0.5mL、lmL、3mL 之柿單寧（三桝嘉七商店股份有限公司製強力sumiol) ，攪拌後，以離心分離（SOOOrpm ’ 15分鐘）進行固液分 離。 加入5mL之硝酸於lmL之各處理後之上清液及未處 理之魚醬油，進行加熱分解。 自已進行各處理之魚醬油去除Cd之結果如表3所示 〇 分解液之Cd濃度（ppm)係以ICP發光分析法測定 〇In 10 mL of fish sauce, add O.lmL, 0.5 mL, 1 mL, 3 mL of persimmon tannin (strong sumiol made by Sancha Jiaqi Store Co., Ltd.), stir, and centrifuge for separation (SOOO rpm '15 minutes) for solid-liquid separation. . 5 mL of nitric acid was added to 1 mL of each of the supernatant and the untreated fish sauce for heat decomposition. The results of removing Cd from the fish soy sauce of each treatment are shown in Table 3. C The Cd concentration (ppm) of the decomposition liquid is determined by ICP emission spectrometry.
Cd去除率係由處理前後之Cd濃度算出。 〔表3〕 添加劑 未處理 柿單寧 0.1 mL 0.5 mL 1 mL 3 mL 魚醬油之Cd濃度 (ppm) 3.1 1.1 0.7 0.3 0.2 Cd之去除率 (%) — 65 77 90 94 關於柿單寧，亦添加於魚醬油，進行固液分離’確認 可得到與實施例1相同的之C d去除效果。The Cd removal rate was calculated from the Cd concentration before and after the treatment. [Table 3] Additive untreated persimmon tannin 0.1 mL 0.5 mL 1 mL 3 mL Cd concentration of fish soy sauce (ppm) 3.1 1.1 0.7 0.3 0.2 Cd removal rate (%) — 65 77 90 94 About persimmon tannin, also added In the fish sauce, solid-liquid separation was confirmed, and the same Cd removal effect as in Example 1 was obtained.