JP4227984B2 - Composition for improving flavor and taste of food - Google Patents
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- JP4227984B2 JP4227984B2 JP2005329186A JP2005329186A JP4227984B2 JP 4227984 B2 JP4227984 B2 JP 4227984B2 JP 2005329186 A JP2005329186 A JP 2005329186A JP 2005329186 A JP2005329186 A JP 2005329186A JP 4227984 B2 JP4227984 B2 JP 4227984B2
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Description
本発明は、馬鈴薯蛋白質(ポテトプロテイン)を、酵素分解することにより得られる食品の香味・呈味改善機能を有する蛋白質酵素分解物、該蛋白質酵素分解物を有効成分とする食品の香味・呈味改善用組成物、及びその製造方法に関する。 The present invention relates to a protein enzyme degradation product having a function of improving flavor and taste of food obtained by enzymatic degradation of potato protein (potato protein), and a flavor and taste of food containing the protein enzyme degradation product as an active ingredient. It is related with the composition for improvement, and its manufacturing method.
馬鈴薯蛋白質(ポテトプロテイン)は、馬鈴薯からの澱粉の精製工程で、馬鈴薯から澱粉を取り去った後に、繊維質などの固形分を分離除去した馬鈴薯汁液を加熱により高分子蛋白質を熱凝固させ、該熱凝固した高分子蛋白質を回収したものである。この馬鈴薯蛋白質は、水に対する溶解性が低く、また、カゼインやラクトアルブミンのような他の蛋白質に比べ、その消化率も低いということから、飲料や食品への蛋白質材料としての利用に適さず、従来、馬鈴薯蛋白質の利用としては、専ら飼料用蛋白質の原料として用いられるに留まっていた。 Potato protein (potato protein) is a process for purifying starch from potato, and after removing the starch from potato, the potato soup liquid from which solids such as fibers have been separated and removed is heated to heat the polymer protein to coagulate. This is a collection of coagulated polymer protein. This potato protein has low solubility in water, and its digestibility is low compared to other proteins such as casein and lactalbumin, so it is not suitable for use as a protein material in beverages and foods. Conventionally, potato protein has been used only as a raw material for protein for feed.
近年、この馬鈴薯蛋白質を加水分解し、飼料以外に利用する試みがなされている。馬鈴薯蛋白質を飼料以外に利用するこれまでの利用法としては、例えば、「日本醤油研究所雑誌」、vol.2、No.5(1976)第218〜220頁の「ポテトプロテインの利用に関する研究(第1報)」には、ポテトプロテイン(馬鈴薯蛋白質)をブロメライン、プロナーゼ東洋、プロナーゼASのような蛋白分解酵素でそれぞれ分解してアミノ酸液を製造することが報告されている。また、同じく「日本醤油研究所雑誌」、Vol.3、No.2(1977)第75〜76頁の「ポテトプロテインの利用に関する研究(第2報)」には、ポテトプロテインを原料として製麹し、該麹を使用してアミノ酸液を製造することが報告されている。更に、日本醸造協会雑誌、第71巻、第12号(1976)第971〜974頁「ポテトプロテインの利用に関する研究(第3報)」には、ポテトプロテインを塩酸や蛋白分解酵素コクラーゼSSで分解して製造したアミノ酸液を使用して、みりんの仕込に用いることが報告されている。 In recent years, attempts have been made to hydrolyze this potato protein and use it other than feed. As a conventional method of using potato protein in addition to feed, for example, “Research on the use of potato protein” in pages 218-220 of “Japan Soy Sauce Research Institute Magazine”, vol. 2, No. 5 (1976) ( 1st report) reports that potato protein (potato protein) is produced by proteolytic enzymes such as bromelain, pronase Toyo, and pronase AS to produce an amino acid solution. Similarly, “Studies on the Use of Potato Protein (Part 2)” on pages 75-76 of “Japan Soy Sauce Research Institute Magazine”, Vol. 3, No. 2 (1977), made potato protein as a raw material. However, it has been reported that an amino acid solution is produced using the koji. Furthermore, in the Journal of the Japan Brewing Association, Vol. 71, No. 12 (1976), pages 971 to 974 “Study on the Use of Potato Protein (Part 3)”, potato protein is decomposed with hydrochloric acid or proteolytic enzyme coclase SS. It is reported that the amino acid solution produced in this way is used for the preparation of mirin.
また、特開平7−143861号公報(特許第2967121号公報)には、ポテトプロテインを塩酸等で加水分解して得られたアミノ酸液を、ビートアミノ酸と混合し、精製したものを、醤油標準色度が56以上の一夜漬物類、スープ類、めんつゆ類、海産魚卵類、納豆用のたれ類の調味に用いることについて開示されており、特開昭64−20060号公報(特許第2751161号公報)には、ポテトプロテインを酸性、中性、又はアルカリプロテアーゼを使用して酵素分解して得られる平均アミノ酸残基3〜5の、消化吸収性と栄養価を高めたペプチド組成物を栄養組成物として用いることについて開示されている。 Japanese Patent Application Laid-Open No. 7-143861 (Japanese Patent No. 2967121) discloses a soy sauce standard color obtained by mixing and purifying an amino acid solution obtained by hydrolyzing potato protein with hydrochloric acid or the like with beet amino acid. It is disclosed that it is used for seasoning overnight pickles, soups, noodle soups, marine fish eggs, and natto sauces with a degree of 56 or more, and JP-A 64-20060 (Japanese Patent No. 2751161). ) Includes a peptide composition with an average digestive absorbency and nutritional value of 3 to 5 average amino acid residues obtained by enzymatic degradation of potato protein using acidic, neutral or alkaline protease It is disclosed about using as.
更に、特開平8−140585号公報には、馬鈴薯汁液を約60℃から約120℃に加熱して熱凝固した蛋白質にし、この熱凝固した蛋白質に水酸化ナトリウム水溶液、水酸化カルシウム水溶液などのアルカリ性水溶液を加えて分散した後に、pHを約5.0から約9.0にし、この熱凝固蛋白質分散液に蛋白質分解酵素を加えて高分子の蛋白質を分解して低分子馬鈴薯蛋白質を製造し、馬鈴薯蛋白質を水に溶解し易くして、飲料や食品に蛋白質補強材として利用するに適するようにすることについて開示されている。
上記のように、馬鈴薯蛋白質の利用を図る目的で、馬鈴薯蛋白質の加水分解等の処理が行われているが、該馬鈴薯蛋白質の加水分解処理は、いずれも該蛋白質の低分子化を行い、該蛋白質の溶解性や消化性等を改善して、その飲料や食品への蛋白質材料としての利用を図る程度に留まるものである。
Furthermore, Japanese Patent Application Laid-Open No. 8-140585 discloses that potato juice is heated from about 60 ° C. to about 120 ° C. to be a heat-coagulated protein, and this heat-coagulated protein is subjected to alkaline such as sodium hydroxide aqueous solution or calcium hydroxide aqueous solution. After adding and dispersing the aqueous solution, the pH is adjusted to about 5.0 to about 9.0, and a protein degradation enzyme is added to the thermocoagulated protein dispersion to decompose the high molecular protein to produce a low molecular weight potato protein. It is disclosed that potato protein is easily dissolved in water so as to be suitable for use as a protein reinforcing material in beverages and foods.
As described above, for the purpose of utilizing potato protein, hydrolysis of potato protein and the like are performed, and all of the hydrolysis treatment of potato protein reduces the molecular weight of the protein, The solubility and digestibility of protein are improved, and the use as a protein material for beverages and foods is limited.
一方、従来から、蛋白質を分解したアミノ酸等の調味液の分野で、その調味液の望ましくない臭いを除去する処理が行われている。例えば、特開平9−313130号公報には、酵母エキスに含まれる酵母臭等を、平均膜孔径0.05〜1μmの精密濾過膜で濾過し、除去する方法が開示されている。また、WO98/46089号公報には、酵母エキス特有の着色や臭いをイオン交換樹脂と接触させ、着色や臭い物質を吸着除去する方法が開示されている。 On the other hand, conventionally, in the field of seasoning liquids such as amino acids obtained by decomposing proteins, treatments for removing undesirable odors from the seasoning liquids have been performed. For example, Japanese Patent Application Laid-Open No. 9-313130 discloses a method of removing yeast odor and the like contained in a yeast extract by filtering with a microfiltration membrane having an average membrane pore size of 0.05 to 1 μm. Further, WO98 / 46089 discloses a method of bringing a coloring or odor peculiar to a yeast extract into contact with an ion exchange resin and adsorbing and removing the coloring or odorous substance.
他方、蛋白質を分解したアミノ酸等の調味液の分野で、麹や麹菌を用いて、蛋白質分解物の臭気等を抑え、香味良好なアミノ酸等の調味液を製造する方法も開示されている。例えば、特開平9−75031号公報には、豚皮を蛋白質分解酵素で加水分解して得た水溶性蛋白質に、食塩及び醤油麹を添加して発酵、熟成させ、豚皮の異臭成分による臭いを抑えた、風味豊かな醤油風味の調味料を製造する方法について、開示されている。また、特開平8−224062号公報には、動物性或いは植物性の蛋白質の分解物(酸分解、酵素分解等)に、アスペルギルス・オリゼに属する微生物由来の酵素を添加し、所定時間、所定温度で処理することにより、動物性或いは植物性の蛋白質に存在する生体特有の臭気を望ましい風味に改良する方法について開示されている。 On the other hand, in the field of seasoning liquids such as amino acids obtained by decomposing proteins, a method for producing a seasoning liquid such as amino acids having good flavor while suppressing odor of protein degradation products using koji or koji molds is also disclosed. For example, Japanese Patent Application Laid-Open No. 9-75031 discloses that a water-soluble protein obtained by hydrolyzing pig skin with a proteolytic enzyme is fermented and aged by adding salt and soy sauce cake, and smells due to off-flavor components of pig skin A method for producing a flavorful soy sauce-flavored seasoning that suppresses the above is disclosed. Further, JP-A-8-224062 discloses that an enzyme derived from a microorganism belonging to Aspergillus oryzae is added to a degradation product (acid degradation, enzymatic degradation, etc.) of an animal or plant protein, for a predetermined time at a predetermined temperature. The method of improving the odor peculiar to the living body which exists in animal protein or vegetable protein to desirable flavor by processing by this is disclosed.
上記のように、蛋白質を酸や酵素を用いて分解することにより、呈味の強い調味料を製造することができることから、その蛋白質分解物の利用性を向上するために、種々の蛋白質の分解方法や風味・呈味の改善方法が提案されている。しかしながら、従来の蛋白質を酸や酵素を用いて分解する方法における改良は、その蛋白質分解物の風味・呈味を向上する範囲に留まり、今までに、その分解された蛋白質が、動物系エキスや酵母エキスのような蛋白質分解物の風味・呈味を向上する機能や、サルファー臭(けもの様臭)のマスキング機能を有するようなものは得られていない。例えば、上記特開平9−75031号公報や特開平8−224062号公報に開示されるもののように、酸や酵素で分解された蛋白質を、麹や麹菌で処理するものも知られているが、該処理も該処理によって製造される蛋白質の分解物の風味や呈味を向上する範囲に留まるもので、得られた分解物が、動物系エキスや酵母エキス等の風味・呈味を向上する機能や、サルファー臭(けもの様臭)のマスキング機能を有するようなものでは無い。 As described above, a seasoning with a strong taste can be produced by degrading a protein using an acid or an enzyme, so that the degradation of various proteins can be improved in order to improve the utilization of the protein degradation product. Methods and methods for improving flavor and taste have been proposed. However, improvements in the conventional method for degrading proteins using acids and enzymes are limited to the extent of improving the flavor and taste of the protein degradation products. Nothing has been obtained that has the function of improving the flavor and taste of protein degradation products such as yeast extract and the masking function of sulfur odor (kemono-like odor). For example, as disclosed in the above-mentioned JP-A-9-75031 and JP-A-8-224062, there is also known a method in which a protein decomposed with an acid or an enzyme is treated with koji or koji. The treatment also remains within the range of improving the flavor and taste of the protein degradation product produced by the treatment, and the obtained degradation product has a function of improving the flavor and taste of animal extracts and yeast extracts. In addition, it does not have a masking function of sulfur odor (kemono-like odor).
本発明の課題は、動物系エキス及び酵母エキス等において、望ましくないサルファー臭等の特異の臭気を抑えてその風味・呈味を向上する方法、及び、その他の酸、酵素分解物或いは発酵生産物、又は調味食品等におけるサルファー臭(けもの様臭、例えば、生臭さ、固有の動物臭、鳥獣肉特有の臭みのような臭い)のマスキングを行い、該分解物或いは発酵生産物、、又は調味食品等の風味・呈味を向上する方法、及び、そのための食品の風味・呈味改善機能を有する物質、更には、該物質を有効成分とする食品の風味・呈味改善用組成物を提供することにある。 The object of the present invention is to improve the flavor and taste of animal extracts and yeast extracts by suppressing specific odors such as undesired sulfur odor, and other acids, enzymatic degradation products or fermentation products. Or masking sulfur odor (food-like odor, such as raw odor, peculiar animal odor, odor peculiar to poultry meat) in seasoned foods, etc., and the decomposed product or fermentation product, or seasoning Provided are a method for improving the flavor and taste of foods, a substance having a function of improving the flavor and taste of foods, and a composition for improving the taste and taste of foods containing the substance as an active ingredient There is to do.
本発明者は、馬鈴薯蛋白質(ポテトプロテイン)の利用に関し、該馬鈴薯蛋白質の加水分解物について鋭意検討する中で、馬鈴薯蛋白質を、麹菌及び蛋白分解酵素で分解することにより得られる蛋白質酵素分解物が、動物系エキス及び酵母エキスの望ましくないサルファー臭等の特異の臭気を抑えて、該動物系エキス及び酵母エキス等の風味・呈味を向上する機能を有することを見い出し、本発明を完成するに至った。
本発明の蛋白質酵素分解物は、その他の酸、酵素分解物或いは発酵生産物、又はその他の調味エキスのような調味食品等においても、サルファー臭(けもの様臭)をマスキングする効果を有し、該分解物或いは発酵生産物等の風味・呈味を向上する機能を有する。
The present inventor has intensively studied the hydrolyzate of potato protein with respect to the use of potato protein (potato protein). In order to complete the present invention, it has been found that the animal extract and yeast extract have a function of suppressing the characteristic odor of undesirable sulfur odor and the like and improving the flavor and taste of the animal extract and yeast extract. It came.
The protein enzyme degradation product of the present invention has an effect of masking a sulfur odor (kemono-like odor) even in seasoned foods such as other acids, enzyme degradation products or fermentation products, or other seasoning extracts. In addition, it has a function of improving the flavor and taste of the decomposed product or fermentation product.
本発明において、本発明の蛋白質酵素分解物は馬鈴薯蛋白質を麹菌及び蛋白分解酵素で分解することにより製造することができる。馬鈴薯蛋白質を麹菌及び蛋白分解酵素で分解して、本発明の蛋白質酵素分解物を製造するに際しては、馬鈴薯蛋白質を麹菌及び蛋白分解酵素で分解した分解液を、キレート樹脂で処理することにより、精製、色度の調整をすることができる。更に、本発明においては、馬鈴薯蛋白質を、麹菌及び蛋白分解酵素で分解し、キレート樹脂で処理した酵素分解液を、真空乾燥し、粉末化することによって、本発明の蛋白質酵素分解物を粉末状の蛋白質酵素分解物として製造することができる。
本発明は、本発明の製造方法によって製造された蛋白質酵素分解物を有効成分とする食品の香味・呈味改善用組成物を包含する。
In the present invention, the protein enzyme degradation product of the present invention can be produced by degrading potato protein with koji mold and protease. When producing potato protein by degrading potato protein with Aspergillus or proteolytic enzyme to produce the protein enzyme degradation product of the present invention, purification is performed by treating a decomposition solution obtained by digesting potato protein with Aspergillus or proteolytic enzyme with a chelating resin. The chromaticity can be adjusted. Furthermore, in the present invention, the potato protein is decomposed with koji mold and proteolytic enzyme, and the enzyme degradation solution treated with chelate resin is vacuum-dried and pulverized, whereby the protein enzyme degradation product of the present invention is powdered. It can be produced as a protein enzyme degradation product.
The present invention includes a composition for improving the flavor and taste of foods comprising as an active ingredient a protein enzyme degradation product produced by the production method of the present invention.
すなわち具体的には本発明は、(1)馬鈴薯蛋白質を、麹菌及び蛋白分解酵素で分解することにより得られる蛋白質酵素分解物を有効成分とする食品の香味・呈味改善剤や、(2)食品の香味・呈味改善が、動物系エキス及び/又は酵母エキスの香味・呈味改善、或いはサルファー臭のマスキングであることを特徴とする上記(1)記載の蛋白質酵素分解物を有効成分とする食品の香味・呈味改善剤や、(3)食品の香味・呈味改善剤が、サルファー臭のマスキング剤であることを特徴とする上記(1)記載の蛋白質酵素分解物を有効成分とする食品の香味・呈味改善剤からなる。 Specifically, the present invention relates to (1) a flavor / taste improving agent for foods comprising, as an active ingredient, a protein enzyme degradation product obtained by degrading potato protein with Aspergillus or protease. flavor-improving taste of food, and animal-based extract and / or flavor-improving taste of yeast extract, or above, wherein the a masking sulfur smell (1) protein enzymatic decomposition products of the active ingredient according And ( 3 ) the food flavor / taste improving agent, or ( 3 ) the food flavor / taste improving agent is a sulfur odor masking agent; It consists of flavor and taste improvers for foods .
また本発明は、(4)馬鈴薯蛋白質を、麹菌及び蛋白分解酵素で分解することにより得られる蛋白質酵素分解物を、食品に添加することを特徴とする食品の香味・呈味改善方法や、(5)食品の香味・呈味改善が、動物系エキス及び/又は酵母エキスの香味・呈味の改善、或いはサルファー臭のマスキングであることを特徴とする上記(4)記載の食品の香味・呈味改善方法や、(6)食品の香味・呈味改善方法が、サルファー臭のマスキング方法であることを特徴とする上記(4)記載の食品の香味・呈味改善方法や、(7)馬鈴薯蛋白質を、麹菌及び蛋白分解酵素で分解することを特徴とする食品の香味・呈味改善剤の製造方法や、(8)馬鈴薯蛋白質を、麹菌及び蛋白分解酵素で分解し、該分解液をキレート樹脂で処理することを特徴とする上記(7)記載の食品の香味・呈味改善剤の製造方法や、(9)キレート樹脂で処理した酵素分解液を乾燥し、粉末化することを特徴とする上記(8)記載の香味・呈味改善剤の製造方法からなる。 In addition, the present invention provides ( 4 ) a method for improving flavor and taste of food, characterized by adding to the food a protein enzyme degradation product obtained by degrading potato protein with koji mold and proteolytic enzyme, 5) flavor, taste-improving foods, animal-based extracts and / or improvement of flavor-taste of yeast extract, or the (4, characterized in that the masking of sulfur smell) flavor Tei food according The method for improving flavor and taste of foods as described in (4) above , wherein the method for improving taste and ( 6 ) the method for improving flavor and taste of foods are masking methods for sulfur odor, and ( 7 ) potato A method for producing a flavor and taste improver for foods characterized by degrading a protein with koji mold and a proteolytic enzyme; and ( 8 ) decomposing potato protein with koji mold and a proteolytic enzyme and chelating the decomposition solution. Treat with resin And manufacturing method of the above (7), wherein the food flavor, taste-improving agent characterized, (9) drying the enzyme hydrolyzate was treated with a chelating resin, characterized in that powdered above (8) It consists of the manufacturing method of the flavor and taste improvement agent of description.
本発明の馬鈴薯蛋白質酵素分解物は、動物系エキス及び酵母エキスの望ましくないサルファー臭等の特異の臭気を抑えて、該動物系エキス及び酵母エキス等の風味・呈味を向上する機能を有し、また、その他の酸、酵素分解物或いは発酵生産物、又は調味食品等におけるサルファー臭(けもの様臭)のマスキングを行い、該分解物或いは発酵生産物等の風味・呈味を向上する機能を有することから、動物系エキス及び酵母エキス、或いは、その他の酸、酵素分解物或いは発酵生産物、又は調味食品等における香味・呈味改善用組成物として用いることができる。また、本発明の蛋白質酵素分解物は、従来、専ら飼料用蛋白質の原料としてか利用できなかった馬鈴薯蛋白質を、風味・呈味を向上する機能を有する蛋白質材料として、種々の飲料や食品へ利用することを可能とする。従来より、酵素と麹菌を使用して、蛋白質を分解し、利用することが行われていたが、それらは概して長期間の反応時間を要しているのに、本発明の方法は、比較的短期間の反応で有用な蛋白質酵素分解物を得ることができるというメリットがある。 The potato protein enzyme degradation product of the present invention has a function of suppressing the specific odor such as an undesired sulfur odor of animal extracts and yeast extracts and improving the flavor and taste of the animal extracts and yeast extracts. In addition, masking of sulfur odor (kemono-like odor) in other acids, enzyme degradation products or fermentation products, or seasoning foods, etc., and the function of improving the flavor and taste of the degradation products or fermentation products Therefore, it can be used as a composition for improving flavor and taste in animal extracts and yeast extracts, or other acids, enzyme degradation products, fermentation products, seasoning foods, and the like. In addition, the protein enzyme degradation product of the present invention can be used in various beverages and foods as a protein material having a function of improving flavor and taste, using potato protein, which could not be used exclusively as a raw material for protein for feed. It is possible to do. Conventionally, enzymes and koji molds have been used to decompose and use proteins, but they generally require a long reaction time, but the method of the present invention is relatively There is a merit that a useful protein enzyme degradation product can be obtained in a short-term reaction.
本発明は、馬鈴薯蛋白質を、麹菌及び蛋白分解酵素で分解することにより得られる食品の香味・呈味改善機能を有する蛋白質酵素分解物からなる。該本発明の蛋白質酵素分解物は、動物系エキス及び酵母エキスの望ましくないサルファー臭等の特異の臭気を抑えて、該動物系エキス及び酵母エキス等の風味・呈味を向上する機能、及び、その他の酸、酵素分解物或いは発酵生産物、又は調味食品等におけるサルファー臭(けもの様臭)のマスキングを行い、該分解物或いは発酵生産物等の風味・呈味を向上する機能を有する。 The present invention comprises a protein enzyme degradation product having a function of improving the flavor and taste of foods obtained by degrading potato protein with koji mold and protease. The protein enzyme degradation product of the present invention suppresses a specific odor such as an undesired sulfur smell of animal extracts and yeast extracts, and improves the flavor and taste of the animal extracts and yeast extracts, and It masks sulfur odor (kemono-like odor) in other acids, enzyme degradation products or fermentation products, seasoning foods, etc., and has a function of improving the flavor and taste of the decomposition products or fermentation products.
本発明の蛋白質酵素分解物の製造原料となる馬鈴薯蛋白質は、水洗した馬鈴薯を磨砕し、該馬鈴薯の磨砕汁液から固形物を分離、除去し、該磨砕汁液を約60℃〜120℃に加熱して熱凝固した蛋白質を回収することにより、製造することができる。一般的に、工業的製法としては、馬鈴薯からデンプンを製造する際に、そのデンプン精製工程で、馬鈴薯からデンプンを取り去った後に、分離、濃縮、乾燥することにより製造することができる。 The potato protein used as a raw material for producing the protein-enzyme degradation product of the present invention grinds potato washed with water, separates and removes solids from the ground mash of the potato, and removes the ground mash from about 60 ° C to 120 ° C. It can be produced by recovering the heat-coagulated protein after heating. In general, as an industrial production method, when starch is produced from potato, it can be produced by removing, concentrating and drying starch from potato in the starch purification step.
本発明において、本発明の蛋白質酵素分解物を製造するために用いられる麹菌及び蛋白分解酵素としては、特に限定されないが、麹菌としては、特に適する菌としてアスペルギルス・オリゼ(Aspergillus oryzae)を挙げることができる。また、望ましい蛋白分解酵素としては、微生物由来或いは動植物由来のアルカリ性プロテアーゼ、中性プロテアーゼ、酸性プロテアーゼ等の蛋白分解酵素を挙げることができる。麹菌は、麹の形で用いることができ、例えば、麹菌アスペルギルス・オリゼは米麹の形で用いることができる。 In the present invention, the koji mold and proteolytic enzyme used for producing the proteolytic enzyme of the present invention are not particularly limited, but as koji mold, particularly suitable bacteria include Aspergillus oryzae. it can. Examples of desirable proteolytic enzymes include proteolytic enzymes such as alkaline proteases, neutral proteases, and acidic proteases derived from microorganisms or animals and plants. Aspergillus can be used in the form of a cocoon, for example, Aspergillus oryzae can be used in the form of a rice bran.
本発明において、本発明の蛋白質酵素分解物を製造するには、例えば、上記のようにして調製した馬鈴薯蛋白質に加水し、pH及び温度を調整し、これに蛋白質分解酵素及び米麹のような麹菌を加えて、穏やかに分解することにより、製造することができる。この酵素分解反応における、pH、温度、蛋白質分解酵素又は麹菌の添加量、反応時間については、最適な組み合わせを適宜選択して、本発明の蛋白質酵素分解物を製造することができる。該分解物は、不溶成分を除去した後に、キレート樹脂で処理し、該分解物の精製と色度の調整とを行うことができる。また、該キレート樹脂で処理した酵素分解液は、乾燥し、粉末化することにより、粉末状の蛋白質酵素分解物として製造することができる。該乾燥手段としては、真空乾燥、噴霧乾燥等、適宜の乾燥手段を用いることができるが、真空乾燥を特に好ましい乾燥手段として用いることができる。 In the present invention, the protein-enzyme degradation product of the present invention can be produced by, for example, adding water to the potato protein prepared as described above, adjusting the pH and temperature, and adding it to proteolytic enzymes and rice bran. It can be produced by adding gonococci and gently degrading. In the enzymatic decomposition reaction, the optimal combination of the pH, temperature, the amount of proteolytic enzyme or koji mold added, and the reaction time can be appropriately selected to produce the protein enzymatic degradation product of the present invention. The decomposition product can be treated with a chelate resin after removing insoluble components to purify the decomposition product and adjust the chromaticity. In addition, the enzyme degradation solution treated with the chelate resin can be produced by drying and pulverizing it as a powdery protein enzyme degradation product. As the drying means, suitable drying means such as vacuum drying and spray drying can be used, but vacuum drying can be used as a particularly preferable drying means.
本発明の蛋白質酵素分解物は、種々の飲料や食品へ利用する蛋白質材料として、及び、動物系エキス及び酵母エキスの望ましくないサルファー臭等の特異の臭気を抑えて、該動物系エキス及び酵母エキス等の風味・呈味を向上する機能、及び、その他の酸、酵素分解物或いは発酵生産物、又は調味食品等におけるサルファー臭(けもの様臭)のマスキングを行い、該分解物或いは発酵生産物等の風味・呈味を向上する機能を有する蛋白質酵素分解物として、該蛋白質酵素分解物を有効成分とする食品の香味・呈味改善用組成物として用いることができる。本発明の蛋白質酵素分解物を食品の香味・呈味改善用組成物として用いる場合の、該蛋白質酵素分解物の食品に対する添加量は、好ましくは0.1〜1.5%の範囲で添加されるが、適用食品に応じて、好ましい添加量を広い範囲で設定することができる。 The protein enzyme degradation product of the present invention is a protein material for use in various beverages and foods, and suppresses a specific odor such as an undesired sulfur odor of animal extracts and yeast extracts, and the animal extracts and yeast extracts. The function of improving the flavor and taste such as, and the masking of sulfur odor (kemono-like odor) in other acids, enzyme degradation products or fermentation products, seasoning foods, etc., and the degradation products or fermentation products As a protein enzyme degradation product having a function of improving the flavor and taste of the food, it can be used as a composition for improving flavor and taste of foods containing the protein enzyme degradation product as an active ingredient. When the protein enzyme degradation product of the present invention is used as a food flavor / taste improving composition, the amount of the protein enzyme degradation product added to the food is preferably 0.1 to 1.5%. However, a preferable addition amount can be set in a wide range depending on the food to be applied.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
<実施例 I>
馬鈴薯蛋白150gに水1500mlを加えて懸濁させ、水酸化ナトリウムを3g加えてpH7.7に調整し、90〜95℃に15分間保持した後50℃まで冷却し、蛋白分解酵素(ノボザイムズジャパン株式会社製「アルカラーゼ2.4L」)1.5gと米麹(阿部商店製)30gを加えて、攪拌しながら40時間反応させたところ、反応液のpHは5.0であった。反応終了後、90〜95℃に加熱して15分間保持して蛋白分解酵素と米麹の活性を失活させて流水中で約60℃に冷却した。
<Example I>
Add 1500 ml of water to 150 g of potato protein and suspend it, add 3 g of sodium hydroxide to adjust the pH to 7.7, hold at 90-95 ° C. for 15 minutes, cool to 50 ° C., and remove protease (Novozymes) When 1.5 g of "Alcalase 2.4L" manufactured by Japan Co., Ltd.) and 30 g of rice bran (Abe Shoten) were added and reacted for 40 hours with stirring, the pH of the reaction solution was 5.0. After completion of the reaction, the mixture was heated to 90 to 95 ° C. and held for 15 minutes to deactivate the protease and rice bran activity and cooled to about 60 ° C. in running water.
冷却後の反応液にろ過助剤としてのパーライト(東興パーライト工業株式会社製「トプコ・パーライトNo.34」)50gを加えて15分間攪拌した後吸引ろ過して、残渣を水洗し、黒みかかった淡褐黄色液1470mlを得た。得られた液体は、水分93.7%、Brix8.0、全窒素0.6%であった。次いで、弱酸性陽イオン交換樹脂(味の素ファインテクノ株式会社製「キレート樹脂ホクエツPF」)200mlを内径3cmのガラス円筒に充填したカラムに上記ろ液を流速200ml/時で通過させた後、更に、イオン交換水を流速200ml/時で通してカラム内に残留するろ液を流出させて処理液1450mlを得た。この淡黄色の処理液に30%水酸化ナトリウム溶液5.6ml加えてpH5.7に調整し、この調整液を真空乾燥して、淡黄色粉末状の蛋白加水分解物82.3gを得た。
得られた蛋白加水分解物は、水分4.45%、食塩0.68%、全窒素8.0%であった。該得られた蛋白加水分解物のアミノ酸アナライザー分析の結果と分子量分布測定結果を図4に示す(アミノ酸アナライザー分析値:図4a;分子量分布測定結果:図4b)。実施例Iの製造工程をフロー図として、図1に示す。
50 g of pearlite (“Topco Pearlite No. 34” manufactured by Toko Perlite Kogyo Co., Ltd.) as a filter aid was added to the reaction solution after cooling, and the mixture was stirred for 15 minutes and then suction filtered, the residue was washed with water and darkened. 1470 ml of pale brown yellow liquid was obtained. The obtained liquid had a water content of 93.7%, Brix 8.0, and total nitrogen of 0.6%. Next, after passing the filtrate through a column filled with 200 ml of a weakly acidic cation exchange resin (“Chelate Resin Hokuetsu PF” manufactured by Ajinomoto Fine Techno Co., Ltd.) in a glass cylinder having an inner diameter of 3 cm, the flow rate was further 200 ml / hour. Ion exchange water was passed at a flow rate of 200 ml / hour to flow out the filtrate remaining in the column to obtain 1450 ml of a treatment liquid. 5.6 ml of 30% sodium hydroxide solution was added to this pale yellow treatment solution to adjust the pH to 5.7, and this adjustment solution was vacuum dried to obtain 82.3 g of a pale yellow powdery protein hydrolyzate.
The obtained protein hydrolyzate had a water content of 4.45%, sodium chloride of 0.68%, and total nitrogen of 8.0%. The results of amino acid analyzer analysis and molecular weight distribution measurement results of the obtained protein hydrolyzate are shown in FIG. 4 (amino acid analyzer analysis values: FIG. 4a; molecular weight distribution measurement results: FIG. 4b). The manufacturing process of Example I is shown as a flow chart in FIG.
<実施例 II>
米麹を株式会社秋田今野商店製「特別吟醸用種麹」に変更し、実施例Iと同様の手法を用いて淡黄色粉末状の蛋白加水分解物85.2gを得た。得られた蛋白加水分解物は、水分2.96%、食塩0.63%、全窒素8.5%であった。
<Example II>
The rice bran was changed to “special brewer's seeds” manufactured by Akita Imano Co., Ltd., and 85.2 g of a light yellow powdery protein hydrolyzate was obtained using the same method as in Example I. The obtained protein hydrolyzate had a water content of 2.96%, sodium chloride of 0.63%, and total nitrogen of 8.5%.
<実施例 III>
酵素を天野エンザイム株式会社製「パパインW−40」に変更し、実施例Iと同様の手法を用いて淡黄色粉末状の蛋白加水分解物46.5gを得た。得られた蛋白加水分解物は、水分2.22%、食塩1.96%、全窒素5.7%であった。該得られた蛋白加水分解物のアミノ酸アナライザー分析の結果と分子量分布測定結果を図4に示す(アミノ酸アナライザー分析値:図4a;分子量分布測定結果:図4c)。
<Example III>
The enzyme was changed to “Papain W-40” manufactured by Amano Enzyme Co., Ltd., and 46.5 g of a light yellow powdery protein hydrolyzate was obtained using the same method as in Example I. The obtained protein hydrolyzate had a water content of 2.22%, sodium chloride of 1.96% and total nitrogen of 5.7%. The results of amino acid analyzer analysis and molecular weight distribution measurement results of the obtained protein hydrolyzate are shown in FIG. 4 (amino acid analyzer analysis values: FIG. 4a; molecular weight distribution measurement results: FIG. 4c).
<実施例 IV>
酵素をヤクルト薬品工業株式会社製「パンチダーゼNP−2」に変更し、実施例Iと同様の手法を用いて淡黄色粉末状の蛋白加水分解物52.9gを得た。得られた蛋白加水分解物は、水分4.45%、食塩0.81%、全窒素6.3%であった。
<Example IV>
The enzyme was changed to “Pantidase NP-2” manufactured by Yakult Pharmaceutical Co., Ltd., and 52.9 g of a light yellow powdery protein hydrolyzate was obtained using the same method as in Example I. The obtained protein hydrolyzate had a water content of 4.45%, sodium chloride of 0.81% and total nitrogen of 6.3%.
<比較例 I(麹を利用して分解)>
馬鈴薯蛋白100gに水1000mlを加えて懸濁させ、水酸化ナトリウムを2g加えてpH7.8に調整し、80〜85℃に15分間保持した後50℃まで冷却し、米麹(株式会社樋口松之助商店製「ダイヤモンドC」)20gを加えて、攪拌しながら44時間反応させたところ、反応液のpHは4.6であった。反応終了後、80〜85℃に加熱して15分間保持して米麹の活性を失活させて、流水中で約60℃に冷却した。冷却後の反応液にろ過助剤としてパーライト(東興パーライト工業株式会社製「トプコ・パーライトNo.34」)20gを加えて15分間攪拌した後吸引ろ過して、残渣を水洗し、淡黄色液900mlを得た。得られた液体は、水分97%、Brix3.2、全窒素0.05%であった。この液体を真空乾燥して、淡黄色粉末状の蛋白加水分解物27gを得た。得られた蛋白加水分解物は、水分3.86%、食塩1.3%、全窒素1.7%であった。比較例Iの製造工程をフロー図として、図2に示す。
<Comparative Example I (decomposition using soot)>
Add 1000 ml of water to 100 g of potato protein, suspend it, add 2 g of sodium hydroxide to adjust the pH to 7.8, hold at 80-85 ° C. for 15 minutes, cool to 50 ° C., rice bran (Matsunosuke Higuchi Co., Ltd.) When 20 g of “Diamond C” (trade name) was added and reacted for 44 hours with stirring, the pH of the reaction solution was 4.6. After completion of the reaction, the mixture was heated to 80 to 85 ° C. and held for 15 minutes to deactivate the rice bran activity, and cooled to about 60 ° C. in running water. To the reaction liquid after cooling, 20 g of pearlite (“Topco Pearlite No. 34” manufactured by Toko Perlite Kogyo Co., Ltd.) as a filter aid was added and stirred for 15 minutes, followed by suction filtration, the residue was washed with water, and 900 ml of a pale yellow liquid Got. The resulting liquid was 97% moisture, Brix 3.2, and 0.05% total nitrogen. This liquid was vacuum-dried to obtain 27 g of a light yellow powdery protein hydrolyzate. The obtained protein hydrolyzate had a water content of 3.86%, sodium chloride of 1.3% and total nitrogen of 1.7%. The manufacturing process of Comparative Example I is shown as a flow chart in FIG.
<比較例 II(蛋白分解酵素を利用して分解)
馬鈴薯蛋白100gに水1000mlを加えて懸濁させ、水酸化ナトリウムを2g加えてpH7.5に調整し、90〜95℃に15分間保持した後50℃まで冷却し、蛋白分解酵素(ノボザイムズジャパン株式会社製「アルカラーゼ2.4L」)1.0gを加えて、攪拌しながら18時間反応させたところ、反応液のpHは6.8であった。この反応液に蛋白分解酵素(ノボザイムズジャパン株式会社製「フレーバーザイム500L」)2.0gと蛋白分解酵素(天野エンザイム株式会社製「プロテアーゼM」)0.5gを加え、50℃にて攪拌しながら24時間反応させた。)
<Comparative Example II (degradation using proteolytic enzyme)
1000 g of potato protein was suspended in 1000 ml of water, 2 g of sodium hydroxide was added to adjust to pH 7.5, maintained at 90-95 ° C. for 15 minutes, cooled to 50 ° C., and proteolytic enzyme (Novozymes) When 1.0 g of “Alcalase 2.4 L” manufactured by Japan Corporation was added and reacted for 18 hours with stirring, the pH of the reaction solution was 6.8. To this reaction solution, 2.0 g of proteolytic enzyme (“Flavorzyme 500L” manufactured by Novozymes Japan Co., Ltd.) and 0.5 g of proteolytic enzyme (“Protease M” manufactured by Amano Enzyme Co., Ltd.) are added and stirred at 50 ° C. The reaction was continued for 24 hours. )
反応終了後、90〜95℃に加熱して30分間保持して蛋白分解酵素を失活させて、流水中で約60℃に冷却した。冷却後の反応液にろ過助剤としてのパーライト10gを加えて15分間攪拌した後吸引ろ過して、残渣を水洗し、黒ずんだ黄色い液765mlを得た。得られた液体は、水分93.3%、Brix7.8、全窒素0.74%であった。この液体を活性炭(二村化学工業株式会社製「S−W50」)を22g加えて30分間攪拌した後吸引ろ過して、残渣を水洗し、朝黒く黄色い液800mlを得た。この液体を真空乾燥して、淡黄褐色粉末状の蛋白加水分解物47.0gを得た。得られた蛋白加水分解物は、水分4.65%、食塩0.91%、全窒素9.97%であった。比較例IIの製造工程をフロー図として、図3に示す。 After completion of the reaction, the mixture was heated to 90 to 95 ° C. and held for 30 minutes to deactivate the protease and cooled to about 60 ° C. in running water. 10 g of pearlite as a filter aid was added to the cooled reaction solution and stirred for 15 minutes, followed by suction filtration. The residue was washed with water to obtain 765 ml of a dark yellow liquid. The obtained liquid had a water content of 93.3%, Brix7.8, and total nitrogen of 0.74%. To this liquid, 22 g of activated carbon (“S-W50” manufactured by Nimura Chemical Co., Ltd.) was added and stirred for 30 minutes, followed by suction filtration, and the residue was washed with water to obtain 800 ml of a dark yellow liquid. This liquid was vacuum-dried to obtain 47.0 g of protein hydrolyzate in the form of a light tan powder. The obtained protein hydrolyzate had a water content of 4.65%, sodium chloride of 0.91%, and total nitrogen of 9.97%. The manufacturing process of Comparative Example II is shown in FIG. 3 as a flowchart.
<風味・呈味の比較試験1>
本発明の実施例で製造した本発明の蛋白質酵素分解物を用いて、豚肉抽出エキスに対する風味・呈味改善の比較試験を行った。すなわち、豚肉10gに、水100ml及び食塩0.3gを加え、加熱・抽出した。該抽出エキスに、前記実施例I及び実施例IIで調製した馬鈴薯蛋白質の酵素分解物を0.1g添加して、豚肉抽出エキスに対する風味・呈味改善の効果について比較評価した。比較試験の結果を、図5bに示す。図5bの表中、「マスキング効果」とは、主として豚肉抽出エキス中におけるサルファー臭のマスキング効果を表す。なお、この比較試験例1の操作のフローを、図5aに示す。
<Flavoration /
Using the protein enzyme degradation product of the present invention produced in the examples of the present invention, a flavor / taste improvement test for pork extract was performed. That is, 100 ml of water and 0.3 g of sodium chloride were added to 10 g of pork, followed by heating and extraction. 0.1 g of the enzymatic degradation product of potato protein prepared in Example I and Example II was added to the extract, and the effects of flavor and taste improvement on the pork extract were compared and evaluated. The result of the comparative test is shown in FIG. In the table of FIG. 5b, “masking effect” mainly represents the masking effect of sulfur odor in the pork extract. In addition, the flow of operation of this comparative test example 1 is shown in FIG. 5a.
<風味・呈味の比較試験2>
比較試験1に準じて、本発明の実施例で製造した本発明の蛋白質酵素分解物を用いて、豚肉抽出エキスに対する風味・呈味改善の比較試験を行った。すなわち、比較試験例1の操作に従って、豚肉抽出エキスを調製した。該抽出エキスに、前記実施例I及び実施例 IIIで調製した馬鈴薯蛋白質の酵素分解物を1.0g添加して、豚肉抽出エキスに対する風味・呈味改善の効果について比較評価した。比較試験の結果を、図6bに示す。図6bの表中、「マスキング効果」とは、主として豚肉抽出エキス中におけるサルファー臭のマスキング効果を表す。なお、この比較試験例2の操作のフローを、図6aに示す。
<Flavoration / Taste Comparison Test 2>
In accordance with
<風味・呈味の比較試験3>
本発明の実施例で製造した本発明の蛋白質酵素分解物を用いて、チキン抽出エキスに対する風味・呈味改善の比較試験を行った。すなわち、チキンエキス4gに、水100mlを加え、加熱し、該抽出エキスに、前記実施例I及び実施例例IIIで調製した馬鈴薯蛋白質の酵素分解物を0.2g添加して、チキン抽出エキスに対する風味・呈味改善の効果について比較評価した。比較試験の結果を、図7bに示す。図7bの表中、「マスキング効果」とは、主としてチキン抽出エキス中におけるサルファー臭のマスキング効果を表す。なお、この比較試験例3の操作のフローを、図7aに示す。
<Flavoration / Taste Comparison Test 3>
Using the protein enzyme degradation product of the present invention produced in the examples of the present invention, a flavor / taste improvement test for chicken extract was conducted. That is, 100 ml of water was added to 4 g of the chicken extract, heated, and 0.2 g of the enzymatic decomposition product of the potato protein prepared in Example I and Example III was added to the extract. The effect of flavor and taste improvement was compared and evaluated. The result of the comparative test is shown in FIG. In the table of FIG. 7b, “masking effect” mainly represents the masking effect of sulfur odor in the chicken extract. In addition, the flow of operation of this comparative test example 3 is shown in FIG. 7a.
<風味・呈味の比較試験4>
上記比較試験に準じて調製した酵母エキス及びチキンエキスを、本発明の実施例 IIで製造した本発明の蛋白質酵素分解物と処方に従って混合し、加熱し、100℃に達した後、冷却した。該抽出エキスおける風味・呈味の改善の効果について比較評価した。比較試験の結果を、図8に示す。図8の表中、「マスキング効果」とは、該抽出エキス中におけるサルファー臭のマスキング効果を表す。図8に示されるように、酵母エキスとチキンエキスのような混合食品でも、マスキング効果がある。
<Flavoration and taste comparison test 4>
The yeast extract and chicken extract prepared according to the above comparative test were mixed with the protein enzyme degradation product of the present invention produced in Example II of the present invention in accordance with the prescription, heated, reached 100 ° C., and then cooled. A comparative evaluation was made on the effect of improving the flavor and taste of the extract. The result of the comparative test is shown in FIG. In the table of FIG. 8, “masking effect” represents the masking effect of sulfur odor in the extract. As shown in FIG. 8, mixed foods such as yeast extract and chicken extract also have a masking effect.
<風味・呈味の向上比較試験5>
本発明の実施例で製造した本発明の蛋白質酵素分解物を用いて、豚肉抽出エキスに対する風味・呈味向上の比較試験を行った。すなわち、豚肉10gに、水100ml、食塩0.3gを加え、加熱し、該抽出エキスに、前記実施例Iで調製した馬鈴薯蛋白質の酵素分解物を0.1g添加して、豚肉抽出エキスに対する風味・呈味向上の効果について比較評価した。試料C〜Fは、試料Bを0.3%食塩水にて2倍、3倍、4倍、5倍に希釈した試料をそれぞれ試料C、試料D、試料E、試料Fとして用意した。比較試験(官能検査)の結果を、図9bに示す。比較試験の結果、風味・呈味ともに向上することが確認された。得られた発明品添加エキスは発明品無添加品よりも、風味・呈味の力価が、3−4倍程度向上するという効果が得られた。なお、この比較試験例5の操作のフローを、図9aに示す。
<Flavor / taste improvement comparative test 5>
Using the protein enzyme degradation product of the present invention produced in the examples of the present invention, a comparative test of flavor and taste improvement with respect to the pork extract was performed. That is, 100 g of water and 0.3 g of salt are added to 10 g of pork, heated, and 0.1 g of the enzymatic decomposition product of the potato protein prepared in Example I is added to the extract to obtain a flavor of the pork extract. -Comparative evaluation was made on the effect of improving taste. Samples C to F were prepared as Sample C, Sample D, Sample E, and Sample F, respectively, in which Sample B was diluted 2 times, 3 times, 4 times, and 5 times with 0.3% saline. The result of the comparative test (sensory test) is shown in FIG. 9b. As a result of the comparative test, it was confirmed that both flavor and taste were improved. The obtained invention-added extract had an effect that the flavor and taste titers were improved by about 3 to 4 times that of the product without invention. In addition, the operation flow of this comparative test example 5 is shown in FIG. 9a.
<風味・呈味の比較試験6>
本発明の実施例 Iおよび比較例 I及び比較例 IIで製造した本発明の蛋白質酵素分解物を用いて、豚肉抽出エキスに対する風味・呈味改善の比較試験を行った。すなわち、豚肉10gに、水100ml及び食塩0.3gを加え、加熱・抽出した。該抽出エキスに、前記実施例 I及び比較例 I及び比較例 IIで調整した馬鈴薯蛋白質の酵素分解物を0.1g添加して、豚肉抽出エキスに対する風味・呈味改善の効果について比較評価した(「風味向上」、「呈味向上」、「マスキング効果」について、「大きな効果あり」、「効果あり」、「効果なし」の3つの基準で評価を行なった。)。比較試験の結果を、図10に示す。図10bの表中、「マスキング効果」とは、主として豚肉抽出エキス中におけるサルファー臭のマスキング効果を表す。なお、この比較試験例6の操作フローを、図10aに示す。
<Flavoration and taste comparison test 6>
Using the protein enzyme degradation product of the present invention produced in Example I, Comparative Example I and Comparative Example II of the present invention, a comparative test of flavor / taste improvement for the pork extract was performed. That is, 100 ml of water and 0.3 g of sodium chloride were added to 10 g of pork, followed by heating and extraction. 0.1 g of the enzymatic degradation product of potato protein prepared in Example I, Comparative Example I, and Comparative Example II was added to the extract, and the effects of flavor and taste improvement on the pork extract were compared and evaluated . ( "wind taste improvement", "improving taste", for the "masking effect", "there is a big effect", "Yes effect", was evaluated at the three criteria of "no effect".). The result of the comparative test is shown in FIG. In the table of FIG. 10b, “masking effect” mainly represents the masking effect of sulfur odor in the pork extract. In addition, the operation flow of this comparative test example 6 is shown in FIG.
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JP5680284B2 (en) * | 2009-04-22 | 2015-03-04 | 株式会社東洋新薬 | Method for producing potato protein with improved taste and aroma |
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CA1198072A (en) * | 1982-02-22 | 1985-12-17 | Nicholas Melachouris | Process for the preparation of protein hydrolysates |
US4871575A (en) * | 1988-03-07 | 1989-10-03 | Deltown Chemurgic Corporation | Flavor and texture improved canned animal flesh and process |
JPH0339049A (en) * | 1989-07-07 | 1991-02-20 | Ajinomoto Co Inc | Production of low-molecular peptide mixture |
DE4339743C1 (en) * | 1993-11-22 | 1995-08-31 | Waldemar Dr Neumueller | Process for the preparation of proteins from a protein-containing substance |
JP3448344B2 (en) * | 1994-04-18 | 2003-09-22 | 日本食品化工株式会社 | Peptide composition |
JPH09100297A (en) * | 1995-10-03 | 1997-04-15 | Ajinomoto Co Inc | New pyroglutamylpeptide |
JP3373156B2 (en) * | 1998-06-29 | 2003-02-04 | コスモ食品株式会社 | Method for producing water-soluble potato peptide |
WO2002032231A1 (en) * | 2000-10-19 | 2002-04-25 | Edens, Luppo | Protein hydrolysates |
WO2002036802A1 (en) * | 2000-10-30 | 2002-05-10 | Ajinomoto Co., Inc. | Method for producing protein hydrolysate |
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