JP2005278522A - New mirin and method for producing the same - Google Patents
New mirin and method for producing the same Download PDFInfo
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本発明は、経時的な褐変増色が起こりにくく、かつ香味良好なみりん及びその製造方法に関する。 The present invention relates to mirin that is less prone to browning over time and has a good flavor, and a method for producing the same.
一般にみりんは、蒸きょうした糯米を米麹及びアルコールと共に仕込み、糖化、熟成して得られる調味料であるが、多量の糖類、アミノ酸やペプチド等を含有するために、清酒等の他の醸造物と比較すると経時的に褐変増色しやすく、この点が品質劣化の要因となっている。みりんの褐変増色は糖類とアミノ酸やペプチド等の窒素成分からアミノカルボニル反応によって生成するものに起因すると考えられている。みりん中の糖類、あるいはアミノ酸やペプチドを低減させるとアミノカルボニル反応の基質が減少することになり褐変増色すなわち着色が抑制される。しかしながら、糖類は甘みを付与するというみりんの最も重要な機能を担う必須成分であり、それを低減することはみりんの風味や調味料としての機能に大きな影響を及ぼすために好ましくない。また、アミノ酸やペプチドはみりんの成分中、経時的な褐変増色への寄与が最も高いが、旨みやコクの付与に関与するみりんにとって必須の成分であり、これらも糖類と同様に低減することはみりんの品質低下につながるので好ましくない。 Generally, mirin is a seasoning that is obtained by adding steamed rice with rice bran and alcohol, saccharification and aging, but contains a large amount of sugar, amino acids, peptides, etc., so other brews such as sake Compared to the above, it is easy to brown and increase in color over time, and this is a factor of quality deterioration. It is thought that the browning of mirin is caused by the aminocarbonyl reaction generated from saccharides and nitrogen components such as amino acids and peptides. When sugars, amino acids, or peptides in mirin are reduced, the substrate for aminocarbonyl reaction is reduced, and browning, that is, coloring is suppressed. However, saccharide is an essential component that plays the most important function of mirin, which imparts sweetness, and it is not preferable to reduce it because it greatly affects the taste of mirin and its function as a seasoning. In addition, amino acids and peptides have the highest contribution to browning and color increase over time, but they are essential for mirin, which is involved in the addition of umami and richness. It is not preferable because it leads to a decrease in quality of mirin.
アミノカルボニル反応を抑制する方法として、基質を低減させる以外の方法としてはpHの調整が挙げられる。アミノカルボニル反応はpHが高いほど反応が促進されることが知られており、みりんにおいてもpHを下げると経時着色が抑制されることが知られている。これまでみりんのpHを下げる方法として、生酸性を有する焼酎麹菌(特開昭57−105183号公報)やリゾープス属麹菌(特開昭63−152970号公報)を使用したみりんの製造方法や、掛米である糯米を、乳酸菌を添加した水に浸漬し、水切りした後蒸煮して得られる蒸し糯米を使用することにより、pHを下げる方法(特開平11―113555号公報)が提案されている。しかしながら、これらの方法はみりん醪の状態でpHを低下する方法であり、その場合、醪中のpHの低下に伴い醪中の米麹に由来する酸性プロテアーゼの活性が上昇するため、生成されるみりんは着色反応の基質であるアミノ酸やペプチドの含有量が必要以上に多くなり、pHの低下による経時褐変増色抑制効果が十分に発揮されない。また、みりん醪、みりん醪圧搾液、みりん等にグルコースオキシダーゼを添加、作用させてみりんのpHを低下させる方法(特開2003−304860公報)が提案されている。この方法はみりん醪圧搾液やみりんにも適用可能であるが、十分にpHが低下したみりんを得るためには数日を要し、また過酸化水素の除去が必要であるなど製造上の問題がある。以上はすべて有機酸を増量することによりpHを低下させる方法であるが、過剰な有機酸は香味に影響を及ぼすためみりんの品質にとって望ましくない。 As a method for suppressing the aminocarbonyl reaction, pH adjustment may be mentioned as a method other than reducing the substrate. It is known that the higher the pH of the aminocarbonyl reaction, the more the reaction is promoted. In mirin, it is known that coloring with time is suppressed when the pH is lowered. Conventionally, as a method for lowering the pH of mirin, a method for producing mirin using shochu-bacteria having bioacidity (Japanese Patent Laid-Open No. 57-105183) or Rhizopus spp. (Japanese Patent Laid-Open No. 63-152970), There has been proposed a method (JP-A-11-113555) for lowering pH by using steamed glutinous rice obtained by immersing glutinous rice, which is rice, in water to which lactic acid bacteria have been added, draining it, and steaming. However, these methods are methods for lowering the pH in the state of mirin koji, and in this case, the activity of acidic protease derived from rice koji in koji increases with a decrease in pH in koji, so that it is generated. Mirin has an excessive content of amino acids and peptides which are substrates for the coloring reaction, and the effect of inhibiting browning and increase in color due to a decrease in pH is not sufficiently exhibited. In addition, there has been proposed a method for reducing the pH of mirin by adding glucose oxidase to mirinpox, mirinpox pressed liquid, mirin, etc., and causing it to act (JP-A-2003-304860). This method can also be applied to mirin-squeezed juice and mirin, but it takes several days to obtain mirin with a sufficiently low pH, and it is necessary to remove hydrogen peroxide. There is. All of the above are methods of lowering the pH by increasing the amount of organic acid, but excessive organic acid affects the flavor and is undesirable for mirin quality.
溶液のpHを調整する公知の技術としてはイオン交換体を用いる方法がある。特にH型強酸性陽イオン交換体で溶液を処理することにより、有機酸を増加させることなく溶液のpHを低下させることができる。カラム状のH型強酸性陽イオン交換体に溶液を通液する場合、ある一定量を通液すると交換体の水素イオンがすべて溶液中に溶出してしまうため、それ以上通液を行っても通過液のpHは低下しない。したがって、H型強酸性陽イオン交換体を用いて溶液のpHを低下させる場合、1バッチにおける溶液の処理量は通過液のpH低下が終了する量より少なくして行われている。しかしながら、従来の方法でみりんをH型の陽イオン交換体で処理すると、pHが低下すると共にみりん中のアミノ酸やペプチド等の窒素成分がイオン交換体の樹脂に交換されることにより低減してしまい、旨みやコクの少ない品質の劣ったみりんとなってしまう。また、みりん中の香気成分も同様に低減してしまう。このように、従来の方法により単にH型強酸性陽イオン交換体処理するだけでは香味良好なみりんを製造することは困難であった。 As a known technique for adjusting the pH of the solution, there is a method using an ion exchanger. In particular, by treating the solution with an H-type strongly acidic cation exchanger, the pH of the solution can be lowered without increasing the organic acid. When passing a solution through a columnar H-type strongly acidic cation exchanger, if a certain amount is passed, all the hydrogen ions in the exchanger will elute into the solution. The pH of the flow-through does not decrease. Therefore, when the pH of the solution is lowered using the H-type strongly acidic cation exchanger, the treatment amount of the solution in one batch is made smaller than the amount at which the pH drop of the passing solution is completed. However, when mirin is treated with an H-type cation exchanger by a conventional method, the pH is lowered and nitrogen components such as amino acids and peptides in mirin are reduced by being exchanged with an ion exchanger resin. , It will be inferior mirin of quality with less umami and richness. Moreover, the aroma component in mirin will also reduce similarly. Thus, it has been difficult to produce mirin having a good flavor only by treating the H-type strongly acidic cation exchanger with the conventional method.
以上のように、従来技術では糖類やアミノ酸、ペプチド等の窒素成分といったみりんにとっての必須成分含量を維持しつつ、また有機酸を過剰に含有しない、経時的な褐変増色が抑制され、かつ香味良好なみりんの製造方法は存在せず、その技術開発が望まれていた。 As described above, in the prior art, while maintaining the essential components for mirin such as nitrogen components such as sugars, amino acids, peptides, etc., it does not contain excessive organic acids, suppresses browning and color increase over time, and flavor. There is no good method for producing mirin, and its technical development has been desired.
本発明の目的は、上記従来技術にかんがみ、糖類やアミノ酸、ペプチド等の窒素成分を十分に含有すると共に、有機酸を過剰に含有することなくpHが通常のみりんより低い、経時的な褐変増色が起こりにくく、かつ香味良好なみりん及びその製造方法を提供することにある。 In view of the above prior art, the object of the present invention is to sufficiently contain nitrogen components such as sugars, amino acids, peptides, etc., and not to contain organic acids in excess, but to have a pH lower than that of ordinary phosphorus, and increase browning over time. An object of the present invention is to provide a mirin that does not easily cause color and has a good flavor, and a method for producing the same.
本発明を概説すれば、本発明の第1の発明は、pHが4.2以上5.2以下であり、クエン酸、リンゴ酸、コハク酸、乳酸、フマル酸、ギ酸、酢酸、ピログルタミン酸、及びグルコン酸からなる有機酸、更にそれらの塩の含有量の合計が400ppm以下であり、かつ窒素含有量が60mg%(w/v)以上であるみりんに関する。また、本発明の第2の発明は、みりん醪のろ過液又はみりんを強酸性陽イオン交換体と接触させる工程を包含する方法により上記第1の発明のみりんを製造する方法において、みりん醪のろ過液又はみりんの処理容量を、強酸性陽イオン交換体に接触後の溶液のpHの低下が実質上終了するに足る容量以上の容量とするみりんの製造方法に関する。 To summarize the present invention, the first invention of the present invention has a pH of 4.2 or more and 5.2 or less, citric acid, malic acid, succinic acid, lactic acid, fumaric acid, formic acid, acetic acid, pyroglutamic acid, And an organic acid composed of gluconic acid, and a total content of their salts is 400 ppm or less, and a nitrogen content is 60 mg% (w / v) or more. The second invention of the present invention is the method for producing mirin by the method of the first invention, comprising the step of contacting mirin koji filtrate or mirin with a strongly acidic cation exchanger. The present invention relates to a method for producing mirin in which the treatment volume of the filtrate or mirin is set to a volume greater than or equal to a volume that is sufficient for the pH reduction of the solution after contact with the strongly acidic cation exchanger to be substantially completed.
本発明者らは、前記従来技術の問題点について鋭意検討を重ねた結果、みりん醪のろ過液又はみりんをH型強酸性陽イオン交換体で処理する場合において、H型強酸性陽イオン交換体に接触後の溶液のpHの低下が実質上終了する容量以上の多量のみりんを一度に処理することにより、一度イオン交換体に交換された窒素成分や香気成分をより選択性の高いみりん中のミネラルなどの陽イオン成分等と交換させることにより再溶出させることができ、その結果、窒素成分含有量を維持しつつ効率的にpHを低下させることができ、着色の進行が顕著に抑制され、かつ香味良好なみりんを製造することができることを見出した。この製造方法を用いることにより、pHが4.2以上5.2以下であり、クエン酸、リンゴ酸、コハク酸、乳酸、フマル酸、ギ酸、酢酸、ピログルタミン酸、及びグルコン酸からなる有機酸、更にそれらの塩の含有量の合計が400ppm以下であり、かつ窒素含有量が60mg%(w/v)以上というこれまでのみりんと比較して着色の進行が顕著に抑制され、かつ香味良好な新規みりんが得られることを見出し、本発明の完成に至った。 As a result of intensive investigations on the problems of the prior art, the inventors of the present invention have used an H-type strongly acidic cation exchanger in the case of treating mirin koji filtrate or mirin with an H-type strongly acidic cation exchanger. By treating a large amount of phosphorus more than the capacity at which the decrease in pH of the solution after contact is substantially terminated at a time, the nitrogen and fragrance components once exchanged into the ion exchanger are more highly selective in mirin. It can be re-eluted by exchanging it with a cation component such as mineral, and as a result, the pH can be lowered efficiently while maintaining the nitrogen component content, and the progress of coloring is remarkably suppressed, It was also found that mirin having a good flavor can be produced. By using this production method, the pH is 4.2 or more and 5.2 or less, and an organic acid comprising citric acid, malic acid, succinic acid, lactic acid, fumaric acid, formic acid, acetic acid, pyroglutamic acid, and gluconic acid, Furthermore, the total content of those salts is 400 ppm or less, and the nitrogen content is 60 mg% (w / v) or more, so far only the progress of coloring is remarkably suppressed and the flavor is good. The present inventors have found that a new mirin can be obtained and have completed the present invention.
みりん醪のろ過液又はみりんの一定量以上を、強酸性陽イオン交換体、特に対イオンが水素イオンであるH型強酸性陽イオン交換体と接触させるという簡便な方法により、糖類やアミノ酸、ペプチド等の窒素成分が維持され、また有機酸を過剰に含有しない、経時的な褐変増色が顕著に抑制され、かつ香味良好なみりんを提供することができる。本発明は、みりんの着色の増加を簡単かつ効率的に抑制することができるので、みりんの品質劣化防止に有用なものである。 Saccharides, amino acids, and peptides can be obtained by a simple method of bringing a certain amount or more of mirin koji filtrate or mirin into contact with a strongly acidic cation exchanger, particularly an H-type strongly acidic cation exchanger whose counter ion is a hydrogen ion. Thus, it is possible to provide mirin having a good flavor and a browning color increase over time, which does not contain an excessive amount of organic acid, is maintained. The present invention can easily and efficiently suppress an increase in coloring of mirin, and is useful for preventing quality degradation of mirin.
以下に本発明を具体的に説明する。
本発明におけるみりんとは、酒税法で言うみりんであればよい。また、その製造方法は酒税法に則ったみりんの製造方法であれば特に限定はない。例えば、一般的なみりんの製造方法は、搗精、洗米などの原料処理を行い、麹などを添加して仕込醪となし、糖化、熟成する。糖化、熟成を終えた醪は圧搾機で上槽して搾汁と粕に分離する。得られた搾汁は精製工程で火入れし、滓下げして清澄な製品みりんとなる。ここでいう原料処理には、精白、洗浄、浸漬、水切り、蒸煮、放冷の工程があるが、更に掛原料の液化及び/又は糖化工程も含んでいる。原料は米、米麹、醸造アルコール又は焼酎以外に、ぶどう糖、デンプン部分加水分解物を使用してもよい。また、必要に応じて酵素製剤を掛原料の処理の液化及び/又は糖化工程並びに醪へ添加してもよい。また、本発明におけるみりん醪のろ過液とは、みりん製造において熟成後のみりん醪をろ過して得られる清澄液のことをいう。例えば、本発明の製造方法により第1の発明のみりんを製造する場合には、その成分含有量としてクエン酸、リンゴ酸、コハク酸、乳酸、フマル酸、ギ酸、酢酸、ピログルタミン酸、及びグルコン酸からなる有機酸、更にそれらの塩の含有量の合計が400ppm以下であり、かつ窒素含有量が60mg%(w/v)以上であるみりん醪のろ過液又はみりんを用いればよい。
The present invention will be specifically described below.
The mirin in the present invention may be mirin referred to in the liquor tax law. Moreover, the manufacturing method will not be specifically limited if it is a manufacturing method of mirin according to liquor tax law. For example, in a general method for producing mirin, raw materials such as koji and washed rice are processed, and koji is added to form a koji, which is saccharified and aged. After the saccharification and ripening, the koji is separated into juice and koji by using a press machine. The resulting juice is fired in the refining process and lowered into a clear product mirin. The raw material treatment here includes steps of whitening, washing, dipping, draining, steaming, and allowing to cool, but further includes a step of liquefaction and / or saccharification of the hanging raw material. In addition to rice, rice bran, brewed alcohol or shochu, the raw material may be glucose or a partially hydrolyzed starch. Moreover, you may add an enzyme formulation to the liquefaction and / or saccharification process of a processing of a hanging raw material, and a koji as needed. Moreover, the filtrate of mirin koji in the present invention refers to a clarified liquid obtained by filtering koji koji only after ripening in mirin production. For example, when producing only phosphorus according to the first invention by the production method of the present invention, the component content thereof is citric acid, malic acid, succinic acid, lactic acid, fumaric acid, formic acid, acetic acid, pyroglutamic acid, and gluconic acid. An organic acid consisting of the above-mentioned organic acid, and the total content of salts thereof may be 400 ppm or less, and the filtrate of mirin cake or mirin having a nitrogen content of 60 mg% (w / v) or more may be used.
本発明の製造方法の主要部は、強酸性陽イオン交換体を使用することにある。他のイオン交換体では十分な効率でpHを低下させることができない。強酸性陽イオン交換体とは、イオン交換基が強酸性の交換基を有するイオン交換体のことをいう。交換基を保持する担体としては、非特異的吸着が少ない不溶性高分子であればいずれも本発明に使用でき、例えば、ダイヤイオンSK1B、SK104、SK110、SK112、SK116、PK208、PK212、PK216、PK220、PK228(いずれも三菱化学株式会社製)、アンバーライトIR120B Na、IR120BN Na、IR124 Na、1006F H、200CT Na、252 Na、IR118 H、IR120B H AG(いずれもローム&ハース社製)、ダウエックスHCR−S、HCR−W2、HGR−W2、マラソンC、モノスフィアー650C、MSC−1、88、モノスフィアー88(いずれもダウ・ケミカル社製)、デュオライトC20S、C20、C20LF、C26A(いずれもローム&ハース社製)等を例示することができる。 The main part of the production method of the present invention is to use a strongly acidic cation exchanger. Other ion exchangers cannot lower the pH with sufficient efficiency. The strong acid cation exchanger refers to an ion exchanger in which the ion exchange group has a strongly acidic exchange group. Any carrier capable of holding an exchange group can be used in the present invention as long as it is an insoluble polymer with little nonspecific adsorption. For example, Diaion SK1B, SK104, SK110, SK112, SK116, PK208, PK212, PK216, PK220 , PK228 (all manufactured by Mitsubishi Chemical Corporation), Amberlite IR120B Na, IR120BN Na, IR124 Na, 1006F H, 200CT Na, 252 Na, IR118 H, IR120B H AG (all manufactured by Rohm & Haas), Dowex HCR-S, HCR-W2, HGR-W2, Marathon C, Monosphere 650C, MSC-1, 88, Monosphere 88 (all manufactured by Dow Chemical), Duolite C20S, C20, C20LF, C26A (all It is possible to illustrate the over-time & Haas Co., Ltd.), and the like.
本発明に使用する強酸性陽イオン交換体の対イオンとしては、水素イオンを用いることが好ましい。以下、対イオンが水素イオンである強酸性陽イオン交換体を本発明ではH型強酸性陽イオン交換体と略述する。したがって、例えばNa型の強酸性陽イオン交換体を使用する場合は、使用する前に塩酸などの強酸性溶液を通液させることによりH型強酸性陽イオン交換体とすればよい。みりん中のミネラルやアミノ酸等の陽イオン成分とH型強酸性陽イオン交換体の樹脂からの水素イオンとが交換することによりみりん中の水素イオン濃度が上昇しpHが低下する。 As a counter ion of the strongly acidic cation exchanger used in the present invention, it is preferable to use a hydrogen ion. Hereinafter, a strongly acidic cation exchanger whose counter ion is a hydrogen ion is abbreviated as an H-type strongly acidic cation exchanger in the present invention. Therefore, for example, when using a Na-type strongly acidic cation exchanger, an H-type strongly acidic cation exchanger may be obtained by passing a strongly acidic solution such as hydrochloric acid before use. Exchange of cation components such as minerals and amino acids in mirin and hydrogen ions from the resin of the H-type strongly acidic cation exchanger raises the hydrogen ion concentration in mirin and lowers the pH.
本発明においてH型強酸性陽イオン交換体と接触させる工程は、みりん醪のろ過後であればいずれの工程においても適用できる。接触方法はカラム法やバッチ法が一般的に用いられるが、特に限定はなく、製造の観点からはカラム法が望ましい。接触温度はイオン分子の交換に支障がない温度であればよく、10〜40℃、好ましくは20〜30℃である。 In the present invention, the step of bringing into contact with the H-type strongly acidic cation exchanger can be applied to any step as long as it is after filtration of mirin koji. As the contact method, a column method or a batch method is generally used, but there is no particular limitation, and the column method is desirable from the viewpoint of production. The contact temperature may be any temperature that does not hinder the exchange of ion molecules, and is 10 to 40 ° C, preferably 20 to 30 ° C.
一般にみりんのpHは5.5〜6.2であるが、例えば本発明のH型強酸性陽イオン交換体による処理を行うことによりみりんのpHを元の液のpHより低下させることができる。pHが4.2未満の場合、酸味が強くなり、また香気が弱くなるなど品質に問題が生じる。pHが5.2超の場合は実質的に有効なだけの経時的褐変増色抑制効果を得ることができない。したがって、pHは4.2以上5.2以下の範囲、香味の点から好ましくは4.5以上5.2以下、より好ましくは4.8以上5.2以下の範囲がよい。pHの調整はイオン交換体容量に対する溶液の処理容量により行う。処理容量が少ないほど処理後の溶液全体のpHの低下が著しい。例えばみりんをH型強酸性陽イオン交換体で処理すると水素イオンが溶出する代りにアミノ酸等の窒素成分や香気成分がイオン交換体に交換される。香味良好なみりんを製造するためには、これらの窒素成分や香気成分を再溶出させるために強酸性陽イオン交換体に接触後の溶液のpHの低下が実質上終了するに足る容量以上の多量のみりんを処理すればよい。本発明でいう「pHの低下が実質上終了するに足る容量」とは、例えばカラム法でH型強酸性陽イオン交換体による処理を行う場合、イオン交換体を通過した瞬間の溶液のpHが通過する前の溶液のpHと実質的に同じとなる状態にまでなった時点におけるイオン交換体を通過した溶液の総容量のこという。上限としては、pHが5.2となるまでである。少量のみりんを処理して著しくpHの低いみりんを調整後、適当なアルカリを用いて、所望のpHに調整する、あるいは未処理のみりんを混合するなどして目的のpHに調整することも可能ではあるが、この場合、イオン交換体に交換された窒素成分や香気成分が回収されず品質的に良好なみりんを得ることができない。みりん醪のろ過液又はみりんの具体的な処理容量は、処理するみりん醪のろ過液又はみりんの成分組成、あるいは使用するイオン交換体の交換容量をはじめとする性能の違いによるため、予め小規模試験により量的関係を最適化しておく必要があるが、その方法自体は公知のものである。例えばpH5.8の一般的なみりんを、イオン交換体の母体がスチレン系であり、総交換容量2.0meq/mL、架橋度8%の一般的な強酸性陽イオン交換体を用いて処理する場合、イオン交換体容量の200倍のみりんを通液するとpHの低下が実質上終了する。したがって、この場合、イオン交換体容量の200倍以上、好ましくは300倍以上のみりんを通液することが望ましい。通液速度に関しても処理するみりん醪のろ過液又はみりん、あるいは使用する強酸性陽イオン交換体に応じて適宜最適な条件を設定すればよい。 In general, mirin has a pH of 5.5 to 6.2. For example, the treatment with the H-type strongly acidic cation exchanger of the present invention can reduce the pH of mirin from that of the original solution. When the pH is less than 4.2, there is a problem in quality such as a strong acidity and a weak aroma. When the pH is over 5.2, it is not possible to obtain the effect of suppressing browning increase in color over time that is substantially effective. Accordingly, the pH is in the range of 4.2 to 5.2, preferably from 4.5 to 5.2, more preferably from 4.8 to 5.2 in terms of flavor. The pH is adjusted by the treatment volume of the solution with respect to the ion exchanger volume. The smaller the treatment volume, the more markedly the pH of the solution after treatment is lowered. For example, when mirin is treated with an H-type strongly acidic cation exchanger, nitrogen components such as amino acids and aroma components are exchanged for ion exchangers instead of elution of hydrogen ions. In order to produce mirin having a good flavor, a large amount exceeding the capacity sufficient for the decrease in pH of the solution after contact with the strong acid cation exchanger to be substantially eluted to re-elute these nitrogen and aroma components. The mirin can be processed. In the present invention, the “capacity sufficient for the pH reduction to end substantially” means, for example, when the treatment with an H-type strongly acidic cation exchanger is performed by the column method, the pH of the solution at the moment of passing through the ion exchanger is The total volume of the solution that has passed through the ion exchanger at the time when the pH reaches substantially the same as the pH of the solution before passing through. The upper limit is until the pH reaches 5.2. It is also possible to adjust mirin with a very low pH by treating only a small amount of phosphorus and then adjusting to the desired pH using an appropriate alkali, or by mixing untreated mirin with the target pH. However, in this case, the nitrogen component and the fragrance component exchanged with the ion exchanger are not recovered, and good quality mirin cannot be obtained. The specific processing capacity of mirin koji filtrate or mirin depends on the difference in performance, including the composition of the mirin koji filtrate or mirin, or the exchange capacity of the ion exchanger used. Although it is necessary to optimize the quantitative relationship by testing, the method itself is known. For example, a general mirin having a pH of 5.8 is treated with a general strongly acidic cation exchanger having a total exchange capacity of 2.0 meq / mL and a cross-linking degree of 8%. In this case, when the phosphorus is passed through only 200 times the ion exchanger capacity, the pH reduction is substantially completed. Therefore, in this case, it is desirable to pass phosphorus through 200 times or more, preferably 300 times or more of the ion exchanger capacity. The optimum conditions may be set as appropriate according to the filtrate or mirin of the mirin cake to be treated or the strongly acidic cation exchanger to be used.
このようにして、本発明の製造方法により製造されたみりんは、従来の製造方法により製造されたみりんより、経時的な褐変増色が起こりにくく品質的に安定したものであり、かつ香味良好なものとなる。 In this way, mirin produced by the production method of the present invention is more stable in quality and less fragile over time than mirin produced by the conventional production method, and has a good flavor. It will be a thing.
本発明の製造方法を用いれば、一般的なみりん醪のろ過液又はみりんより、pHが4.2以上5.2以下であり、クエン酸、リンゴ酸、コハク酸、乳酸、フマル酸、ギ酸、酢酸、ピログルタミン酸、及びグルコン酸からなる有機酸、更にそれらの塩の含有量の合計が400ppm以下であり、かつ窒素含有量が60mg%(w/v)以上である新規みりんを製造することができる。なお、クエン酸、リンゴ酸、コハク酸、乳酸、フマル酸、ギ酸、酢酸、ピログルタミン酸、及びグルコン酸からなる有機酸、更にそれらの塩の含有量の合計が400ppmを超えると、酸味が強く、酸が浮くものとなり、また、窒素含有量が60mg%(w/v)未満では、旨みやコクに欠けるものとなる。有機酸及びそれらの塩の分析方法は、通常用いられる方法に従って行えばよく、例えばイオン排除クロマトグラフィーによる方法が挙げられる。なお、本発明では、有機酸換算としてppmを単位に算出しているが、これは濃度の単位mg/Lと同義である。クエン酸、リンゴ酸、コハク酸、乳酸、フマル酸、ギ酸、酢酸、ピログルタミン酸、及びグルコン酸からなる有機酸、更にそれらの塩の含有量というのは、前記した分析方法で分析可能な含有量であり、9種の有機酸のうちで被検みりん中にない(又は分析で検出できない)酸及びそれらの塩は除外して算出すればよく、また、そのようなみりんも本発明に含まれる。本発明のみりんは、経時的な褐変増色が起こりにくく、また香味の面では有機酸を過剰に含有しないため余分な酸味がなく、かつアミノ酸やペプチドを高含有するため旨みやコクが豊かな従来にない優れたみりんとなる。本発明のみりんはこれまでの製造方法では製造することができず、また実際に市販みりんの分析を行った結果、本発明が規定するpH、有機酸の含有量の合計、かつ窒素含有量を満たすみりんは存在しなかった。 If the production method of the present invention is used, the pH is 4.2 or more and 5.2 or less from a common mirin koji filtrate or mirin, and citric acid, malic acid, succinic acid, lactic acid, fumaric acid, formic acid, A novel mirin having a total content of organic acids consisting of acetic acid, pyroglutamic acid, and gluconic acid, and salts thereof of 400 ppm or less and a nitrogen content of 60 mg% (w / v) or more. it can. In addition, when the total of the content of the organic acid consisting of citric acid, malic acid, succinic acid, lactic acid, fumaric acid, formic acid, acetic acid, pyroglutamic acid, and gluconic acid, and their salts exceeds 400 ppm, the acidity is strong, The acid floats, and if the nitrogen content is less than 60 mg% (w / v), the taste and richness are lacking. The analysis method of organic acids and their salts may be performed according to a commonly used method, for example, a method by ion exclusion chromatography. In the present invention, ppm is calculated in terms of organic acid in terms of ppm, which is synonymous with the unit of concentration mg / L. Organic acids consisting of citric acid, malic acid, succinic acid, lactic acid, fumaric acid, formic acid, acetic acid, pyroglutamic acid, and gluconic acid, and the content of their salts is the content that can be analyzed by the above-described analysis method Of the nine types of organic acids, acids that are not present in test phosphorus (or that cannot be detected by analysis) and salts thereof may be excluded from the calculation, and such mirin is also included in the present invention. . Mirin of the present invention is less prone to browning over time, and in terms of flavor, it does not contain an excessive amount of organic acid, so there is no excess acidity, and since it contains a high amount of amino acids and peptides, it has a rich taste and richness. An excellent mirin that has never been seen before. The present phosphorus cannot be produced by the conventional production methods, and as a result of actually analyzing commercially available mirin, the pH, the total content of organic acids, and the nitrogen content specified by the present invention are determined. There was no filling Sumirin.
なお、経時的な褐変増色の抑制効果を評価する方法としては一般的な方法が用いられる。例えば、増色度を評価する方法としては、まず本発明で得られたみりん(以下、本発明品という)について色調の指標となる10mmセルの430nmの吸光度(A1)を測定する。以下、吸光度の測定はすべて10mmセルでの測定とする。本発明品を適当な温度、例えば40℃で一定期間、例えば1ヵ月間保持し、430nmの吸光度(A2)を測定する。一方、強酸性陽イオン交換体の処理を行わなかったみりん(以下、対照品という)に関しても、430nmの吸光度(A3)を測定した後、同条件で保持し、430nmの吸光度(A4)を測定する。両者の吸光度から、下記式により増色度である△OD430nmを算出する。
△OD430nm(本発明品)=A2−A1
△OD430nm(対照品) =A4−A3
また、上記式で得られた増色度を用いて下記式により着色抑制率を算出することもできる。
着色抑制率(%)=〔{△OD430nm(対照品)−△OD430nm(本発明品)}÷△OD430nm(対照品)〕×100
経時的な褐変増色の抑制効果を評価するには、増色度での比較を行ってもよいし、着色抑制率を算出して比較を行うこともできる。
In addition, a general method is used as a method for evaluating the effect of suppressing the browning increase in color over time. For example, as a method for evaluating the degree of color increase, first, the absorbance (A 1 ) of 430 nm of a 10 mm cell serving as a color tone index is measured for mirin obtained in the present invention (hereinafter referred to as the product of the present invention). Hereinafter, the measurement of absorbance is all performed with a 10 mm cell. The product of the present invention is held at an appropriate temperature, for example, 40 ° C. for a certain period, for example, for one month, and the absorbance (A 2 ) at 430 nm is measured. On the other hand, for mirin (hereinafter referred to as a control product) that was not treated with a strongly acidic cation exchanger, the absorbance at 430 nm (A 3 ) was measured and then held under the same conditions, and the absorbance at 430 nm (A 4 ). Measure. From the absorbance of both, ΔOD 430 nm which is a color increase degree is calculated by the following formula.
ΔOD 430 nm (product of the present invention) = A 2 −A 1
ΔOD 430 nm (control product) = A 4 −A 3
Moreover, the coloring suppression rate can also be calculated by the following formula using the color increase degree obtained by the above formula.
Coloration inhibition rate (%) = [{ΔOD 430 nm (control product) −ΔOD 430 nm (product of the present invention)} ÷ ΔOD 430 nm (control product)] × 100
In order to evaluate the effect of suppressing browning color increase over time, a comparison may be made with the degree of color increase, or a color suppression rate may be calculated and compared.
以下、実施例によって本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
様々な処理容量でみりんを強酸性陽イオン交換体で処理した実施例を以下に示す。強酸性陽イオン交換体、ダイヤイオンSK1B(三菱化学株式会社製)5mlを内径10mmのクロマトグラフ管に充填し、水洗した後、7%塩酸30mlを通液しH型にした。更に水洗した後、本みりん(宝酒造株式会社製)をSV8の流速で通液した。なお、本発明でいうSVとは、通液の速度であり、空間速度(S.V.と略記)、あるいは液空間速度(LHSVと略記)のことであり、以下SVと略述する。予備試験の結果、本実施例の条件ではイオン交換体容量の200倍のみりんを通液した段階で通過液のpHの低下が実質上終了した。みりん400ml通液したもの(イオン交換体容量の80倍)を試験例1、600ml通液したもの(イオン交換体容量の120倍)を試験例2、800ml通液したもの(イオン交換体容量の160倍)を試験例3、1000ml通液したもの(イオン交換体容量の200倍)を本発明1、1500ml通液したもの(イオン交換体容量の300倍)を本発明2、2000ml通液したもの(イオン交換体容量の400倍)を本発明3とした。未処理の本みりんを比較例1とした。得られた処理液について分析、官能検査及び保存試験を行った。官能検査は10名のパネラーで行い、3点法(1;良、2;普通、3;悪)で評価した。各パネラーによる官能検査の平均値より、1.0〜1.5を◎、1.5超〜2.0を○、2.0超〜2.5を△、2.5超〜3.0を×で示した。保存試験は40℃暗所にて静置保存をし、1ヵ月間の増色度である△OD430nm(10mmセルの430nmの吸光度の差)を測定し着色抑制率を計算した。結果を表1に示す。また、40℃での保存試験において、定期的にサンプリングを行い着色の指標となる10mmセルの430nmの吸光度の経時変化を測定した結果を図1に示す。
なお、図1においては、縦軸を430nmの吸光度、横軸を保存期間(日)として、結果をグラフ化した。
Examples in which mirin was treated with a strongly acidic cation exchanger at various treatment volumes are shown below. A strongly acidic cation exchanger, Diaion SK1B (manufactured by Mitsubishi Chemical Co., Ltd.) 5 ml was filled in a chromatograph tube having an inner diameter of 10 mm, washed with water, and then 30 ml of 7% hydrochloric acid was passed through to form an H type. After further washing with water, Hon Mirin (Takara Shuzo Co., Ltd.) was passed at a flow rate of SV8. The SV in the present invention is a liquid passing speed, which is a space velocity (abbreviated as SV) or a liquid space velocity (abbreviated as LHSV), and is hereinafter abbreviated as SV. As a result of the preliminary test, under the conditions of this example, the decrease in pH of the flow-through substantially ended at the stage where phosphorus was passed through only 200 times the ion exchanger capacity. 400 ml of mirin (80 times the capacity of the ion exchanger), Test Example 1, 600 ml of the water (120 times the capacity of the ion exchanger), 2nd test example, 800 ml (the capacity of the ion exchanger) 160 times) of Example 3, 1000 ml (200 times the ion exchanger capacity) of the present invention 1, 1500 ml (300 times the ion exchanger capacity) of the present invention 2, 2000 ml The product (400 times the ion exchanger capacity) was designated as Invention 3. Untreated main mirin was used as Comparative Example 1. The obtained treatment liquid was subjected to analysis, sensory inspection and storage test. The sensory test was performed by 10 panelists and evaluated by a three-point method (1; good, 2; normal, 3; bad). From average value of sensory test by each panel, 1.0 to 1.5 is ◎, 1.5 to 2.0 is ◯, 2.0 to 2.5 is △, 2.5 to 3.0 Is indicated by ×. In the storage test, the sample was stored in a dark place at 40 ° C., and ΔOD 430 nm (difference in absorbance at 430 nm of a 10 mm cell), which was a color increase for one month, was measured to calculate a coloring inhibition rate. The results are shown in Table 1. In addition, in a storage test at 40 ° C., the results of measuring the change over time of the absorbance at 430 nm of a 10 mm cell that is periodically sampled and serves as a coloring index are shown in FIG.
In FIG. 1, the results are graphed with the vertical axis representing the absorbance at 430 nm and the horizontal axis representing the storage period (days).
表1に示すように、H型強酸性陽イオン交換体で処理することによりみりんのpHが低下した。イオン交換体容量に対するみりんの処理容量が少ないほどpHの低下が著しく、また窒素成分の低減が大きかった。しかしながら、窒素成分の低減はみりんの処理容量をイオン交換体容量の200倍以上にすれば10%以下に抑制することができた。官能検査の結果より、みりんの処理容量がイオン交換体容量の200倍以上であれば良好であり、特に300倍及び400倍を通液した本発明2及び本発明3の評価が高かった。これは窒素成分や香気成分を十分量含有し、かつみりんの香味にとって適当なpHであるためである。表1及び図1に示すように、保存試験の結果、処理容量が少ないほど着色が抑制されていた。しかしながら、イオン交換体容量の400倍のみりんを処理した本発明3でも着色抑制率が35%以上であり十分な着色抑制効果を示した。 As shown in Table 1, the pH of mirin was lowered by treatment with an H-type strongly acidic cation exchanger. The smaller the mirin treatment capacity relative to the ion exchanger capacity, the more the pH was lowered and the nitrogen component was greatly reduced. However, the reduction of the nitrogen component could be suppressed to 10% or less if the treatment capacity of mirin was increased to 200 times or more of the ion exchanger capacity. From the results of the sensory test, it was satisfactory if the treatment capacity of mirin was 200 times or more of the ion exchanger capacity, and the evaluations of the present invention 2 and the present invention 3 through which 300 times and 400 times passed were particularly high. This is because it contains a sufficient amount of a nitrogen component and a fragrance component and has a pH suitable for the flavor of bonito. As shown in Table 1 and FIG. 1, as a result of the storage test, the smaller the processing capacity, the more the coloring was suppressed. However, even in the present invention 3 in which phosphorus was treated only 400 times the ion exchanger capacity, the coloring suppression rate was 35% or more, and a sufficient coloring suppression effect was shown.
本発明3と比較例1を用いて、めんつゆと高野豆腐の含め煮を調理し官能検査を行った。めんつゆは、みりん18ml、濃口しょうゆ30ml、上白糖4.4g、食塩0.3gを配合し、更に水を加えて全量を200mlとして調製した。高野豆腐の含め煮に関しては、まず以下のように調味液を調製した。すなわち、みりん250ml、薄口しょうゆ30ml、上白糖15g、だししるべK超淡色(宝酒造株式会社製)14g、だししるべL−2(宝酒造株式会社製)10gを配合し、更に水を加えて全量を1000mlとした。この調味液に予めお湯で戻し2cm角程度にカットした高野豆腐を加え沸騰するまで強火で加熱し、沸騰後は弱火で20分間煮た。官能検査は10名のパネラーで行い、3点法で評価した。その結果、本発明3で調理したサンプルは比較例1で調理したサンプルと同様に、旨みやコクが強く、また香りも豊かであり非常においしいという評価が得られた。以上より本発明のみりんは調理時においても優れた調理効果を示すことがわかった。 Using the present invention 3 and comparative example 1, cooked boiled noodles including mentsuyu and Koya tofu were subjected to sensory test. Mentsuyu was prepared by mixing 18 ml of mirin, 30 ml of thick soy sauce, 4.4 g of super white sugar and 0.3 g of sodium chloride, and further adding water to make a total volume of 200 ml. For boiled with Koya tofu, a seasoning solution was first prepared as follows. That is, 250 ml of mirin, 30 ml of thin soy sauce, 15 g of super white sugar, 14 g of dashi shirube K ultra-light color (made by Takara Shuzo), 10 g of dashi shirube L-2 (made by Takara Shuzo), and further add water The total volume was 1000 ml. To this seasoning liquid, Takano tofu which had been returned to hot water in advance and cut to about 2 cm square was added and heated to a boil until boiled, and then boiled for 20 minutes on a low heat. The sensory test was conducted by 10 panelists and evaluated by a three-point method. As a result, similar to the sample cooked in Comparative Example 1, the sample cooked in the present invention 3 was evaluated as having a strong taste and richness, rich in fragrance, and very delicious. From the above, it was found that the present phosphorus shows an excellent cooking effect even during cooking.
他の強酸性陽イオン交換体でみりんを処理した実施例を以下に示す。アンバーライトIR120B Na(ローム&ハース社製)及びダウエックスHCR−S(ダウ・ケミカル社製)各5mlを内径10mmのクロマトグラフ管に充填し、水洗した後、7%塩酸30mlを通液しH型にした。更に水洗した後、実施例1において比較例1とした本みりん(宝酒造株式会社製)2000ml(イオン交換体容量の400倍)をSV8の流速で通液した。なお、予備試験の結果、本実施例の条件ではいずれの強酸性陽イオン交換体の場合においてもイオン交換体容量の200倍のみりんを通液した段階で通過液のpHの低下が実質上終了した。得られた処理液についてIR120B Naで処理したものを本発明4、HCR−Sで処理したものを本発明5とした。SK1Bを用いて全く同条件で処理を行った本発明3の結果と併せて、分析、官能検査及び保存試験を行った。官能検査及び保存試験は実施例1と同様の方法で行った。結果を表2に示す。 Examples of treating mirin with other strongly acidic cation exchangers are shown below. Amberlite IR120B Na (made by Rohm & Haas) and Dowex HCR-S (made by Dow Chemical Co., Ltd.) 5 ml each were filled into a chromatograph tube having an inner diameter of 10 mm, washed with water, and then 30 ml of 7% hydrochloric acid was passed through. Made a mold. After further washing with water, 2000 ml of Hon Mirin (manufactured by Takara Shuzo Co., Ltd.) (400 times the ion exchanger capacity) as Comparative Example 1 in Example 1 was passed at a flow rate of SV8. In addition, as a result of the preliminary test, in the case of any strongly acidic cation exchanger under the conditions of this example, the drop in the pH of the passing liquid substantially ended at the stage where phosphorus was passed only 200 times the ion exchanger capacity. did. The obtained treatment solution treated with IR120B Na was treated as Invention 4 and treated with HCR-S as Invention 5. The analysis, sensory test and storage test were performed together with the result of the present invention 3, which was processed under the same conditions using SK1B. The sensory test and the storage test were performed in the same manner as in Example 1. The results are shown in Table 2.
表2に示すように、いずれの強酸性陽イオン交換体で処理した場合においても、官能検査の結果より、処理前のみりんと同等に高い評価が得られた。また、保存試験の結果、いずれの強酸性陽イオン交換体で処理した場合においても処理前のみりんと比較して顕著に経時的な褐変増色が抑制されていた。いずれの強酸性陽イオン交換体で処理した場合も分析値や保存試験結果がほぼ同じ数値になったのは、通過液のpHの低下が実質上終了するに足る容量以上のみりんを通液するという同じ条件に設定することにより、それぞれの強酸性陽イオン交換体の性能を引出すことができたものである。 As shown in Table 2, in the case of treatment with any strongly acidic cation exchanger, evaluation as high as that of phosphorus before treatment was obtained from the result of sensory test. In addition, as a result of the storage test, the browning increase in color over time was significantly suppressed when treated with any strongly acidic cation exchanger as compared with phosphorus before treatment. The analytical value and the storage test result are almost the same in any of the treatments with any strongly acidic cation exchanger. The phosphorus is passed only over the volume that is sufficient for the pH drop of the passing liquid to be substantially completed. By setting the same conditions as above, the performance of each strongly acidic cation exchanger could be brought out.
様々な市販みりんを本発明の方法により処理した実施例を以下に示す。ダイヤイオンSK1B(三菱化学株式会社製)5mlを内径10mmのクロマトグラフ管に充填し、水洗した後、7%塩酸30mlを通液しH型にした。更に水洗した後、市販みりんA(比較例2とする)、市販みりんB(比較例3とする)及び市販みりんC(比較例4とする)各2000ml(イオン交換体容量の400倍)をSV8の流速で通液した。なお、予備試験の結果、本実施例の条件ではいずれのみりんを処理した場合においてもイオン交換体容量の200倍のみりんを通液した段階で通過液のpHの低下が実質上終了した。市販みりんAを処理したものを本発明6、市販みりんBを処理したものを本発明7、市販みりんCを処理したものを本発明8とした。それぞれ処理して得られたみりんについて分析、官能検査及び保存試験を行った。官能検査及び保存試験は実施例1と同様の方法で行った。結果を表3に示す。 Examples of treating various commercially available mirin by the method of the present invention are shown below. After filling 5 ml of Diaion SK1B (manufactured by Mitsubishi Chemical Corporation) into a chromatograph tube having an inner diameter of 10 mm and washing with water, 30 ml of 7% hydrochloric acid was passed through to form an H-shape. Further, after washing with water, 2000 ml each of commercially available mirin A (referred to as Comparative Example 2), commercially available Mirin B (referred to as Comparative Example 3), and commercially available Mirin C (referred to as Comparative Example 4) (400 times the ion exchanger capacity) was subjected to SV8. The liquid was passed at a flow rate of. As a result of the preliminary test, even when phosphorus was only treated under the conditions of this example, the drop in the pH of the passing solution was substantially completed at the stage where phosphorus was passed only 200 times the ion exchanger capacity. A product obtained by treating commercially available mirin A is designated as the present invention 6, a product obtained by treating commercially available mirin B as the present invention 7, and a product obtained by treating commercially available mirin C as the present invention 8. Analyzes, sensory tests, and storage tests were conducted on mirin obtained by each treatment. The sensory test and the storage test were performed in the same manner as in Example 1. The results are shown in Table 3.
表3に示すように、いずれの市販みりんを本発明の方法により処理した場合においても、官能検査の結果より、処理前のみりんと同等に高い評価が得られた。また、保存試験の結果、いずれの市販みりんを本発明の方法により処理した場合においても処理前のみりんと比較して顕著に経時的な褐変増色が抑制されていた。 As shown in Table 3, even when any commercially available mirin was treated by the method of the present invention, evaluation as high as that of phosphorus before treatment was obtained from the result of sensory test. In addition, as a result of the storage test, when any commercially available mirin was treated by the method of the present invention, the browning increase in color over time was significantly suppressed as compared with phosphorus only before the treatment.
本発明によれば、みりんの種類、強酸性陽イオン交換体の種類を問わず、工業的規模で簡便に経時的な褐変増色が抑えられた、かつ香味良好なみりんを得ることができるので、本発明は有用なみりん及びその製造方法である。 According to the present invention, it is possible to obtain mirin with good flavor and reduced browning over time on an industrial scale, regardless of the type of mirin and the type of strong acid cation exchanger. The present invention is a useful mirin and a method for producing the same.
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JP2011092066A (en) * | 2009-10-28 | 2011-05-12 | Nissin Foods Holdings Co Ltd | Reduced-salt food flavor improver, method for improving flavor of reduced-salt food, and savory reduced-salt food |
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JPS63152970A (en) * | 1986-12-16 | 1988-06-25 | Takara Shuzo Co Ltd | Seasoning having high saccharide concentration |
JPH05111373A (en) * | 1991-10-22 | 1993-05-07 | Fukushima Pref Gov | Production of refined japanese wine and fermented seasoning using loose reverse osmosis membrane |
JPH11113555A (en) * | 1997-10-13 | 1999-04-27 | Kikkoman Corp | Production of sweet rice wine |
JP2003304860A (en) * | 2002-04-16 | 2003-10-28 | Kikkoman Corp | Method for producing alcohol-containing seasoning |
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JPS63152970A (en) * | 1986-12-16 | 1988-06-25 | Takara Shuzo Co Ltd | Seasoning having high saccharide concentration |
JPH05111373A (en) * | 1991-10-22 | 1993-05-07 | Fukushima Pref Gov | Production of refined japanese wine and fermented seasoning using loose reverse osmosis membrane |
JPH11113555A (en) * | 1997-10-13 | 1999-04-27 | Kikkoman Corp | Production of sweet rice wine |
JP2003304860A (en) * | 2002-04-16 | 2003-10-28 | Kikkoman Corp | Method for producing alcohol-containing seasoning |
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WO2006118090A1 (en) * | 2005-04-28 | 2006-11-09 | Taiyokagaku Co., Ltd. | Water-containing food |
US10905764B2 (en) | 2005-04-28 | 2021-02-02 | Taiyokagaku Co., Ltd. | Hydrated food |
JP2011092066A (en) * | 2009-10-28 | 2011-05-12 | Nissin Foods Holdings Co Ltd | Reduced-salt food flavor improver, method for improving flavor of reduced-salt food, and savory reduced-salt food |
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