JP6292930B2 - Seafood fermentation composition and liquid seasoning containing the same - Google Patents
Seafood fermentation composition and liquid seasoning containing the same Download PDFInfo
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- JP6292930B2 JP6292930B2 JP2014044422A JP2014044422A JP6292930B2 JP 6292930 B2 JP6292930 B2 JP 6292930B2 JP 2014044422 A JP2014044422 A JP 2014044422A JP 2014044422 A JP2014044422 A JP 2014044422A JP 6292930 B2 JP6292930 B2 JP 6292930B2
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Landscapes
- Soy Sauces And Products Related Thereto (AREA)
- Seasonings (AREA)
Description
本発明は、魚介類発酵調味料特有の不快臭が抑制された魚介類発酵組成物、および該魚介類発酵組成物を含む液状調味料に関する。 The present invention relates to a fish and shellfish fermentation composition in which an unpleasant odor peculiar to a fish and shellfish seasoning is suppressed, and a liquid seasoning containing the fish and shellfish fermentation composition.
魚醤に代表される魚介類発酵調味料は、魚介類を原料に食塩を添加し、数か月にわたって発酵・熟成させ、ろ過して製造される調味料の一種であり、大豆や小麦を原料とする一般の醤油とは異なる独特の旨みを有することが知られている。魚介類発酵調味料は、発酵・熟成中に、原料となる魚介類が元来有している酵素による自己消化や環境および原料由来の微生物によるタンパク分解が進み、グルタミン酸などのアミノ酸が豊富に生成されるために少量で非常に旨みがある。しかしながら、魚介類発酵調味料には、発酵・熟成中に発生するアミン類(トリメチルアミンやトリメチルアミンオキサイドなど)に起因する不快臭があり、また特有の魚臭さもあるため、嗜好的に受け入れがたく、食品への用途が拡大しない、あるいは、使用量に制限があるなどの問題がある。これらの問題は魚介類発酵調味料で一般的にみられる問題である。 Seafood fermented seasonings represented by fish soy are a type of seasoning that is made by adding salt to seafood, fermenting and aging for several months, and filtering. It is known to have a unique taste different from general soy sauce. During fermentation and ripening, seafood fermented seasonings are rich in amino acids such as glutamic acid due to the progress of self-digestion by enzymes originally contained in raw fish and shellfish and proteolysis by microorganisms derived from the environment and raw materials. It is very delicious with a small amount. However, seafood fermented seasonings have an unpleasant odor due to amines (trimethylamine, trimethylamine oxide, etc.) generated during fermentation and aging, and also have a unique fishy odor, so it is unacceptable to taste. There is a problem that the use for food does not expand or the amount of use is limited. These problems are commonly seen with seafood fermented seasonings.
このような魚介類発酵調味料特有の不快臭を抑制する方法として、これまで、イオン交換膜処理や水蒸気蒸留などの物理的方法(特許文献1、2等)、魚介類発酵調味料の有する不快香気をマスキングする効果を有する香気物質又はその処理物を使用する方法(特許文献3等)、微生物スターターを使用する方法などが提案されている。しかしながら、物理的方法では、そのための設備や処理工程が必要であり、香気物質などのマスキング成分を使用する方法では、不快臭の抑制効果があっても、魚介類発酵調味料特有の風味や旨みを損ねるなどの問題があった。これに対し、微生物スターターを使用する方法は、通常の醸造工程の流れに組み入れて容易に実施ができるので、製造効率の面において有利であり、最も多く行われている方法である。しかしながら、魚介類発酵調味料の製造工程における発酵は、微生物にとって過酷な高食塩濃度下で行われること、穀類を原料とする通常の醤油とは異なって糖質が少ないといったような事情から、微生物の種類や組み合わせ、添加時期について様々な検討がされている。例えば、耐塩性乳酸菌と耐塩性酵母を併用する方法(特許文献4、5等)、もろみ仕込み時に魚介類に食塩及び麹を加えてから、さらに乳酸菌及び酵母を10:1以上の割合で添加し、その後、もろみを低温で発酵熟成させる方法(特許文献6)、魚介類に食塩及び麹を原料とし、耐塩性乳酸菌とチゴサッカロミセス(Zygosaccharomyces)属酵母とカンジダ(Candida)属酵母の3種の微生物を併用して、もろみを30〜40℃に加温しながら発酵させる方法(特許文献7)などが提案されている。しかしながら、いずれも微生物の菌数の比率の調整など熟練した醸造技術と温度管理などの煩雑な制御を要する。よって、魚介類発酵調味料特有の不快臭や魚臭さを低減し、かつ、魚介類発酵調味料特有の風味や旨みを保持する簡便かつ有効な手段が望まれるところである。 As a method for suppressing the unpleasant odor peculiar to such seafood fermented seasonings, so far, physical methods such as ion exchange membrane treatment and steam distillation (Patent Documents 1 and 2 etc.), unpleasantness of fish and seafood fermented seasonings. A method using a fragrance substance having an effect of masking a fragrance or a processed product thereof (Patent Document 3, etc.), a method using a microbial starter, and the like have been proposed. However, the physical method requires equipment and processing steps therefor, and the method using a masking component such as a fragrance substance has a flavor and umami characteristic of a fermented seafood seasoning even if it has an effect of suppressing unpleasant odors. There was a problem such as damage. On the other hand, the method using a microorganism starter is advantageous in terms of production efficiency because it can be easily implemented by incorporating it into the flow of a normal brewing process, and is the most frequently performed method. However, fermentation in the production process of seafood fermented seasonings is performed under high salt concentration, which is severe for microorganisms, and unlike normal soy sauce made from cereals, there are few sugars. Various studies have been made on the types, combinations, and timing of addition. For example, a method using salt-resistant lactic acid bacteria and salt-resistant yeast in combination (Patent Documents 4, 5, etc.), adding salt and salmon to fish and shellfish when adding moromi, and then adding lactic acid bacteria and yeast at a ratio of 10: 1 or more. Then, the method of fermenting and ripening moromi at low temperature (Patent Document 6), using sea salt and salt as raw materials, and three types of microorganisms: salt-resistant lactic acid bacteria, Zygosaccharomyces yeast and Candida yeast A method of fermenting moromi while heating it to 30 to 40 ° C. (Patent Document 7) and the like has been proposed. However, both require skilled brewing techniques such as adjusting the ratio of the number of microorganisms and complicated controls such as temperature management. Therefore, there is a demand for a simple and effective means for reducing the unpleasant odor and fishy odor characteristic of fish and shellfish seasonings and retaining the flavor and taste unique to fish and shellfish seasonings.
一方、ニコチン酸エチルは、それ自体はほとんど無味無臭の物質であって、熟成させたビール等に含まれること(非特許文献1)、食酢においてコク味を増強させる成分として知られている(特許文献8)。しかしながら、ニコチン酸エチルが魚介類発酵調味料特有の不快臭を抑制することについてはこれまで全く知られていない。 On the other hand, ethyl nicotinate itself is an almost tasteless and odorless substance, and is known to be contained in aged beer and the like (Non-patent Document 1), and as a component that enhances the body taste in vinegar (patent) Reference 8). However, until now, it has not been known at all that ethyl nicotinate suppresses the unpleasant odor peculiar to seafood fermented seasonings.
本発明の目的は、魚介類発酵調味料特有の不快臭を抑制する簡便かつ有効な手段を提供することにある。 An object of the present invention is to provide a simple and effective means for suppressing the unpleasant odor peculiar to seafood fermented seasonings.
本発明者らは、魚介類発酵調味料特有の不快臭を抑制する手段について鋭意研究を重ねた結果、それ自体はほとんど無味無臭の物質であるニコチン酸エチルを魚介類発酵組成物に特定の濃度範囲で含有させることによって、魚介類発酵調味料特有の不快臭を顕著に抑制でき、また、当該魚介類発酵組成物を原料の一部に用いた液状調味料は、魚介類発酵調味料特有の不快臭が感じられず、旨みと風味に優れることを見出した。本発明者らはまた、ニコチン酸エチルにジエチレングリコールモノブチルエーテルアセタートを併用すれば、ニコチン酸エチルの有する上記効果を一層向上させることを見出した。本発明はかかる知見により完成されたものである。 As a result of intensive studies on the means for suppressing the unpleasant odor peculiar to seafood fermented seasonings, the present inventors have found that ethyl nicotinate, which is an almost tasteless and odorless substance, has a specific concentration in the seafood fermented composition. By containing in a range, the unpleasant odor peculiar to seafood fermented seasonings can be remarkably suppressed, and the liquid seasoning using the seafood fermented composition as a part of the raw material is unique to the seafood fermented seasonings. It was found that an unpleasant odor was not felt and the taste and flavor were excellent. The present inventors have also found that the above-mentioned effects of ethyl nicotinate can be further improved by using ethyl nicotinate in combination with diethylene glycol monobutyl ether acetate. The present invention has been completed based on such findings.
すなわち、本発明は以下の発明を包含する。
(1)ニコチン酸エチルを4〜1000ppbの濃度範囲で含有することを特徴とする、魚介類発酵組成物。
(2)前記ニコチン酸エチルに対し、重量比で0.2〜4.0倍量のジエチレングリコールモノブチルエーテルアセタートをさらに含有することを特徴とする、(1)に記載の魚介類発酵組成物。
(3)(1)または(2)に記載の魚介類発酵組成物を含む液状調味料。
(4)(1)または(2)に記載の魚介類発酵組成物と食酢とを含む、(3)に記載の液状調味料。
(5)(1)または(2)に記載の魚介類発酵組成物と魚節抽出物とを含む、(3)に記載の液状調味料。
(6)液状調味料が、魚介類発酵調味料、ぽん酢、つゆ類、またはたれ類である、(3)に記載の液状調味料。
(7)魚介類発酵組成物にニコチン酸エチルを4〜1000ppbの濃度範囲で含有させることを特徴とする、魚介類発酵組成物または魚介類発酵組成物を含有する液状調味料における魚介類発酵調味料特有の不快臭を抑制する方法。
(8)前記ニコチン酸エチルに対し、重量比で0.2〜4.0倍量のジエチレングリコールモノブチルエーテルアセタートをさらに魚介類発酵組成物に含有させることを特徴とする、(7)に記載の方法。
That is, the present invention includes the following inventions.
(1) A seafood fermentation composition comprising ethyl nicotinate in a concentration range of 4 to 1000 ppb.
(2) The seafood fermentation composition according to (1), further comprising 0.2 to 4.0 times the amount of diethylene glycol monobutyl ether acetate by weight with respect to the ethyl nicotinate.
(3) A liquid seasoning comprising the seafood fermentation composition according to (1) or (2).
(4) The liquid seasoning as described in (3) containing the seafood fermentation composition and vinegar as described in (1) or (2).
(5) The liquid seasoning according to (3), comprising the fish and shellfish fermentation composition according to (1) or (2) and a fish knot extract.
(6) The liquid seasoning according to (3), wherein the liquid seasoning is a seafood fermentation seasoning, ponzu, soup, or sauce.
(7) Fish and seafood fermentation seasoning in a liquid seasoning containing a seafood fermentation composition or a seafood fermentation composition, characterized in that ethyl nicotinate is contained in the fish and seafood fermentation composition in a concentration range of 4 to 1000 ppb. To suppress the unpleasant odor peculiar to food.
(8) The seafood fermentation composition further contains 0.2 to 4.0 times the amount of diethylene glycol monobutyl ether acetate by weight with respect to the ethyl nicotinate. Method.
本発明によれば、魚介類発酵調味料特有の不快臭が顕著に抑制された魚介類発酵組成物が提供される。本発明の魚介類発酵組成物およびこれを含有する液状調味料は、魚介類発酵調味料特有の不快臭が感じられず、旨みと風味に優れる。 ADVANTAGE OF THE INVENTION According to this invention, the seafood fermented composition in which the unpleasant odor peculiar to seafood fermented seasonings was suppressed notably is provided. The fish and shellfish fermented composition of the present invention and the liquid seasoning containing the same do not feel the unpleasant odor peculiar to fish and shellfish fermented seasonings, and are excellent in umami and flavor.
1.魚介類発酵組成物
本発明の魚介類発酵組成物は、ニコチン酸エチルを4〜1000ppbの濃度範囲で含有することを特徴とする。本発明の魚介類発酵組成物はまた、ニコチン酸エチルを4〜1000ppbの濃度範囲で含有し、かつ、該ニコチン酸エチルに対し、重量比で0.2〜4.0倍量のジエチレングリコールモノブチルエーテルアセタートを含有することを特徴とする。
1. Seafood Fermentation Composition The seafood fermentation composition of the present invention is characterized by containing ethyl nicotinate in a concentration range of 4 to 1000 ppb. The fish and shellfish fermentation composition of the present invention also contains ethyl nicotinate in a concentration range of 4 to 1000 ppb, and 0.2 to 4.0 times by weight of diethylene glycol monobutyl ether with respect to the ethyl nicotinate. It is characterized by containing acetate.
本発明の「魚介類発酵組成物」には、魚介類原料を自己消化により分解した組成物、魚介類原料を麹により分解した組成物、酵素製剤を用いて分解した組成物、乳酸菌または酵母を用いて発酵もしくは分解した組成物のいずれもが包含される。 The “fish and shellfish fermentation composition” of the present invention includes a composition obtained by decomposing a seafood raw material by self-digestion, a composition obtained by decomposing a seafood raw material with straw, a composition decomposed using an enzyme preparation, lactic acid bacteria or yeast. Any composition fermented or degraded using is encompassed.
本発明の魚介類発酵組成物は、魚介類発酵調味料特有の不快臭が顕著に抑制されている。ここで、「魚介類発酵調味料」とは、魚介類に食塩を添加して漬け込み、自己消化により組織を分解して得られた諸味を圧搾濾過するという基本的製法、または、呈味や風味の改善を目的として原料や発酵条件等について基本的製法に種々の改変を加えた製法により得られる魚醤または魚醤様調味料をいう。また、「魚介類発酵調味料特有の不快臭」とは、魚介類またはその発酵物中のアミン類、アルデヒド類、不飽和脂肪酸などに起因する刺激臭、酸化臭、魚臭さなどをいう。 In the seafood fermentation composition of the present invention, the unpleasant odor peculiar to seafood fermentation seasonings is remarkably suppressed. Here, “seafood fermented seasoning” is a basic production method in which salt is added to seafood and soaked, and the taste obtained by decomposing tissues by self-digestion is squeezed and filtered. It is a fish soy or fish soy-like seasoning obtained by a production method in which various modifications are made to the basic production method for the purpose of improving the raw materials and fermentation conditions. In addition, “unpleasant odor peculiar to a fermented seafood seasoning” refers to an irritating odor, an oxidized odor, a fish odor, etc. caused by amines, aldehydes, unsaturated fatty acids, etc. in the seafood or its fermented product.
本発明の魚介類発酵組成物に含有させるニコチン酸エチル(慣用名:ニコチン酸エチルエステル、3−ピリジンカルボン酸エチル、ピリジン−3−カルボン酸エチル、エチル ニコチナート、英文表記:Nicotinic acid ethyl, Nicotinic acid ethyl ester, 3-Pyridinecarboxylic acid ethyl, 3-Pyridinecarboxylic acid ethyl ester, Ethyl nicotinate)は分子式C8H9NO2(分子量:151.16)を有し、下記の構造式(I)で示される公知の物質である。また、CAS登録番号は614−18−6である。 Ethyl nicotinate (common name: ethyl nicotinate, ethyl 3-pyridinecarboxylate, ethyl pyridine-3-carboxylate, ethyl nicotinate, English text: Nicotinic acid ethyl, Nicotinic acid) Ethyl ester, 3-Pyridinecarboxylic acid ethyl, 3-Pyridinecarboxylic acid ethyl ester, Ethyl nicotinate) has the molecular formula C 8 H 9 NO 2 (molecular weight: 151.16) and is represented by the following structural formula (I) It is a substance. The CAS registration number is 614-18-6.
上記ニコチン酸エチルは、公知の合成方法、例えばニコチン酸とエタノールの縮合反応によって得ることができる。 The ethyl nicotinate can be obtained by a known synthesis method, for example, a condensation reaction of nicotinic acid and ethanol.
また、ニコチン酸エチル単体に代えて、ニコチン酸含有物を含有させてもよい。ニコチン酸エチルは、天然には熟成させたビール(European Food Research and Tecnology, Vol.215, No.3, pp.235-239, 2002)等にその存在が知られている。従って、ニコチン酸含有物として熟成させたビールを用いることができる。また、上記熟成させたビールとは、通常のビール製造工程において醗酵工程終了後の貯蔵タンクでの熟成工程を長期間行ったビールをいい、熟成期間としては、温度により異なるが、例えば、10〜15℃で、約2ヶ月〜約2年程度が例示できる。 Moreover, it may replace with ethyl nicotinate single-piece | unit and may contain a nicotinic acid containing material. The existence of ethyl nicotinate is known in natural aged beer (European Food Research and Tecnology, Vol. 215, No. 3, pp. 235-239, 2002). Therefore, aged beer can be used as the nicotinic acid-containing material. The aged beer refers to a beer that has been subjected to a aging process in a storage tank after completion of the fermentation process in a normal beer production process for a long period of time. An example is about 2 months to about 2 years at 15 ° C.
ニコチン酸含有物の他の例としては、米に分解酵素や米麹を加えて糖化させた「米糖化液」を100℃〜130℃で加熱処理した「米糖化液の加熱処理物」が挙げられる。ニコチン酸エチル含有物として「米糖化液の加熱処理物」を含有させる場合には、「米糖化液」を加熱処理することによってニコチン酸エチルが増加し、かつ「米糖化液」自体が焦げ付きによって風味を損なっていない状態の「米糖化液の加熱処理物」を含有させることが好ましい。「米糖化液の加熱処理物」の製造は、例えば以下のようにして行うことができる。まず原料米を破砕または粉砕してメッシュに通した後、水に混合する。この米混合液に、麹及び/又は酵素製剤(液化酵素、糖化酵素、タンパク質分解酵素等)を添加して分解し、圧搾ろ過して「米糖化液」を得、続いて、この「米糖化液」を100℃〜130℃で30分〜180分間加熱する。 Other examples of the nicotinic acid-containing material include “rice saccharified solution heat-treated product” obtained by heat-treating “rice saccharified solution” obtained by adding a degrading enzyme or rice bran to rice and saccharifying it at 100 ° C. to 130 ° C. It is done. When the “rice saccharified solution heat-treated product” is contained as the ethyl nicotinate-containing material, the heat treatment of the “rice saccharified solution” increases ethyl nicotinate, and the “rice saccharified solution” itself is burnt. It is preferable to contain “a heat-treated product of rice saccharified solution” that does not impair the flavor. The “heated product of rice saccharified solution” can be produced, for example, as follows. First, raw rice is crushed or crushed and passed through a mesh, and then mixed with water. To this rice mixture, koji and / or enzyme preparations (liquefaction enzyme, saccharification enzyme, proteolytic enzyme, etc.) are added and decomposed, and pressed and filtered to obtain “rice saccharified solution”. The “liquid” is heated at 100 to 130 ° C. for 30 to 180 minutes.
本明細書において、「ニコチン酸エチル含有物」は、上記に挙げたニコチン酸エチル含有物の抽出液や希釈液を含む意味で用いられる。また、ニコチン酸エチル含有物は、ニコチン酸エチル含有物の抽出液や希釈液に対して種々の処理を施し、種々の形態に加工したものであってもよい。 In the present specification, the “ethyl nicotinate-containing product” is used to include an extract or a diluted solution of the ethyl nicotinate-containing product listed above. Further, the ethyl nicotinate-containing material may be obtained by performing various treatments on the extract or dilution liquid of the ethyl nicotinate-containing material and processing into various forms.
ニコチン酸エチルを単体で使用する場合は、化学合成によって得られたものを使用してもよいが、上記のニコチン酸エチル含有物から抽出し、単離精製して得られたものを使用してもよい。抽出は、水、水溶性溶媒又はこれらの混合溶媒を用いて行えばよく、水溶性溶媒としては、エタノール、n−プロピルアルコール、イソプロピルアルコール等の低級アルコール類、ジメチルアセトンアミド、ジメチルホルムアミド等が挙げられる。単離精製は、上記抽出物を必要により減圧濃縮した後、常用される精製手段(例えば、イオン交換樹脂、膜分画、吸着クロマトグラフィー、(高速)液体クロマトグラフィー、逆相クロマトグラフィー、親和性クロマトグラフィーなど)を単独でまたは組合せて用いて行うことができる。 When ethyl nicotinate is used alone, it may be obtained by chemical synthesis, but it is extracted from the above ethyl nicotinate-containing material and is isolated and purified. Also good. Extraction may be performed using water, a water-soluble solvent, or a mixed solvent thereof. Examples of the water-soluble solvent include lower alcohols such as ethanol, n-propyl alcohol, and isopropyl alcohol, dimethylacetamide, dimethylformamide, and the like. It is done. In the isolation and purification, the above extract is concentrated under reduced pressure if necessary, and then commonly used purification means (for example, ion exchange resin, membrane fractionation, adsorption chromatography, (high-speed) liquid chromatography, reverse phase chromatography, affinity Chromatography, etc.) can be used alone or in combination.
本発明の魚介類発酵組成物におけるニコチン酸エチルの含有量は、4〜1000ppb、好ましくは8〜100ppb、より好ましくは10〜50ppb(重量割合)である。ニコチン酸エチルの含有量が4ppbよりも少ないと、魚介類発酵調味料特有の不快臭が十分に抑制されず好ましくない。また、ニコチン酸エチルの含有量が1000ppbを超えても、それ以上は魚介類発酵調味料特有の不快臭の抑制効果は得られず、かえってニコチン酸エチル自体の味が感じられるようになり、味に違和感が生じ好ましくない。 The content of ethyl nicotinate in the fish and shellfish fermentation composition of the present invention is 4 to 1000 ppb, preferably 8 to 100 ppb, more preferably 10 to 50 ppb (weight ratio). If the content of ethyl nicotinate is less than 4 ppb, the unpleasant odor peculiar to fish and shellfish seasonings is not sufficiently suppressed, which is not preferable. Moreover, even if the content of ethyl nicotinate exceeds 1000 ppb, the effect of suppressing unpleasant odor peculiar to seafood fermented seasonings cannot be obtained, and the taste of ethyl nicotinate itself can be felt. This is not preferable because of an uncomfortable feeling.
本発明の魚介類発酵組成物において、上記ニコチン酸エチルに併せて含有させるジエチレングリコールモノブチルエーテルアセタート(慣用名:ブチルカルビトールアセテート、ジエチレングリコ-ルモノブチルエ-テルアセテート、酢酸2-(2-N-ブトキシエトキシ)エチル、酢酸N-ブチルカルビトール)、英文表記:2-(2-Butoxyethoxy)ethyl acetate)は分子式C10H20O4(分子量:204.26)を有し、下記の構造式(II)で示される公知の物質である。また、CAS登録番号は124−17−1である Diethylene glycol monobutyl ether acetate (common names: butyl carbitol acetate, diethylene glycol monobutyl ether acetate, 2- (2-N-butoxyethoxy acetate) ) Ethyl, N-butylcarbitol acetate), English: 2- (2-Butoxyethoxy) ethyl acetate) has the molecular formula C 10 H 20 O 4 (molecular weight: 204.26) and has the following structural formula (II) It is a well-known substance shown by. The CAS registration number is 124-17-1.
上記ジエチレングリコールモノブチルエーテルアセタートは、塗料、印刷インキ用溶剤、樹脂溶剤として用いられる有機化合物であるが、これまで食品素材に含まれるという報告はない。 Although the said diethylene glycol monobutyl ether acetate is an organic compound used as a paint, a solvent for printing inks, and a resin solvent, it has not been reported to be contained in a food material until now.
本発明の魚介類発酵組成物におけるジエチレングリコールモノブチルエーテルアセタートの含有量は、上記の濃度範囲で含有するニコチン酸エチルに対し、重量比で0.2〜4.0倍量、好ましくは0.26〜3.33倍量、より好ましくは0.28〜1.67倍量である。ジエチレングリコールモノブチルエーテルアセタートの含有量がニコチン酸エチルに対し、重量比で0.2倍量より少ないと、ニコチン酸エチルとの相乗的な効果が明確に認められず、また、重量比で4.0倍量を超えても、それ以上は特有の不快臭の抑制効果は向上せず、かえってジエチレングリコールモノブチルエーテルアセタート自体の味が感じられるようになり、味に違和感が生じ好ましくない。 The content of diethylene glycol monobutyl ether acetate in the fish and shellfish fermentation composition of the present invention is 0.2 to 4.0 times, preferably 0.26, in weight ratio with respect to ethyl nicotinate contained in the above concentration range. The amount is 3.33 times, more preferably 0.28 to 1.67 times. When the content of diethylene glycol monobutyl ether acetate is less than 0.2 times the weight of ethyl nicotinate, a synergistic effect with ethyl nicotinate is not clearly observed, and the weight ratio of 4. Even if the amount exceeds 0 times, the effect of suppressing the peculiar unpleasant odor is not improved, and the taste of diethylene glycol monobutyl ether acetate itself can be felt.
本発明の魚介類発酵組成物は、ニコチン酸エチルが前記の所定の濃度範囲になるように含有していればよく、含有させる手段は特に問わない。よって、ニコチン酸エチルやニコチン酸エチル含有物を魚介類発酵組成物の原料に添加する方法に限られず、ニコチン酸エチルが前記の所定の濃度範囲の範囲となるように、魚介類発酵組成物の原料や手段を適宜選択してもよい。例えば、ニコチン酸を高含有する魚介類の選択、ニコチン酸高生産性の微生物種の選択、エタノールの高濃度化、これら成分のエステル化の促進などがその手段として挙げられ、魚介類発酵組成物の風味を損なわない程度に適宜検討すればよい。 The fish and shellfish fermentation composition of this invention should just contain so that ethyl nicotinate may become the said predetermined concentration range, and the means to contain is not ask | required in particular. Therefore, the method is not limited to the method of adding ethyl nicotinate or ethyl nicotinate-containing material to the raw material of the fish and shellfish composition, but the fish and fish composition of the fish and shellfish composition is adjusted so that ethyl nicotinate falls within the predetermined concentration range. You may select a raw material and a means suitably. For example, selection of fish and shellfish containing a high content of nicotinic acid, selection of microbial species with high productivity of nicotinic acid, high concentration of ethanol, promotion of esterification of these components, etc. What is necessary is just to consider suitably to such an extent that the flavor of this is not impaired.
同様に、本発明の魚介類発酵組成物は、ジエチレングリコールモノブチルエーテルアセタートを、ニコチン酸エチルに対して前記の所定の重量比となるよう含有していればよく、含有させる手段は特に問わない。 Similarly, the fish and shellfish fermentation composition of this invention should just contain diethylene glycol monobutyl ether acetate so that it may become said predetermined weight ratio with respect to ethyl nicotinate, and the means to contain is not ask | required in particular.
従って、本発明の魚介類発酵組成物は、ニコチン酸エチルまたはニコチン酸エチル含有物を魚介類発酵組成物中のニコチン酸エチルが前記の所定の濃度範囲となるよう含有させる工程、または、前記ニコチン酸エチル含量に対し、ジエチレングリコールモノブチルエーテルアセタートを前記の所定の重量比となるように含有させる工程を含む以外は、原料の仕込み工程、発酵・熟成工程、火入れ工程、およびろ過(オリ引き)工程を含む公知の魚介類発酵調味料の製造方法に従って製造すればよい。 Therefore, the fish and shellfish fermentation composition of the present invention comprises a step of containing ethyl nicotinate or an ethyl nicotinate-containing material so that the ethyl nicotinate in the fish and shellfish fermentation composition is within the predetermined concentration range, or the nicotine Except for including the step of adding diethylene glycol monobutyl ether acetate to the above-mentioned predetermined weight ratio with respect to the ethyl acid content, the raw material charging step, the fermentation / ripening step, the firing step, and the filtration (orientation) step What is necessary is just to manufacture according to the manufacturing method of the well-known fermented seafood seasoning containing this.
例えば、伝統的な魚介類発酵調味料の製造方法に従い、魚介類を食塩水に漬け込み、数ヶ月から数年にわたって長期熟成を行う製法を採用してよく、仕込み原料に、魚介類発酵調味料製造に通常使用されている麹、酵母、乳酸菌、酵素製剤などを加えて発酵熟成させる方法を採用してもよい。 For example, according to the traditional method for producing fermented seafood seasonings, a method may be adopted in which seafood is soaked in saline and aged for a long period of time from several months to several years. A method of fermenting and ripening by adding koji, yeast, lactic acid bacteria, enzyme preparations and the like, which are usually used, may be employed.
原料となる「魚介類」の種類は、魚介類発酵調味料の原料として一般に使用されるものであれば特に限定はされない。例えば、いわし、さば、にしん、あじ、さんま、かつお、まぐろ、さけ、ます、たら等の魚類、かき、ほたて、あわび、はまぐり、あさり、しじみ等の貝類、いか、たこ、えび、かに等の海産物が挙げられる。これらの魚介類は1種を用いてもよく、2種以上を混合して用いてもよい。また、原料となる魚介類は、その全体を用いてもよく、一部を用いてもよい。例えば、魚体そのもの、切り身、缶詰等の製造工程で生じた魚介類の加工残さい(内臓、鰓、中骨、頭等を含む)、その残さいから内臓や鰓を除去した残さい、魚介類の頭骨、骨等のいずれを使用してもよい。魚介類は、仕込み時の原料混合と発酵・熟成を効率よく行うために、切断、粗砕等の前処理を行うことが好ましい。 The kind of “seafood” used as a raw material is not particularly limited as long as it is generally used as a raw material for fermented seafood seasonings. For example, fish such as sardine, mackerel, herring, horse mackerel, bonito, tuna, salmon, sea bream, oysters, scallops, abalone, clams, clams, clams, sea bream, squid, octopus, shrimp, crab, etc. Seafood. These fish and shellfishes may use 1 type, and may mix and use 2 or more types. Moreover, the whole seafood used as a raw material may be used, and a part may be used. For example, processing residue of fish and shellfish produced in the manufacturing process such as fish itself, fillet and canned food (including internal organs, sea bream, middle bone, head, etc.), residue from removing internal organs and sea bream from the residue, seafood Any of skulls and bones may be used. The fish and shellfish are preferably subjected to pretreatment such as cutting and coarse crushing in order to efficiently perform raw material mixing and fermentation / ripening at the time of preparation.
食塩は、食塩水として使用されるのが好ましい。水に対する食塩の濃度は、特に限定されないが、5〜25%(w/w)の濃度が好ましい。 Salt is preferably used as the saline. Although the density | concentration of the salt with respect to water is not specifically limited, The density | concentration of 5-25% (w / w) is preferable.
仕込み原料の発酵は、28℃〜35℃の温度範囲で行うことが好ましく、14日間〜1ヶ月間の時間をかけて行うことが好ましい。熟成が進行すると、原料固形物が可溶化してくる。熟成の終点は、通常の醤油を製造する場合と同様により決定することができる。例えば、性状(色、におい、濁りの程度、原料の外観等)、分解物中に含まれるアミノ酸等の物質の濃度、分解物のpH等を指標とすることができる。充分に熟成したところで、圧搾、遠心分離、ろ過等の方法により液状物を得る。 Fermentation of the charged raw materials is preferably performed in a temperature range of 28 ° C. to 35 ° C., and is preferably performed over a period of 14 days to 1 month. As aging progresses, the raw material solids become solubilized. The end point of aging can be determined in the same manner as in the case of producing ordinary soy sauce. For example, properties (color, odor, degree of turbidity, appearance of raw materials, etc.), concentration of substances such as amino acids contained in the degradation product, pH of the degradation product, and the like can be used as indicators. When fully aged, a liquid material is obtained by methods such as pressing, centrifugation, and filtration.
得られた液状物は、酵素類を失活させるため、また殺菌のため加熱することができる。またミクロフィルターろ過により、菌体及び微細な固形成分(おり)の除去操作を行ってもよい。 The resulting liquid can be heated to inactivate enzymes and for sterilization. Moreover, you may perform the removal operation of a microbial cell and a fine solid component (cage) by microfilter filtration.
本発明においては、魚介類発酵組成物中のニコチン酸エチルおよびジエチレングリコールモノブチルエーテルアセタートが前記の濃度範囲内となるように正確に調整するために、上記の製造方法のいずれかにより得られた魚介類発酵組成物や、前記のニコチン酸エチル含有物におけるニコチン酸エチル濃度が不明な場合は、その濃度を測定して適宜調整すればよい。 In the present invention, in order to accurately adjust the ethyl nicotinate and diethylene glycol monobutyl ether acetate in the fish and shellfish fermentation composition to be within the above-mentioned concentration range, the fish and shellfish obtained by any of the above production methods If the concentration of ethyl nicotinate in the fermented fermented composition or the ethyl nicotinate-containing material is unknown, the concentration may be measured and adjusted accordingly.
魚介類発酵物中のニコチン酸エチルおよびジエチレングリコールモノブチルエーテルアセタートの濃度は、たとえば、GC/MSなどの公知の方法で定量することができる。 The concentrations of ethyl nicotinate and diethylene glycol monobutyl ether acetate in the fermented seafood can be quantified by a known method such as GC / MS.
GC/MSで定量する場合、試料からニコチン酸エチルおよびジエチレングリコールモノブチルエーテルアセタートを抽出して高濃度にまで濃縮して分析に供する必要がある。 When quantifying by GC / MS, it is necessary to extract ethyl nicotinate and diethylene glycol monobutyl ether acetate from a sample, concentrate them to a high concentration, and use them for analysis.
抽出方法としては、固相マイクロ抽出法や、ポリジメチルシロキサンでコーティングした攪拌子を用いて目的成分を抽出するSBSE法(スターバー抽出法)等が特に好ましい。SBSE法では、試料中のニコチン酸エチルおよびジエチレングリコールモノブチルエーテルアセタートに吸着させ、加熱脱着法などの方法により、吸着したニコチン酸エチルおよびジエチレングリコールモノブチルエーテルアセタートをGC/MSに導入し、定量する。 The extraction method is particularly preferably a solid-phase microextraction method or a SBSE method (starburr extraction method) in which a target component is extracted using a stirrer coated with polydimethylsiloxane. In the SBSE method, ethyl nicotinate and diethylene glycol monobutyl ether acetate in a sample are adsorbed, and the adsorbed ethyl nicotinate and diethylene glycol monobutyl ether acetate are introduced into GC / MS and quantified by a method such as a heat desorption method.
2.液状調味料
本発明の魚介類発酵組成物は単独で魚介類発酵調味料として使用することも可能であるが、他の調味料とともに含有する液状調味料としてもよい。例えば、魚節抽出物または食酢とともに当該魚介類発酵組成物を含有する液状調味料が好ましい。
2. Liquid seasoning Although the seafood fermentation composition of the present invention can be used alone as a seafood fermentation seasoning, it may be a liquid seasoning contained together with other seasonings. For example, a liquid seasoning containing the fishery product extract or vinegar and the seafood fermentation composition is preferred.
一般に、魚介類発酵調味料と魚節抽出物を含む調味料の場合は、節由来の魚臭さと魚介類発酵調味料特有の不快臭が相乗的に不快な香りとして感じやすいので、魚節抽出物とともに本発明の魚介類発酵組成物を用いれば、上記のような相乗的な不快臭を有効に抑制することができる。魚介類発酵組成物を魚節抽出物とともに含有する液状調味料を調製する場合、優れた不快臭の抑制と風味のバランスが得られる上で、魚介類発酵組成物1重量%に対して魚節抽出物1〜20重量%、好ましくは1.33〜4.0重量%、より好ましくは1.67〜2.5重量%を配合すればよい。 In general, in the case of seasonings containing fermented seafood seasonings and fish bun extracts, the fish odor derived from knots and the unpleasant odor unique to fermented seafood seasonings are easily felt synergistically as an unpleasant scent. If the fish and shellfish fermentation composition of this invention is used with a thing, the above synergistic unpleasant odor can be suppressed effectively. When preparing a liquid seasoning containing a seafood fermentation composition together with a fish knot extract, an excellent unpleasant odor control and flavor balance can be obtained. The extract may contain 1 to 20% by weight, preferably 1.33 to 4.0% by weight, more preferably 1.67 to 2.5% by weight.
「魚節」とは、魚体を煮てから固くなるまで乾燥させたものをいい、本鰹節、宗田鰹節、鯖節、あじ節、まぐろ節、いわし節、うるめ節、煮干などが含まれる。また、「魚節抽出物」としては、上記の魚節を熱水抽出して得られるだし(出汁)や、エタノール等のアルコールで抽出して調製される抽出エキスなどが挙げられ、それらの冷凍物、濃縮物や粉末化物、ペースト状物なども含まれる。節類から抽出する条件に特に限定はなく、一般的に用いられている条件を用いることができる。 “Fish Bun” refers to the fish that has been boiled and then dried until it becomes solid, and includes bonito, soda bonito, bonito, aji, tuna, sardine, urushi, and boiled sardines. Examples of the “fish section extract” include soup stock obtained by hot water extraction of the above fish section (extraction) and extract extracts prepared by extraction with alcohol such as ethanol. Products, concentrates, powdered products, pastes, and the like. There are no particular limitations on the conditions for extracting from the knots, and generally used conditions can be used.
本発明の魚節抽出物を含む液状調味料としては、例えば、つゆ類(汎用つゆ、麺つゆ、天つゆ、鍋つゆ、おでんつゆ等)、たれ類(天丼のたれ、蒲焼のたれ、照り焼きのたれ、焼き鳥のたれ、焼肉のたれ、豆腐のたれ、納豆のたれ、すきやきのたれ、しゃぶしゃぶのたれ等)、煮物調味料、だし醤油、だし割り醤油、だし味噌、ラーメン用スープなどが挙げられる。 Examples of the liquid seasoning containing the fish knot extract of the present invention include soy sauces (general soup, noodle soup, tempura soup, hot pot soup, oden soup etc.), sauces (steamed octopus sauce, salmon roasted sauce, teriyaki sauce) Sauce, Yakitori Sauce, Yakiniku Sauce, Tofu Sauce, Natto Sauce, Sukiyaki Sauce, Shabu Shabu Sauce), boiled seasoning, dashi soy sauce, dashi split soy sauce, dashi miso soup, ramen soup, etc.
本発明の魚節抽出物を含む液状調味料は、魚節抽出物を含む液状調味料において通常用いられる原料の一部に、本発明の魚介類発酵組成物を配合する以外は、通常の手法で製造すればよい。例えば、つゆの場合は、魚節抽出物、食塩、砂糖等を含む調味液に、本発明の魚介類発酵組成物を加えればよい。 The liquid seasoning containing the fish knot extract of the present invention is a normal method except that the fish and shellfish fermentation composition of the present invention is blended with a part of the raw materials usually used in the liquid seasoning containing the fish knot extract. Can be manufactured. For example, in the case of soup, the fish and shellfish fermentation composition of the present invention may be added to a seasoning liquid containing a fish knot extract, salt, sugar and the like.
また、食酢を含有しpHが4以下となる液状調味料の場合においては、この酸性領域で魚介類発酵調味料特有の不快臭が強くなるため、食酢とともに本発明の魚介類発酵組成物を用いることによって、上記のような酸性領域における不快臭を有効に抑制することができる。魚介類発酵組成物を食酢とともに含有する液状調味料調製する場合、優れた不快臭の抑制と風味のバランスが得られる上で、魚介類発酵組成物1重量%に対して食酢を0.33〜5重量%、好ましくは0.5〜1.67重量%、より好ましくは0.63〜1.0重量%を配合すればよい。 Moreover, in the case of a liquid seasoning containing vinegar and having a pH of 4 or less, the unpleasant odor peculiar to seafood fermentation seasonings is strong in this acidic region, so the fishery product composition of the present invention is used together with vinegar. Thus, the unpleasant odor in the acidic region as described above can be effectively suppressed. When preparing a liquid seasoning containing a seafood fermentation composition together with vinegar, 0.33 vinegar is added to 1% by weight of the seafood fermentation composition in order to obtain an excellent unpleasant odor suppression and flavor balance. 5 wt%, preferably 0.5 to 1.67 wt%, more preferably 0.63 to 1.0 wt% may be blended.
ここで、「食酢」には、醸造酢、米酢、黒酢、玄米酢、粕酢、麦芽酢、はと麦酢などの穀物酢や、リンゴ酢、ブドウ酢、レモン酢、カボス酢や梅酢などの果実酢が含まれる。 Here, “food vinegar” includes brewed vinegar, rice vinegar, black vinegar, brown rice vinegar, rice bran vinegar, malt vinegar, hato vinegar and other grain vinegar, apple vinegar, grape vinegar, lemon vinegar, kabosu vinegar and plum vinegar Contains fruit vinegar.
本発明の食酢を含む液状調味料としては、例えば、加工食酢(ぼん酢、すし酢、甘酢など)、マヨネーズ、ドレッシング(分離液状、乳化液状、ノンオイルなど)などが挙げられる。 Examples of the liquid seasoning containing the vinegar of the present invention include processed vinegar (bon vinegar, sushi vinegar, sweet vinegar, etc.), mayonnaise, dressing (separated liquid, emulsified liquid, non-oil, etc.) and the like.
本発明の食酢を含む液状調味料は、食酢を含む液状調味料において通常用いられる原料の一部に、本発明の魚介類発酵組成物を配合する以外は、通常の手法で製造すればよい。例えば、ぽん酢の場合は、食酢、砂糖、塩、醤油、柑橘果汁、香辛料等を含む調味液に、本発明の魚介類発酵組成物を加えればよい。 What is necessary is just to manufacture the liquid seasoning containing the vinegar of this invention by a normal method except mix | blending the seafood fermentation composition of this invention with a part of raw material normally used in the liquid seasoning containing vinegar. For example, in the case of ponzu, the fish and shellfish fermentation composition of the present invention may be added to a seasoning liquid containing vinegar, sugar, salt, soy sauce, citrus juice, spices, and the like.
以下、実施例によって本発明を更に具体的に説明するが、これらの実施例は本発明を限定するものでない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but these examples do not limit the present invention.
(参考例)成分の測定方法
以下の実施例および比較例において、試料中のニコチン酸エチル、ジエチレングリコールモノブチルエーテルアセタート濃度の測定は、以下の方法で行った。
(Reference example) Measuring method of component In the following examples and comparative examples, the concentration of ethyl nicotinate and diethylene glycol monobutyl ether acetate in the samples was measured by the following method.
(1)ニコチン酸エチル濃度の測定方法
試料20mlを平底のバイアル瓶に計り取り、SBSE(Stir Bar Sorptive Extraction)法にて試料中の香気成分を抽出した。ポリジメチルシロキサンでコーティングしたスターラーバー(Gestel社製)に吸着した香気成分を、加熱脱着システムを用いて加熱脱着させ、得られた試料をガスクロマトグラフィー分析装置に導入し、ガスクロマトグラフィー分析を行った。
(1) Method for measuring ethyl nicotinate concentration 20 ml of a sample was weighed into a flat-bottomed vial, and aroma components in the sample were extracted by the SBSE (Stir Bar Sorptive Extraction) method. Aroma components adsorbed on a stirrer bar (Gestel) coated with polydimethylsiloxane are heat desorbed using a heat desorption system, and the resulting sample is introduced into a gas chromatography analyzer for gas chromatography analysis. It was.
ガスクロマトグラフィー分析装置はAgilent 6890 Series GC System(Agilent社製)を用い、カラムはINERTCAP-WAX(内径0.25mm、長さ60m、膜厚0.25μm)(Gl-Sciences社製)を用い、キャリアガスはヘリウムガスを用いた。昇温プログラムは40℃にて5分間保持し、その後、5℃/分にて230℃まで昇温した後、230℃にて20分間保持した。 The gas chromatography analyzer uses an Agilent 6890 Series GC System (Agilent), and the column uses INERTCAP-WAX (inner diameter 0.25 mm, length 60 m, film thickness 0.25 μm) (Gl-Sciences). Helium gas was used as the carrier gas. The temperature raising program was held at 40 ° C. for 5 minutes, then heated to 230 ° C. at 5 ° C./min and then held at 230 ° C. for 20 minutes.
その後、試料の一部を質量分析計にかけてマススペクトルを求め、ニコチン酸エチルの関連イオンで確認を行った。質量分析計は5973 Mass Selective Detector(Agilent社製)を用い、イオン化法:EI+、イオン化電圧:70eVの条件でマススペクトル分析を行い、結果をスキャンモードで取り込み、ニコチン酸エチルに特徴的な質量電荷比78、106、123のイオンのうち、106をターゲットイオン、78と123を関連イオンとして用いて同定を行った。 Thereafter, a part of the sample was subjected to a mass spectrometer to obtain a mass spectrum, which was confirmed with related ions of ethyl nicotinate. The mass spectrometer uses 5973 Mass Selective Detector (Agilent), performs mass spectrum analysis under the conditions of ionization method: EI +, ionization voltage: 70 eV, captures the results in scan mode, and the mass charge characteristic of ethyl nicotinate Of the ions having ratios of 78, 106, and 123, identification was performed using 106 as a target ion and 78 and 123 as related ions.
また、別途、ニコチン酸エチルの標品(和光純薬工業社製)を0.5%エタノール溶液によって10ppb、1ppb、0.1ppb、0.01ppbに希釈したものを上記の条件にて分析に供した。そのマススペクトルパターンから保持時間36.557分付近のピークをニコチン酸エチルと判定し、それらのターゲットイオン(質量電荷比106)のピーク面積の比較によって、試料中のニコチン酸エチルの定量を行った。 Separately, a sample of ethyl nicotinate (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 10 ppb, 1 ppb, 0.1 ppb, and 0.01 ppb with a 0.5% ethanol solution was subjected to analysis under the above conditions. From the mass spectrum pattern, the peak at a retention time of 36.557 minutes was determined to be ethyl nicotinate, and the amount of ethyl nicotinate in the sample was determined by comparing the peak areas of those target ions (mass-to-charge ratio 106). .
(2)ジエチレングリコールモノブチルエーテルアセタート濃度の測定
試料20mlを平底のバイアル瓶に計り取り、SBSE(Stir Bar Sorptive Extraction)法にて試料中の香気成分を抽出した。ポリジメチルシロキサンでコーティングしたスターラーバー(Gestel社製)に吸着した香気成分を、加熱脱着システムを用いて加熱脱着させ、得られた試料をガスクロマトグラフィー分析装置に導入し、ガスクロマトグラフィー分析を行った。
(2) Measurement of diethylene glycol monobutyl ether acetate concentration 20 ml of a sample was weighed into a flat-bottomed vial, and an aroma component in the sample was extracted by the SBSE (Stir Bar Sorptive Extraction) method. Aroma components adsorbed on a stirrer bar (Gestel) coated with polydimethylsiloxane are heat desorbed using a heat desorption system, and the resulting sample is introduced into a gas chromatography analyzer for gas chromatography analysis. It was.
ガスクロマトグラフィー分析装置はAgilent 5983 Network Mass Selctive Detector (Agilent社製)を用い、カラムはINERTCAP-WAX(内径0.25mm、長さ60m、膜厚0.25μm)(Gl-Sciences社製) (Gl-Sciences社製)を用い、キャリアガスはヘリウムガスを用いた。昇温プログラムは40℃にて5分間保持し、その後、5℃/分にて230℃まで昇温した後、230℃にて20分間保持した。 The gas chromatography analyzer uses Agilent 5983 Network Mass Selctive Detector (Agilent), and the column is INERTCAP-WAX (inner diameter 0.25 mm, length 60 m, film thickness 0.25 μm) (Gl-Sciences) (Gl -Sciences) and helium gas was used as the carrier gas. The temperature raising program was held at 40 ° C. for 5 minutes, then heated to 230 ° C. at 5 ° C./min and then held at 230 ° C. for 20 minutes.
その後、試料の一部を質量分析計にかけてマススペクトルを求め、ジエチレングリコールモノブチルエーテルアセタートの関連イオンで確認を行った。質量分析計は5973 Mass Selective Detector(Agilent社製)を用い、イオン化法:EI+、イオン化電圧:70eVの条件でマススペクトル分析を行い、結果をスキャンモードで取り込み、ニコチン酸エチルに特徴的な質量電荷比57、81、43のイオンのうち、57をターゲットイオン、
81と43を関連イオンとして用いて同定を行った。
Thereafter, a part of the sample was subjected to a mass spectrometer to obtain a mass spectrum, which was confirmed with related ions of diethylene glycol monobutyl ether acetate. The mass spectrometer uses 5973 Mass Selective Detector (Agilent), performs mass spectrum analysis under the conditions of ionization method: EI +, ionization voltage: 70 eV, captures the results in scan mode, and the mass charge characteristic of ethyl nicotinate Of the ions of ratio 57, 81, 43, 57 is the target ion,
Identification was performed using 81 and 43 as related ions.
また、別途、ジエチレングリコールモノブチルエーテルアセタートの標品(和光純薬工業社製)を0.5%エタノール溶液によって10ppb、1ppb、0.1ppb、0.01ppbに希釈したものを上記の条件にて分析に供した。そのマススペクトルパターンから保持時間33.28分付近のピークをジエチレングリコールモノブチルエーテルアセタートと判定し、それらのターゲットイオン(質量電荷比57)のピーク面積の比較によって、試料中のジエチレングリコールモノブチルエーテルアセタートの定量を行った。 Separately, a diethylene glycol monobutyl ether acetate preparation (manufactured by Wako Pure Chemical Industries, Ltd.) diluted to 10 ppb, 1 ppb, 0.1 ppb and 0.01 ppb with a 0.5% ethanol solution is subjected to the analysis under the above conditions. did. From the mass spectrum pattern, a peak at a retention time of 33.28 minutes was determined as diethylene glycol monobutyl ether acetate, and by comparison of the peak areas of those target ions (mass-to-charge ratio 57), the diethylene glycol monobutyl ether acetate in the sample was compared. Quantification was performed.
(3)全窒素濃度の測定
試料を高感度窒素・リン検出器にかけ、(1)または(2)の質量分析計による解析と同時に試料中の窒素化合物量を分析した。高感度窒素・リン検出器は、Agilent 6890 Series GC System(Agilent社製)に付属のNPD(Nitrogen-phosphor-detector)検出器を用いた。
(3) Measurement of total nitrogen concentration The sample was subjected to a highly sensitive nitrogen / phosphorus detector, and the amount of nitrogen compounds in the sample was analyzed simultaneously with the analysis by the mass spectrometer of (1) or (2). As the highly sensitive nitrogen / phosphorus detector, the NPD (Nitrogen-phosphor-detector) detector attached to the Agilent 6890 Series GC System (Agilent) was used.
(実施例1)ニコチン酸エチルの含有量の検討
(1)試験品の調製
参考例に示した方法に従ってニコチン酸エチル濃度を測定し、当該成分が検出限界(0.01ppb以下)であることが確認された市販の魚介類発酵調味料(富士食品工業製)に対し、ニコチン酸エチル(東京化成工業製)を下記表1に示す各試験区(試験区1、2、10:比較品、試験区3〜9:本発明品)に応じて添加し、試験品の魚発酵組成物を調製した。
(Example 1) Examination of content of ethyl nicotinate (1) Preparation of test product According to the method shown in the reference example, the concentration of ethyl nicotinate is measured, and the component is at the detection limit (0.01 ppb or less). For each of the confirmed commercial seafood fermented seasonings (Fuji Food Industries), ethyl nicotinate (Tokyo Chemical Industry) is shown in each test section shown in Table 1 below (Test sections 1, 2, 10: comparative product, test) (3) to (9): products according to the present invention) to prepare a test fish fermentation composition.
(2)官能評価方法
(1)で調製した試験品について、官能検査によって不快臭の抑制効果と、風味と呈味の両面からの好ましさ(総合評価)を評価した。官能評価は、熟練したパネル3名で行い、各試験項目の評価基準は以下のとおりである。
(2) Sensory evaluation method About the test article prepared by (1), the unpleasant odor suppression effect and the preference (comprehensive evaluation) from both sides of flavor and taste were evaluated by a sensory test. The sensory evaluation is performed by three skilled panels, and the evaluation criteria for each test item are as follows.
<不快臭抑制効果>
×:不快臭抑制効果がない。
△:不快臭抑制効果がやや認められる。
◇:不快臭抑制効果が認められる。
○:不快臭抑制効果が高く認められる。
◎:不快臭抑制効果が極めて高く認められる。
<Unpleasant odor suppression effect>
X: No unpleasant odor suppression effect
Δ: An unpleasant odor suppressing effect is slightly recognized.
◇: An unpleasant odor control effect is recognized.
○: Highly effective in suppressing unpleasant odor.
(Double-circle): The unpleasant odor suppression effect is recognized extremely high.
<総合評価>
×:悪い
△:やや悪い
◇:良い
○:非常に良い
◎:極めて良い
<Comprehensive evaluation>
×: Bad △: Slightly bad ◇: Good ○: Very good ◎: Very good
(3)結果
評価結果を下記表1に示す。
(3) Results The evaluation results are shown in Table 1 below.
表1に示されるように、ニコチン酸エチルが4ppb以上含まれる魚発酵組成物は、無添加の魚発酵組成物に比べて不快臭の抑制効果があった。また、この効果は、ニコチン酸エチルの添加量を増加させるにつれて向上したが、ニコチン酸エチルの含有量が増えるにつれて、風味の違和感が徐々に強くなり、3000ppb以上であるとそれが無視しがたくなり、味が劣ってくることがが判明した。表1の各試験区のデータにより、魚発酵組成物のニコチン酸エチルの含有量の好ましい範囲は4〜1000ppb、より好ましい範囲は8〜100ppbであると判断された。 As shown in Table 1, the fish fermentation composition containing 4 ppb or more of ethyl nicotinate had an effect of suppressing unpleasant odor compared to the fish fermentation composition without addition. In addition, this effect improved as the amount of ethyl nicotinate was increased. However, as the content of ethyl nicotinate increased, the unpleasant taste of the flavor gradually increased, and it was difficult to ignore when it was 3000 ppb or more. It turned out that the taste is inferior. From the data of each test section in Table 1, it was determined that the preferable range of the content of ethyl nicotinate in the fish fermentation composition was 4 to 1000 ppb, and the more preferable range was 8 to 100 ppb.
(実施例2)ニコチン酸エチル含有量とジエチレングリコールモノブチルエーテルアセタート含有量の割合の検討
(1)試験品の調製
参考例に示した方法に従ってニコチン酸エチル濃度とジエチレングリコールモノブチルエーテルアセタート濃度を測定し、当該成分が検出限界(0.01ppb)以下であることが確認された市販の魚介類発酵調味料(富士食品工業製)に対し、ニコチン酸エチル(東京化成工業製)とジエチレングリコールモノブチルエーテルアセタート(東京化成工業製)を下記表2に示す各試験区(試験区11:比較品、試験区12〜17:本発明品)に応じて添加し、試験品の魚発酵組成物を調製した。
(Example 2) Examination of ratio of ethyl nicotinate content and diethylene glycol monobutyl ether acetate content (1) Preparation of test article According to the method shown in the reference example, ethyl nicotinate concentration and diethylene glycol monobutyl ether acetate concentration were measured. In contrast to commercially available fermented seafood seasonings (manufactured by Fuji Shokuhin Kogyo Co., Ltd.), which are confirmed to be below the detection limit (0.01 ppb), ethyl nicotinate (manufactured by Tokyo Chemical Industry) and diethylene glycol monobutyl ether acetate (Manufactured by Tokyo Chemical Industry Co., Ltd.) was added according to each test section shown in Table 2 below (test section 11: comparative product, test sections 12-17: product of the present invention) to prepare a fish fermentation composition of the test product.
調製した試験品について、実施例1と同様にして官能検査を行った。結果を下記表2に示す。 The prepared test article was subjected to a sensory test in the same manner as in Example 1. The results are shown in Table 2 below.
表2に示されるように、ニコチン酸エチルにジエチレングリコールモノブチルエーテルアセタートを併用することにより、不快臭抑制効果を相乗的に向上させることがわかった。 As shown in Table 2, it was found that the use of diethylene glycol monobutyl ether acetate in combination with ethyl nicotinate synergistically improves the effect of suppressing unpleasant odors.
表2の各試験区のデータにより、ニコチン酸エチルを30ppb含有する魚発酵組成物におけるジエチレングリコールモノブチルエーテルアセタート含有量の好ましい範囲は8〜100ppb(ニコチン酸エチルに対して重量比で0.26〜3.33倍量)であると判断された。 According to the data of each test section in Table 2, the preferable range of the diethylene glycol monobutyl ether acetate content in the fish fermentation composition containing 30 ppb of ethyl nicotinate is 8 to 100 ppb (0.26 to 0.26 by weight with respect to ethyl nicotinate). 3.33 times the amount).
(実施例3)本発明品の魚節抽出物含有調味料(つゆ)への適用
粉砕した鰹荒節33.3gを90℃に加温した水1000mLに加え、90℃で30分間保持して、節成分を抽出した。その後、ろ過を行って、ろ液を得て、得られたろ液に水を加えて、魚節抽出物(3.3%節含量換算)1000mLを得た。
(Example 3) Application of the product of the present invention to a seasoning containing fish knot extract (tsuyu) 33.3 g of ground koji koji was added to 1000 mL of water heated to 90 ° C. and held at 90 ° C. for 30 minutes. The knot component was extracted. Thereafter, filtration was performed to obtain a filtrate, and water was added to the obtained filtrate to obtain 1000 mL of fishfish extract (converted to 3.3% clause content).
得られた鰹節抽出物に、魚発酵組成物、食塩、砂糖を添加し、試験品のつゆを調製した(実施例3−1〜3−7、比較例3−1〜3−3)。魚発酵組成物としては、前記試験区1の比較品(ニコチン酸エチル:0ppb)、試験区6の本発明品(ニコチン酸エチル:30ppb)、または試験区14の本発明品(ニコチン酸エチル:30ppb、ジエチレングリコールモノブチルエーテルアセタート:10ppb)を用い、いずれの試験品についても食塩はつゆの塩分濃度が6%になるように、砂糖はつゆのBrixが16%になるように添加した。調製した試験品について、実施例1と同様にして官能検査を行った。各試験品の配合処方(重量部)および官能検査の結果を表3に示す(表中、+は上記の所定濃度となるように成分を添加したことを示す)。 To the obtained bonito extract, a fish fermentation composition, salt and sugar were added to prepare test soup (Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-3). As the fish fermentation composition, the comparative product of the test group 1 (ethyl nicotinate: 0 ppb), the test product of the test group 6 (ethyl nicotinate: 30 ppb), or the test product of the test group 14 (ethyl nicotinate: 30 ppb, diethylene glycol monobutyl ether acetate: 10 ppb), and in each test sample, salt was added so that the salt concentration of soup was 6%, and sugar was added so that the Brix of soup was 16%. The prepared test article was subjected to a sensory test in the same manner as in Example 1. The compounding prescription (parts by weight) of each test product and the results of the sensory test are shown in Table 3 (in the table, + indicates that the component was added so as to have the above-mentioned predetermined concentration).
表3に示されるように、ニコチン酸エチルを含有しない魚発酵組成物を配合したつゆは、魚介類発酵調味料の臭いが感じられ、また節(カツオ)の臭いが強くなり、風味が劣ることがわかった。これに対し、ニコチン酸エチルを含有する魚発酵組成物、ニコチン酸エチルとジエチレングリコールモノブチルエーテルアセタートを含有する魚発酵組成物を配合したつゆは、魚介類発酵調味料の臭いが感じられず、魚介類発酵調味料の旨みがあり、風味が良好であることがわかった。表3の各試験区のデータにより、魚節抽出物含有調味料(つゆ)における魚発酵組成物と魚節抽出物の配合割合は、魚発酵組成物1重量部に対して、魚節抽出物(3.3%節含量換算)が1〜20重量部が好ましいと判断された。 As shown in Table 3, the soy sauce containing a fish fermentation composition that does not contain ethyl nicotinate has a smell of seafood fermented seasoning, and the smell of katsuo is strong and the flavor is poor. I understood. In contrast, fish soy sauce containing ethyl nicotinate and fish fermented composition containing ethyl nicotinate and diethylene glycol monobutyl ether acetate do not feel the smell of seafood fermentation seasonings. It was found that there was a taste of fermented seasonings and the flavor was good. According to the data of each test section in Table 3, the mixing ratio of the fish fermented composition and the fish knot extract in the seasoning containing the fish knot extract (tsuyu) is 1 fish part of the fish fermented composition. It was judged that 1 to 20 parts by weight (in terms of 3.3% content) was preferable.
(実施例4)本発明品の食酢含有調味料(ぽん酢)への適用
食酢(酸度15%)に、魚発酵組成物、果汁、食塩、砂糖を添加し、試験品のぽん酢を調製した(実施例4−1〜4−7、比較例4−1〜4−3)。魚発酵組成物としては、前記試験区1の比較品(ニコチン酸エチル:0ppb)、試験区6の本発明品(ニコチン酸エチル:30ppb)、または試験区14の本発明品(ニコチン酸エチル:30ppb、ジエチレングリコールモノブチルエーテルアセタート:10ppb)を用い、食塩はぽん酢の塩分濃度が5%になるように、砂糖はぽん酢のBrixが12%になるように添加した。調製した試験品について、実施例1と同様にして官能検査を行った。各試験品の配合処方(重量部)および官能検査の結果を表4に示す(表中、+は上記の所定濃度となるように成分を添加したことを示す)。
(Example 4) Application of the product of the present invention to a vinegar-containing seasoning (Ponzu) A fermented fish composition, fruit juice, salt and sugar were added to vinegar (acidity 15%) to prepare a test ponzu (implemented) Examples 4-1 to 4-7, comparative examples 4-1 to 4-3). As the fish fermentation composition, the comparative product of the test group 1 (ethyl nicotinate: 0 ppb), the test product of the test group 6 (ethyl nicotinate: 30 ppb), or the test product of the test group 14 (ethyl nicotinate: 30 ppb, diethylene glycol monobutyl ether acetate: 10 ppb), and salt was added so that the salt concentration of vinegar was 5%, and sugar was added so that Brix of vinegar was 12%. The prepared test article was subjected to a sensory test in the same manner as in Example 1. Table 4 shows the compounding prescription (parts by weight) and sensory test results of each test product (in the table, + indicates that the components were added so as to have the above-mentioned predetermined concentration).
表4に示されるように、ニコチン酸エチルを含有しない魚発酵組成物を配合したぽん酢は、魚介類発酵調味料の臭いが感じられ、また酸味とのバランスが悪かった。これに対し、ニコチン酸エチルを含有する魚発酵組成物、ニコチン酸エチルとジエチレングリコールモノブチルエーテルアセタートを含有する魚発酵組成物を配合したぽん酢は、魚介類発酵調味料の臭いが感じられず、酸味が適度に感じられ、旨みと酸味のバランスが良好であった。表4の各試験区のデータにより、食酢含有調味料(ぽん酢)における魚発酵組成物と食酢の配合割合は、魚発酵組成物1重量部に対して、食酢(酸度15%換算)が0.33〜5.0重量部が好ましいと判断された。 As shown in Table 4, the ponzu blended with the fish fermentation composition containing no ethyl nicotinate felt the smell of the seafood fermented seasoning and had a poor balance with the acidity. On the other hand, Ponzu blended with a fish fermentation composition containing ethyl nicotinate and a fish fermentation composition containing ethyl nicotinate and diethylene glycol monobutyl ether acetate does not feel the smell of seafood fermentation seasonings, sour Was felt moderately, and the balance between umami and sourness was good. According to the data of each test section in Table 4, the mixing ratio of the fish fermentation composition and vinegar in the vinegar-containing seasoning (ponzu vinegar) is 0.1 for vinegar (converted to 15% acidity) relative to 1 part by weight of the fish fermentation composition. It was judged that 33 to 5.0 parts by weight was preferable.
本発明は、魚介類発酵調味料の製造分野において利用できる。 The present invention can be used in the field of production of fermented seafood seasonings.
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