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JP4289730B2 - Sake Maturity Determination Method and Sake Maturity Determination Device - Google Patents
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JP4289730B2 - Sake Maturity Determination Method and Sake Maturity Determination Device - Google Patents

Sake Maturity Determination Method and Sake Maturity Determination Device Download PDF

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JP4289730B2
JP4289730B2 JP23476599A JP23476599A JP4289730B2 JP 4289730 B2 JP4289730 B2 JP 4289730B2 JP 23476599 A JP23476599 A JP 23476599A JP 23476599 A JP23476599 A JP 23476599A JP 4289730 B2 JP4289730 B2 JP 4289730B2
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sake
maturity
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JP2001059830A (en
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秀和 池崎
義和 小林
理江子 東久保
晃 谷口
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株式会社インテリジェントセンサーテクノロジー
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Description

【0001】
【発明の属する技術分野】
本発明は、清酒の熟度の判定を行うための技術に関する。
【0002】
【従来の技術】
清酒は、一般的には、醸造された後に火入れ処理され、火入れ処理後にタンクに貯蔵され(生酒の場合には醸造後に火入れ処理を行わずに貯蔵される)、適度な熟度になったころに容器に詰められて出荷される。
【0003】
このような工程によって清酒の製造、出荷する工場等では、貯蔵している清酒が出荷可能な熟度に達しているか否かを判定する必要がある。
【0004】
この熟度判定は、従来から、官能検査、即ち、専門の検査員が実際に清酒を味見することによって行なっていた。
【0005】
【発明が解決しようとする課題】
しかしながら、前記官能検査では、一人の検査員が判定できるサンプル数に限界がある。即ち、清酒の官能検査では、判定対象の清酒を口に含むだけで飲み込むことはしないが、実際には体内に微量ずつアルコールが吸収されてしまう。このため、判定対象のサンプル数があまり多くなると検査員が酔ってしまい、識別力が低下して正確な判定が行なえなくなる。
【0006】
また、検査員の識別力に個人差があり熟度の判定結果にバラツキが生じる。
【0007】
本発明は、この問題を解決して、官能検査に頼らずに、清酒の熟度を正確に把握できるようにした清酒熟度判定方法および清酒熟度判定装置を提供することを目的としている。
【0008】
【課題を解決するための手段】
前記目的を達成するために、本発明の請求項1の清酒熟度判定方法は、
醸造された直後の清酒のサンプルに、両親媒性物質を含む分子膜を浸漬して該分子膜の電位を初期値として測定する段階と、
前記サンプルを実際に熟成させるときの貯蔵温度より高い温度で保存し熟成を早めた状態で前記分子膜の電位の測定を行い、該測定された電位の前記初期値からの変化量を求め、該変化量のうち実際に出荷に適した熟度に達したときの変化量を判定基準値と決定する段階と、
醸造された直後の判定対象の清酒に、前記分子膜を浸漬して該分子膜の電位を測定する段階と、
前記醸造後の熟成が進行する通常環境下で時間が経過した清酒に、前記分子膜を浸漬して該分子膜の電位を測定する段階と、
前記醸造直後の清酒について測定した電位と、熟成が進行する環境下で時間が経過した清酒について測定した電位との差を求める段階と、
該求めた差と前記判定基準値とを比較し、該比較結果から前記判定対象の清酒が出荷に適した熟度に達したか否かを判定する段階とを含むことを特徴としている。
【0010】
また、本発明の請求項の清酒熟度判定装置は、
参照電極と、両親媒性物質を含む分子膜とを有するプローブ(22)と、
前記プローブの参照電極と分子膜との間の電位差を検出する電圧検出手段(35)と、
醸造された直後の清酒のサンプルに前記プローブを浸漬したときに前記電圧検出手段で得られた電位差を初期値として記憶し、且つ前記サンプルが実際に熟成するときの貯蔵温度より高い温度で保存されて熟成が早められた状態における前記プローブによる測定値の前記初期値からの変化量のうち、出荷に適した熟度に達したときの変化量を判定基準値として記憶している手段(37a)と、
前記プローブを判定対象の清酒に浸漬したときに前記電圧検出手段によって検出された電位差と前記初期値との差を求める減算手段(37)と、
前記減算手段で得られた差と前記判定基準値とを比較し、その比較結果から前記判定対象の清酒の熟度が出荷に適した熟度に達したか否かを判定する判定手段(37)とを備えたことを特徴としている。
【0011】
また、本発明の請求項3の清酒熟度判定装置は、請求項2記載の清酒熟度判定装置において、
前記分子膜は、両親媒性物質と、可塑材と、高分子材とを混合して得られたものであり、前記両親媒性物質は、極性を有し、その膜中の濃度が1〜7パーセントの範囲にあることを特徴としている。
【0012】
【発明の実施の形態】
以下、図面に基づいて本発明の実施形態を説明する。
図1は、清酒の熟度を判定するための清酒熟度判定装置20の構成を示す図である。
【0013】
図1において、清酒熟度判定装置20は、基準液や判定対象の清酒を入れるための容器21と、プローブ22と、プローブ22の出力電圧を検出する電圧検出器35と、電圧検出器35の出力をディジタル値に変換するA/D変換器36と、A/D変換器36の出力に対する演算処理や判定処理を行う演算装置37と、演算装置37の処理結果を出力する出力装置38によって構成されている。
【0014】
プローブ22は、容器21に入れた液体に漬けて使用するものであり、測定の基準電位を出力するための参照電極23と、両親媒性物質または苦み物質を含む分子膜25とを有している。
【0015】
参照電極23の表面は、液体内の脂質に反応しないように、塩化カリウム3.3mole/lを寒天で固定した緩衝層24で覆われており、リード線22aが接続されている。
【0016】
分子膜25は、アクリル等の基材26の表面に一面側を露呈させた状態で固定されており、分子膜25の反対面には、参照電極23の緩衝層24と同等の緩衝層27を介して電極28が設けられ、この電極28にはリード線22bが接続されている。
【0017】
分子膜25は、無極性で疎水性を有する部分と有極性で親水性を有する部分とを有する両親媒性物質が、その親水性部分を表面側に向けた状態で膜をなすように一体化されたものであり、液に漬けたときにその膜の電位が液中の成分に応じて変化する。
【0018】
この模式的な構造を図2に示す。図2において、各分子31は、球状の親水基31aと、親水基31aから原子配列が長く延びる炭化水素鎖31bとからなり、これらの各分子群が、その親水基31a側が表面側に並ぶように、膜部材32(後述の高分子と可塑剤からなる)の表面のマトリクス33(表面構造、平面的な広がりをもつミクロな構造)の中に、一部はマトリクス内部に溶け込んだ形(例えば分子31′)で収容されている。
【0019】
分子膜25は、脂質分子と、ベースとなる高分子と、可塑剤とを所定の割合で混合して作製されたものである。
【0020】
その一例を示すと、高分子にはポリ塩化ビニル(PVC)を用い、可塑剤としてフタル酸ジオクチル(DOP)、ジオクチルフェニルフォスフォネート(DOPP)、リン酸トリクレシル(TCP)あるいはニトロフェニルオクチルエーテル(NPOE)を用いて上記の脂質分子と混合したもの800mgを、THF10ccに溶解し、平底の容器(例えば85mmφのシャーレ)に移し、それを均一な加熱された板上で約30度Cに2時間保って、THFを揮散させることで厚さ約200μmの分子膜を得ることができる。なお、高分子と可塑剤の混合比は1対1程度であるが、後述するように高分子と可塑剤に対して脂質分子の濃度はかなり低くなっている。
【0021】
本願発明者らは、種々の実験からこの分子膜25の両親媒性物質の濃度を選ぶことによって、清酒の熟度に対して顕著な相関性を示す出力が得られることを見いだした。
【0022】
即ち、分子膜25を形成する脂質等の両親媒性物質として、極性を有するものを用い、その濃度を1〜7パーセントの範囲にすることで清酒の熟度に対して顕著に相関する出力が得られ、しかもその相関は、両親媒性物質の種類にほとんど依存しないことが判明した。
【0023】
実験は下記の(a)〜(e)の5つのパラメータで、計36種類の分子膜を作製し、清酒の熟度と感度の関係を調査した。
【0024】
(a)脂質の種類(トリオクチルアンモニウムクロライド、ジオクチルフォスフェート、オレイン酸、フォスファチジルセリン、オレイルアミン)
(b)可塑剤の種類(DOPP、NPOE、TDA)
(c)脂質の濃度
(d)可塑剤の濃度
(e)脂質の混合比
【0025】
また、清酒は、熟成過程に入る直前のもの(一般の清酒では醸造後に火入れ処理された直後のものであり、生酒の場合には醸造直後のものであるが、以下の説明では、この熟成過程に入る直前のものを火入れ処理を含めて醸造直後のものと記す)、醸造されてから40度の環境で1週間単位に、1〜5週間熟成したものを用いた。
【0026】
官能検査の結果では、40度で1週間から2週間で熟度が確実に増加していることが判った。
【0027】
そこで、熟度に対する感度は、各3種類の清酒に対して、初期から第1週間と第2週間の変化の大きさ(計6サンプルのセンサの変化量の絶対値の平均)で評価した。ここで、絶対値を用いたのは、膜の極性により、出力がプラスに変化するものとマイナスに変化するものとがあるからである。
【0028】
測定は3回ずつ行い、測定誤差の小さいものを20種類選択した。その20種類の膜の熟度に対する感度と、極性のある両親媒性物質の膜中の濃度の関係を図3に示す。
【0029】
図3に示しているように、熟度に対する感度は、極性のある両親媒性物質の膜中の濃度に依存して変化することが発見できた。
【0030】
なお、可塑剤に含まれる不純物は、可塑剤の製造過程において数パーセントの含有量で混入する物質で、極性のある両親媒性物質を含んでおり、極性のある両親媒性物質の膜中の濃度には可塑剤中のものも含んでいる。
【0031】
今回の実験では、分析の結果、NPOE自体に2パーセント、DOPP自体に2パーセント、TDA自体に0.5パーセント含まれていた。
【0032】
図3から明らかなように、可塑剤中のものを含んだ膜中の両親媒性物質の濃度が1〜7パーセントの範囲では、誤差に比較して優位な感度があり、熟度に相関する出力が得られており、1〜4パーセントの範囲では感度が2倍近く得られ、さらに、1.5〜3パーセントの範囲では、より高い感度が得られている。
【0033】
なお、清酒内のどの物質に両親媒性物質が感応しているかは現在のところ特定されていないが、味の測定等に従来使用されていた分子膜のように両親媒性物質の濃度が10〜20パーセントのものでは、清酒の熟度に相関を示すような出力は得られておらず、この分子膜25の両親媒性物質の濃度の低さから清酒中の微量物質に感応していると見られ、熟成が進むほどこの微量物質の濃度が高くなるものと予想される。
【0034】
このように、極性を有し、可塑剤に含まれるものを含めた両親媒性物質の膜中の濃度を1〜7パーセントの範囲にすることで、清酒の熟度の判定に適した分子膜を得ることができる。
【0035】
上記の分子膜25と参照電極23とからなるプローブ22を液体に漬ける際には、測定条件が変わらないように、参照電極23と分子膜25の間隔を一定にするが、支持材29によって参照電極23と基材26とを一定の間隔で支持してもよい。
【0036】
プローブ22のリード線22a、22bは、電圧検出器35に接続されている。電圧検出器35は、例えば差動増幅器によって構成され、参照電極23の電位と分子膜25の電位の差(電圧)を検出してA/D変換器36に出力する。
【0037】
A/D変換器36は電圧検出器35の出力電圧をディジタル値に変換して演算装置37に出力する。
【0038】
演算装置37は、マイクロコンピュータによって構成され、図示しない操作部等から記憶指示Mを受けるとA/D変換器36の出力値をメモリ37aに記憶し、演算指令Cを受けるとメモリ37aの記憶値およびA/D変換器36の出力値に基づいて、清酒の熟度判定のために必要な演算処理や判定処理を行い、その結果を出力装置38に出力する。
【0039】
出力装置38は、ランプ、ブザー、表示器、プリンタあるいは他装置との通信装置等によって構成され、演算装置37の処理結果を、点灯、点滅、アラーム音で出力したり、表示出力、印刷出力あるいは他装置へ送信する。
【0040】
この測定システムを用いて清酒の熟度を判定するためには、清酒の熟度と前記した分子膜25の出力との関係を予め把握しておく必要がある。
【0041】
この関係を求めるために、発明者らは3種類の清酒A〜Cについて、醸造直後のものと、醸造後に熟成が進行する環境下で時間が経過したものを、図4に示す手順で測定した。
【0042】
ここで、清酒Aはアミノ酸が非常に少なく淡麗な酒質の清酒、清酒Bは一般的な酒質の醸造酒、清酒Cは一般的な酒質の吟醸酒であり、各清酒A〜Cについて、醸造後のもの(実際には醸造直後に0〜5°Cの間の熟成が進行しない温度環境下で保存したもの)、醸造から40°Cで1週間、2週間、3週間、4週間、5週間熟成させたものを第1〜第6のサンプルとして予め用意する。
【0043】
そして、図4に示しているように、基準液にプローブ22を漬けてそのときの出力電圧Vr(n)をメモリ37aに記憶してから、第nのサンプルにプローブ22を漬けてそのときの出力電圧V(n)をメモリ37aに記憶し、その電圧差Vs(n)=V(n)−Vr(n)を求めてメモリ37aに記憶し、プローブ22を洗浄するという処理を各清酒A〜Cの第1〜第6のサンプルについて行い、これらの測定結果から熟度判定の基準値を決定する。
【0044】
なお、ここで分子膜25としては、可塑剤としてNPOEを1000ml、高分子としてPVC800mg、脂質としてTOMA10mgを混合して作製されたものを用いており、可塑剤中の脂質濃度が2パーセント(膜中換算で1パーセント)、TOMAの膜中換算濃度が0.5パーセントであり、膜中の脂質の総濃度は1.5パーセントである。
【0045】
また、基準液としては、味を清酒に近づけるためのコハク酸30mM、導電率を清酒に近づけるための塩化カリウム(KCl)30mM、アルコール度を清酒に近づけるためのエタノール15パーセントの溶液を用いている。
【0046】
また、洗浄液としては、分子膜25にマイナス極性の両親媒性物質を用いている場合には、アルカリ性のKOH(水酸化カリウム)10mMとエタノール30パーセントの溶液を用い、分子膜25にプラス極性の両親媒性物質を用いている場合には、酸性のHCl(塩酸)10mMとエタノール30パーセントの溶液を用いている。
【0047】
また、ここでは測定時間を短縮するために、実際の工場の貯蔵温度(15°C程度)に比べて格段に高い40°Cという温度で保存して熟成を早めたサンプルを用いている。
【0048】
図5は、上記の測定で得られた各サンプル毎の電圧Vs(1)〜Vs(6)を、醸造直後のサンプルの電圧Vs(1)からの変化量で表したものである。
【0049】
図5から明らかなように、各清酒A〜Cとも、醸造直後から2週間までは、電圧が同一方向(図では減少方向)に単調変化しており、2週間以降はほぼ平坦になる。
【0050】
実際に官能検査で各サンプルを判定した結果、清酒A〜C全体としては、醸造直後から1週間までのものは熟成が足らず味が若く、1週間を超える頃からまろやかさが徐々に増し、3週間を超えるとひね香(劣化の味)がでてきて出荷できない品質となるとの評価が出ている。
【0051】
また、官能検査においては、清酒の種類によって、熟度の度合いがかなり違っている点、清酒Cの場合保存時間の違いによる熟成の度合いの差がはっきりでている点が確認されており、これらの点は図5の測定結果と良く符号している。
【0052】
以上のことから、熟度のひとつの判定基準として、出荷に適した熟度か否かを判定する場合、出荷された清酒が実際に飲まれるまでの期間を考慮して、清酒Aについては醸造直後の電圧からおよそ1.0〜1.2mV低下したものを出荷対象とし、清酒Bについては醸造直後の電圧からおよそ1.5〜1.7mV低下したものを出荷対象とし、清酒Cについては醸造直後の電圧からおよそ1.9〜2.1mV低下したものを出荷対象とすればよく、これらの各値を判定のための基準値として決定する。
【0053】
そして、これら3種の清酒A〜Cが出荷に適した熟度に達したか否かを判定する場合、その清酒についての醸造直後の測定値Vs(1)と、判定の基準値Rx、Ry(清酒AであればRx=1.0、Ry=1.2)とを予め演算装置37のメモリ37aに記憶しておけば、清酒が出荷に適した熟度に達しているか否かを容易に把握することができる。
【0054】
即ち、図6のフローチャートに示しているように、基準液の測定値Vrと判定対象の清酒の測定値Vとの差Vsを求め、この差Vsと醸造直後の電圧Vs(1)との差ΔVを求め、この差ΔVと基準値Rx、Ryとを比較し、差ΔVが基準値Rx、Ryの間にあれば、その清酒が出荷に適した熟度に達していると判定し、差ΔVが基準値Rxより小の場合には、その清酒は熟成不足と判定し、差ΔVが基準値Ryより大の場合には、その清酒が出荷に適した熟度を超えてしまっていると判定する。そして、これらの判定結果を出力装置38から出力することにより、その清酒が出荷に適した熟度に達しているか否かを容易に把握することができる。
【0055】
なお、上記説明では、清酒が出荷に適した熟度に達しているか否かあるいは超えているか否かを判定するようにしているが、予め熟度をより多段階にランク分けし、各ランク毎に基準値を設定し、判定対象の清酒を測定したとき測定値からその清酒がどの熟成段階にあるかを判定してもよい。
【0056】
このように、実施形態の清酒熟度判定方法および装置は、両親媒性物質を含む分子膜25を清酒に浸漬したときの電位が、その清酒の熟度の程度に対応して変化することを利用して、清酒の熟度を判定しているので、官能検査のように検査人の識別力に左右されることなく、再現性が高く正確な判定が行なえる。
【0057】
また、分子膜を形成する脂質等の両親媒性物質として、極性を有するものを用い、その濃度を1〜7パーセントの範囲にすることで、清酒の熟度に対して顕著に相関する出力が得られ、この分子膜を用いることで、清酒の熟度の判定を容易に行なうことができる。
【0058】
【発明の効果】
以上説明したように、本発明の清酒熟度判定方法および装置は、両親媒性物質を含む分子膜を清酒に浸漬したときの電位が、その清酒の熟度の程度に対応して変化することを利用したものであり、醸造された直後の清酒のサンプルに、その分子膜を浸漬したときの電位を初期値とし、サンプルを実際に熟成させるときの貯蔵温度より高い温度で保存し熟成を早めた状態で分子膜で測定された電位の初期値からの変化量を求め、その変化量のうち実際に出荷に適した熟度に達したときの変化量を判定基準値と決定し、醸造された直後の判定対象の清酒に分子膜を浸漬したときの電位と、醸造後の熟成が進行する通常環境下で時間が経過した清酒に分子膜を浸漬したときの電位との差を求め、その差と判定基準値とを比較し、その比較結果から判定対象の清酒が出荷に適した熟度に達したか否かを判定しているので、官能検査のように検査人の識別力に左右されることなく、再現性が高く且つ効率的な測定が行える。
【0059】
また、分子膜を形成する脂質等の両親媒性物質として、極性を有するものを用い、その濃度を1〜7パーセントの範囲にすることで、清酒の熟度に対して顕著に相関する出力が得られ、この分子膜を用いることで、清酒の熟度を容易に把握することができる。
【図面の簡単な説明】
【図1】本発明の実施形態の清酒熟度判定装置の構成を示す図
【図2】分子膜の模式的な構造を示す図
【図3】 膜中の両親媒性物質の濃度と熟度に対する感度との関係を示す図
【図4】分子膜の出力と清酒の熟度との相関を求めるための手順の一例を示すフローチャート
【図5】銘柄が異なる清酒の貯蔵時間の長さに対する分子膜の出力変化を示す図
【図6】清酒の熟度を判定するための手順の一例を示すフローチャート
【符号の説明】
20 清酒熟度判定装置
22 プローブ
23 参照電極
25 分子膜
35 電圧検出器
36 A/D変換器
37 演算装置
37a メモリ
38 出力装置
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a technique for determining the maturity of sake.
[0002]
[Prior art]
Sake is generally brewed after being brewed and stored in a tank after the tempering process (in the case of fresh sake, it is stored without tempering after brewing) and when it has reached an appropriate ripeness Shipped in a container.
[0003]
In a factory or the like that manufactures and ships sake by such a process, it is necessary to determine whether or not the stored sake has reached a maturity level that can be shipped.
[0004]
Conventionally, this maturity determination has been performed by a sensory test, that is, a professional inspector actually tastes sake.
[0005]
[Problems to be solved by the invention]
However, in the sensory test, there is a limit to the number of samples that can be determined by one inspector. That is, in the sensory test for sake, the sake to be judged is simply contained in the mouth and not swallowed, but in reality, the alcohol is absorbed in small amounts in the body. For this reason, if the number of samples to be determined becomes too large, the inspector gets drunk, and the discriminating power is reduced, making accurate determination impossible.
[0006]
In addition, there are individual differences in the inspector's discriminating power, and the determination results of maturity vary.
[0007]
The present invention is to solve this problem, without resorting to a functional test, and its object is to provide a sake maturity determination method and sake ripeness determination equipment was set to the maturity of sake can be accurately grasped .
[0008]
[Means for Solving the Problems]
In order to achieve the above object, the method for determining a sake maturity level of claim 1 of the present invention is:
A step of immersing a molecular film containing an amphiphile into a sample of sake immediately after brewing and measuring the potential of the molecular film as an initial value;
The potential of the molecular film is measured in a state where the sample is stored at a temperature higher than the storage temperature when the sample is actually ripened and the ripening is accelerated, and the amount of change of the measured potential from the initial value is determined, A step of determining a change amount when the maturity that is actually suitable for shipment out of the change amount as a judgment reference value;
Measuring the potential of the molecular film by immersing the molecular film in sake to be judged immediately after brewing;
Measuring the potential of the molecular film by immersing the molecular film in sake that has passed time in a normal environment where aging after the brewing proceeds;
Determining the difference between the potential measured for the sake immediately after brewing and the potential measured for the sake that has passed time in an environment where aging proceeds;
Comparing the obtained difference with the determination reference value, and determining from the comparison result whether or not the sake to be determined has reached a maturity suitable for shipping .
[0010]
Moreover, the sake ripening degree judging device of claim 2 of the present invention is:
A reference electrode, the probe (22) and a molecular film comprising amphipathic Substance,
Voltage detection means (35) for detecting a potential difference between a reference electrode of the probe and a molecular film;
The potential difference obtained by the voltage detection means when the probe is immersed in a sake sample immediately after brewing is stored as an initial value, and stored at a temperature higher than the storage temperature when the sample is actually aged. Means (37a) for storing, as a judgment reference value, a change amount when the maturity suitable for shipment is reached among the change amounts from the initial value of the measured value by the probe in a state where the ripening is accelerated When,
Subtracting means (37) for obtaining a difference between the potential difference detected by the voltage detecting means and the initial value when the probe is immersed in sake to be judged ;
A determination means (37) comparing the difference obtained by the subtraction means with the determination reference value and determining from the comparison result whether or not the maturity of the determination target sake has reached a maturity suitable for shipping. ) .
[0011]
Moreover, the sake maturity determination device according to claim 3 of the present invention is the sake maturity determination device according to claim 2,
The molecular film, an amphiphilic substance quality, and plasticizer, which was obtained by mixing the polymer material, wherein the amphiphilic substance has a polarity, the concentration of the film It is characterized by being in the range of 1 to 7 percent.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a diagram illustrating a configuration of a sake maturity determination device 20 for determining the maturity of sake.
[0013]
In FIG. 1, a sake ripening level determination device 20 includes a container 21 for containing a reference solution and sake to be determined, a probe 22, a voltage detector 35 that detects an output voltage of the probe 22, and a voltage detector 35. An A / D converter 36 that converts the output into a digital value, an arithmetic device 37 that performs arithmetic processing and determination processing on the output of the A / D converter 36, and an output device 38 that outputs the processing result of the arithmetic device 37. Has been.
[0014]
The probe 22 is used by being immersed in a liquid contained in a container 21, and has a reference electrode 23 for outputting a measurement reference potential and a molecular film 25 containing an amphiphilic substance or a bitter substance. Yes.
[0015]
The surface of the reference electrode 23 is covered with a buffer layer 24 in which 3.3 mole / l of potassium chloride is fixed with agar so as not to react with lipid in the liquid, and a lead wire 22a is connected thereto.
[0016]
The molecular film 25 is fixed in a state where one surface side is exposed on the surface of a base material 26 such as acrylic, and a buffer layer 27 equivalent to the buffer layer 24 of the reference electrode 23 is provided on the opposite surface of the molecular film 25. An electrode 28 is provided, and a lead wire 22 b is connected to the electrode 28.
[0017]
Molecular film 25, the amphiphilic substances having a portion with a hydrophilic in part and a polar with a hydrophobic nonpolar is integrally so as to form a film in a state in which the hydrophilic portion on the surface side When immersed in a liquid, the potential of the membrane changes according to the components in the liquid.
[0018]
This schematic structure is shown in FIG. In FIG. 2, each molecule 31 is composed of a spherical hydrophilic group 31a and a hydrocarbon chain 31b whose atomic arrangement extends from the hydrophilic group 31a, and each of these molecular groups is arranged such that the hydrophilic group 31a side is aligned on the surface side. In addition, a part of the matrix 33 (surface structure, micro structure having a planar extension) on the surface of the membrane member 32 (made of a polymer and a plasticizer described later) is partially dissolved in the matrix (for example, Is contained in the molecule 31 ').
[0019]
Molecular film 25, and a lipid component child, and a polymer serving as a base are those which are prepared by mixing the plasticizer in a predetermined ratio.
[0020]
For example, polyvinyl chloride (PVC) is used as the polymer, and dioctyl phthalate (DOP), dioctyl phenyl phosphonate (DOPP), tricresyl phosphate (TCP) or nitrophenyl octyl ether ( the 800mg a mixture with the above lipid content child with NPOE), was dissolved in THF10cc, transferred to a flat bottom of a container (e.g. a Petri dish of 85mmφ), it at about 30 degrees C with uniform heated on the plate 2 A molecular film having a thickness of about 200 μm can be obtained by evaporating THF while keeping the time. The mixing ratio of the polymer and the plasticizer is about 1: 1, the concentration of the lipid component element on the polymer and the plasticizer as described below are much lower.
[0021]
The present inventors have found that by choosing the concentration of the amphiphilic substance in the molecular film 25 from various experiments, the output indicating a significant correlation to sake of maturity can be obtained.
[0022]
That is, the amphiphilic substances such as lipids forming the molecular film 25, using the one having a polar significantly correlated against sake of maturity by the range of its concentration 1 to 7 percent output is obtained which, moreover the correlation, it hardly depends on the kind of amphiphilic substance has been found.
[0023]
In the experiment, a total of 36 types of molecular films were prepared with the following five parameters (a) to (e), and the relationship between the ripeness and sensitivity of sake was investigated.
[0024]
(A) Types of lipids (trioctyl ammonium chloride, dioctyl phosphate, oleic acid, phosphatidylserine, oleylamine)
(B) Type of plasticizer (DOPP, NPOE, TDA)
(C) Lipid concentration (d) Plasticizer concentration (e) Lipid mixing ratio
In addition, sake is just before entering the ripening process (in general sake, it is immediately after being baked after brewing, and in the case of fresh sake, it is immediately after brewing. The one immediately before brewing was described as the one immediately after brewing including the firing process), and the one aged for 1 to 5 weeks in an environment of 40 degrees after brewing was used.
[0026]
As a result of the sensory test, it was found that the maturity surely increased from one week to two weeks at 40 degrees.
[0027]
Therefore, the sensitivity to maturity was evaluated for each of the three types of sake by the magnitude of the change between the first week and the second week from the initial stage (the average of the absolute values of changes in the sensor for a total of 6 samples). Here, the reason why the absolute value is used is that there are a case where the output changes positively and a case where the output changes negatively depending on the polarity of the film.
[0028]
Measurement was performed three times, and 20 types with small measurement errors were selected. FIG. 3 shows the relationship between the sensitivity to the maturity of the 20 types of films and the concentration of polar amphiphiles in the film.
[0029]
As shown in FIG. 3, it was found that the sensitivity to maturity changes depending on the concentration of polar amphiphiles in the film.
[0030]
The impurity is a substance mixed in a content of several percent in the manufacturing process of the plasticizer, it contains an amphiphilic Substance with a polar, membrane of amphiphiles with polar included plasticizers This concentration includes those in the plasticizer.
[0031]
In this experiment, NPOE itself contained 2 percent, DOPP itself contained 2 percent, and TDA itself contained 0.5 percent as a result of analysis.
[0032]
As apparent from FIG. 3, in the concentration range of the amphiphilic substance is a 1-7 percent in the film containing ones in the plasticizer, there are dominant sensitivity compared to the error, correlation maturity In the range of 1 to 4 percent, sensitivity is nearly doubled, and in the range of 1.5 to 3 percent, higher sensitivity is obtained.
[0033]
The concentration of the amphiphilic substance as what material the amphiphilic substance in sake is sensitive is not currently specified, molecular film which has been conventionally used in measurement of taste There are those of 10 to 20 percent, output shown a correlation ripeness of sake is not obtained, sensitive to trace substances in sake from low concentration of the amphiphilic substance in the molecular film 25 The concentration of this trace substance is expected to increase as aging progresses.
[0034]
Thus, having a polarity, by the range of 1-7 percent concentration in the film of the amphiphilic substances, including those contained in the plasticizer molecules suitable for the determination of the ripeness of Sake A membrane can be obtained.
[0035]
When the probe 22 composed of the molecular film 25 and the reference electrode 23 is immersed in a liquid, the distance between the reference electrode 23 and the molecular film 25 is kept constant so that the measurement conditions do not change. You may support the electrode 23 and the base material 26 with a fixed space | interval.
[0036]
Lead wires 22 a and 22 b of the probe 22 are connected to a voltage detector 35. The voltage detector 35 is configured by, for example, a differential amplifier, detects a difference (voltage) between the potential of the reference electrode 23 and the potential of the molecular film 25 and outputs the difference to the A / D converter 36.
[0037]
The A / D converter 36 converts the output voltage of the voltage detector 35 into a digital value and outputs it to the arithmetic unit 37.
[0038]
The arithmetic unit 37 is constituted by a microcomputer, and stores the output value of the A / D converter 36 in the memory 37a when receiving a storage instruction M from an operation unit (not shown) or the like, and stores the output value of the memory 37a when receiving the arithmetic command C. Based on the output value of the A / D converter 36, arithmetic processing and determination processing necessary for determining the maturity of sake is performed, and the result is output to the output device 38.
[0039]
The output device 38 includes a lamp, a buzzer, a display, a printer, a communication device with other devices, and the like, and outputs the processing result of the arithmetic device 37 with lighting, blinking, alarm sound, display output, print output or Send to other device.
[0040]
In order to determine the maturity of sake using this measurement system, it is necessary to grasp in advance the relationship between the maturity of sake and the output of the molecular film 25 described above.
[0041]
In order to determine this relationship, the inventors measured three types of sake A to C immediately after brewing and those that had passed time in an environment where aging proceeds after brewing according to the procedure shown in FIG. .
[0042]
Here, sake A is a pure sake with a very low amino acid content, sake B is a general sake quality brewing sake, sake C is a general sake quality ginjo sake, and each sake A to C After brewing (actually stored in a temperature environment where aging between 0 and 5 ° C does not proceed immediately after brewing), brewing at 40 ° C for 1 week, 2 weeks, 3 weeks, 4 Prepared in advance as first to sixth samples after aging for 5 weeks.
[0043]
Then, as shown in FIG. 4, the probe 22 is immersed in the reference solution and the output voltage Vr (n) at that time is stored in the memory 37a, and then the probe 22 is immersed in the nth sample. The process of storing the output voltage V (n) in the memory 37a, obtaining the voltage difference Vs (n) = V (n) −Vr (n), storing it in the memory 37a, and washing the probe 22 is performed for each sake A This is performed for the first to sixth samples of -C, and the reference value for determining the maturity is determined from these measurement results.
[0044]
Here, the molecular film 25 is prepared by mixing 1000 ml of NPOE as a plasticizer, 800 mg of PVC as a polymer, and 10 mg of TOMA as a lipid, and the lipid concentration in the plasticizer is 2 percent (in the film). The equivalent concentration of TOMA in the membrane is 0.5 percent, and the total lipid concentration in the membrane is 1.5 percent.
[0045]
Further, as the reference solution, a solution of 30 mM succinic acid for bringing the taste closer to sake, 30 mM potassium chloride (KCl) for bringing the conductivity closer to sake, and 15% ethanol for bringing the alcohol degree closer to sake is used. .
[0046]
As the cleaning liquid, when the molecular film 25 is used negative polarity amphiphilic product quality uses an alkaline KOH (potassium hydroxide) 10 mM ethanol 30% solution, positive polarity to the molecular film 25 If you are using the amphiphilic substance quality is used an acid of HCl (hydrochloric acid) 10 mM and ethanol 30% solution.
[0047]
Further, here, in order to shorten the measurement time, a sample which is stored at a temperature of 40 ° C. which is much higher than the actual factory storage temperature (about 15 ° C.) and has been aged is used.
[0048]
FIG. 5 shows the voltage Vs (1) to Vs (6) for each sample obtained by the above measurement as the amount of change from the voltage Vs (1) of the sample immediately after brewing.
[0049]
As is clear from FIG. 5, in each sake A to C, the voltage monotonously changes in the same direction (in the decreasing direction in the figure) from immediately after brewing to 2 weeks, and becomes almost flat after 2 weeks.
[0050]
As a result of actually judging each sample by the sensory test, as for the sake A to C as a whole, the ones from just after brewing to one week were not matured and the taste was young, and the mellowness gradually increased from about one week. It has been evaluated that when it exceeds a week, a scent (degraded taste) appears and the quality cannot be shipped.
[0051]
In addition, in the sensory test, it was confirmed that the degree of maturity varies considerably depending on the type of sake, and in the case of sake C, the difference in the degree of aging due to the difference in storage time is clear. This point is well labeled with the measurement result of FIG.
[0052]
From the above, when judging whether the ripeness is suitable for shipment as one criterion of maturity, considering the period until the shipped sake is actually drunk, sake A is brewed The product that is about 1.0 to 1.2 mV lower than the voltage immediately after is targeted for shipment, the sake B is about 1.5 to 1.7 mV lower than the voltage immediately after brewing, and the product that is about Sake C is brewed. What is necessary is just to make a thing about 1.9-2.1mV lower than the voltage immediately after that into a shipment object, and these each value is determined as a reference value for determination.
[0053]
When determining whether or not these three types of sake A to C have reached ripeness suitable for shipping, the measurement value Vs (1) immediately after brewing for the sake and the reference values Rx and Ry for the determination (If sake A, Rx = 1.0, Ry = 1.2) is stored in advance in the memory 37a of the arithmetic unit 37, it is easy to determine whether the sake has reached a maturity suitable for shipping. Can grasp.
[0054]
That is, as shown in the flowchart of FIG. 6, a difference Vs between the measured value Vr of the reference solution and the measured value V of sake to be judged is obtained, and the difference between this difference Vs and the voltage Vs (1) immediately after brewing. ΔV is obtained, and the difference ΔV is compared with the reference values Rx and Ry. If the difference ΔV is between the reference values Rx and Ry, it is determined that the sake has reached a maturity suitable for shipping, and the difference When ΔV is smaller than the reference value Rx, the sake is determined to be insufficiently matured, and when the difference ΔV is greater than the reference value Ry, the sake has exceeded the ripeness suitable for shipping. judge. Then, by outputting these determination results from the output device 38, it is possible to easily grasp whether or not the sake has reached a maturity suitable for shipping.
[0055]
In the above description, it is determined whether the sake has reached or exceeded the maturity suitable for shipping, but the maturity is ranked in multiple stages in advance, and each rank is determined. A reference value may be set for the sake, and when the sake to be determined is measured, it may be determined which aging stage the sake is from the measured value.
[0056]
Thus, the sake maturity determination method and apparatus of the embodiments, the potential at which the molecular film 25 comprising amphiphilic Substance immersed in sake, changes corresponding to the degree of maturity of the sake Since the determination of the maturity of sake is made by using, the reproducibility and accurate determination can be performed without being influenced by the discriminating power of the inspector as in the sensory test.
[0057]
Further, the amphiphilic substances such as lipids which form a molecular film, with those having a polarity, by the range of its concentration 1 to 7 percent, significantly correlated against sake of ripeness By using this molecular film, it is possible to easily determine the maturity of sake.
[0058]
【The invention's effect】
As described above, sake maturity determination method and apparatus of the present invention, the potential when a molecular film comprising amphipathic Substance immersed in sake, changes corresponding to the degree of maturity of the sake The initial value is the potential when the molecular film is immersed in the sake sample immediately after brewing, and the sample is stored at a temperature higher than the storage temperature when the sample is actually aged. Determine the amount of change from the initial value of the potential measured on the molecular film in the state of accelerating, and determine the amount of change when the maturity that is actually suitable for shipping is reached as the criterion value, Find the difference between the potential when the molecular film is immersed in the sake to be judged immediately after brewing and the potential when the molecular film is immersed in sake that has been aging after brewing under normal conditions. Compare the difference with the criterion value and determine the result of the comparison. As the target of sake is determined whether or not reached maturity appropriate for shipment, without being influenced by the inspector of discrimination as functional testing, high and efficient measurement reproducibility Yes.
[0059]
Further, the amphiphilic substances such as lipids which form a molecular film, with those having a polarity, by the range of its concentration 1 to 7 percent, significantly correlated against sake of ripeness Output is obtained, and by using this molecular film, the maturity of sake can be easily grasped.
[Brief description of the drawings]
[1] The concentration of the amphiphilic substance in Figure 3 shows in the film showing the schematic structure of Figure 2 shows the molecular film showing the configuration of a sake maturity determination device of an embodiment of the present invention and mature Fig. 4 is a flowchart showing an example of a procedure for obtaining a correlation between the output of a molecular film and the maturity of sake. Fig. 5 is a diagram showing the relationship between the storage time of sake with different brands. Fig. 6 is a flow chart showing an output change of a molecular film. Fig. 6 is a flowchart showing an example of a procedure for judging the maturity of sake.
20 Sake Maturity Determination Device 22 Probe 23 Reference Electrode 25 Molecular Film 35 Voltage Detector 36 A / D Converter 37 Computing Device 37a Memory 38 Output Device

Claims (3)

醸造された直後の清酒のサンプルに、両親媒性物質を含む分子膜を浸漬して該分子膜の電位を初期値として測定する段階と、
前記サンプルを実際に熟成させるときの貯蔵温度より高い温度で保存し熟成を早めた状態で前記分子膜の電位の測定を行い、該測定された電位の前記初期値からの変化量を求め、該変化量のうち実際に出荷に適した熟度に達したときの変化量を判定基準値と決定する段階と、
醸造された直後の判定対象の清酒に、前記分子膜を浸漬して該分子膜の電位を測定する段階と、
前記醸造後の熟成が進行する通常環境下で時間が経過した清酒に、前記分子膜を浸漬して該分子膜の電位を測定する段階と、
前記醸造直後の清酒について測定した電位と、熟成が進行する環境下で時間が経過した清酒について測定した電位との差を求める段階と、
該求めた差と前記判定基準値とを比較し、該比較結果から前記判定対象の清酒が出荷に適した熟度に達したか否かを判定する段階とを含む清酒熟度判定方法。
A step of immersing a molecular film containing an amphiphile into a sample of sake immediately after brewing and measuring the potential of the molecular film as an initial value;
The potential of the molecular film is measured in a state where the sample is stored at a temperature higher than the storage temperature when the sample is actually ripened and the ripening is accelerated, and the amount of change of the measured potential from the initial value is determined, A step of determining a change amount when the maturity that is actually suitable for shipment out of the change amount as a judgment reference value;
Measuring the potential of the molecular film by immersing the molecular film in sake to be judged immediately after brewing;
Measuring the potential of the molecular film by immersing the molecular film in sake that has passed time in a normal environment where aging after the brewing proceeds;
Determining the difference between the potential measured for the sake immediately after brewing and the potential measured for the sake that has passed time in an environment where aging proceeds;
A method for determining a sake maturity level, comprising: comparing the obtained difference with the determination reference value, and determining from the comparison result whether the sake to be determined has reached a maturity level suitable for shipping .
参照電極と、両親媒性物質を含む分子膜とを有するプローブ(22)と、
前記プローブの参照電極と分子膜との間の電位差を検出する電圧検出手段(35)と、
醸造された直後の清酒のサンプルに前記プローブを浸漬したときに前記電圧検出手段で得られた電位差を初期値として記憶し、且つ前記サンプルが実際に熟成するときの貯蔵温度より高い温度で保存されて熟成が早められた状態における前記プローブによる測定値の前記初期値からの変化量のうち、出荷に適した熟度に達したときの変化量を判定基準値として記憶している手段(37a)と、
前記プローブを判定対象の清酒に浸漬したときに前記電圧検出手段によって検出された電位差と前記初期値との差を求める減算手段(37)と、
前記減算手段で得られた差と前記判定基準値とを比較し、その比較結果から前記判定対象の清酒の熟度が出荷に適した熟度に達したか否かを判定する判定手段(37)とを備えたことを特徴とする清酒熟度判定装置
A probe (22) having a reference electrode and a molecular film comprising an amphiphile;
Voltage detection means (35) for detecting a potential difference between a reference electrode of the probe and a molecular film;
The potential difference obtained by the voltage detection means when the probe is immersed in a sake sample immediately after brewing is stored as an initial value, and stored at a temperature higher than the storage temperature when the sample is actually aged. Means (37a) for storing, as a judgment reference value, a change amount when the maturity suitable for shipment is reached among the change amounts from the initial value of the measured value by the probe in a state where the ripening is accelerated When,
Subtracting means (37) for obtaining a difference between the potential difference detected by the voltage detecting means and the initial value when the probe is immersed in sake to be judged;
A determination means (37) comparing the difference obtained by the subtraction means with the determination reference value and determining from the comparison result whether or not the maturity of the determination target sake has reached a maturity suitable for shipping. Sake maturity determination device characterized by comprising:
前記分子膜は、両親媒性物質と、可塑材と、高分子材とを混合して得られたものであり、前記両親媒性物質は、極性を有し、その膜中の濃度が1〜7パーセントの範囲にあることを特徴とする請求項2記載の清酒熟度判定装置。 The molecular film is obtained by mixing an amphipathic substance, a plastic material, and a polymer material, and the amphiphilic substance has polarity and has a concentration in the film of 1 to 1. 3. The sake ripening level determination apparatus according to claim 2, wherein the range is 7% .
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013233131A (en) * 2012-05-11 2013-11-21 National Research Inst Of Brewing Method for evaluating sake preservation performance of glass container
JP2013233132A (en) * 2012-05-11 2013-11-21 National Research Inst Of Brewing Method for improving sake preservation performance of glass container

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JP7590715B2 (en) * 2019-12-06 2024-11-27 国立大学法人九州大学 Sensor cleaning solutions containing amphiphiles

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013233131A (en) * 2012-05-11 2013-11-21 National Research Inst Of Brewing Method for evaluating sake preservation performance of glass container
JP2013233132A (en) * 2012-05-11 2013-11-21 National Research Inst Of Brewing Method for improving sake preservation performance of glass container

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