201201710 六、發明說明： 【發明所屬之技術領域】 本發明係關於使用轉麩醯胺酶、葡萄糖氧化酶及/或 α-葡萄糖苷酶之米飯食品等的食品之製造方法及食品改質 用之酵素製劑。 【先前技術】 多數的食品係由澱粉、蛋白質、糖類、脂質等各種的 成分所構成，此等會複合性地創造出食品之口感。其中， 澱粉或蛋白質對口感的影響極大，尤其是澱粉的經時性變 化特別重要。 根據專利文獻1，在含澱粉之食品物性改良劑方面， 係可藉由煮飯時在米中添加α-葡萄糖苷酶之轉葡萄糖苷 酶，而可獲得柔軟、有黏性且經時不易劣化之煮飯米。雖 然可見極佳的效果，但在米粒彼此的鬆動性或物性改良效 果方面，尙有改善的餘地。如此一來，任一種方法都難以 使煮飯後即時的口感向上提昇且其優異的口感可長時間地 維持等2項得以兼顧。 關於轉麩醯胺酶對米飯的利用’在專利文獻2中’係 揭示一種製造煮飯米的方法，其係米類在煮飯時’可藉由 在煮飯水中添加轉麩醯胺酶以及蛋白質部分水解物、少糖 類、糖醇來煮飯，以製造出在煮飯後即使長時間保存下仍 無損其風味，特別是可賦予黏性的煮飯米，在僅添加轉麩 醯胺酶時，雖顯現了嚼勁，但相較於添加了轉麩醯胺酶與 -5- 201201710 小麥蛋白質部分水解物的煮飯米，欠缺了黏性，入喉感覺 差。又，專利文獻3中，雖記載了藉由添加轉麩醯胺酶來 防止多加水米飯在低溫保管或是低溫流通時所導致澱粉劣 化之方法，但一般的煮飯米與多加水米飯在米粒的口感等 全然不同。 專利文獻4中，係記載了以倂用對蛋白質的物性改良 有效的酵素轉麩醯胺酶與a-葡萄糖苷酶可製造出具有單 是葡萄糖苷酶所得不到的粒感或鬆動性，且經長時間 仍可維持口感的米飯。雖在口感及經時變化之改善兩方面 可見到頗高的效果，但在口感面上，卻因粒感的增加而一 方面留下了日本人喜好的Q彈感、膨潤感稍微示弱之課 題。在專利文獻5中，爲解決此課題，而揭示有倂用轉麩 醯胺酶、α-葡萄糖苷酶、葡萄糖氧化酶等3酵素之技術， 目前市售有倂用3酵素之食品物性改良用之酵素製劑「 ACTIVA®」超級米（味之素公司製）。此市售品主要用 爲米飯的物性改良劑，且發揮著充分的改質效果。 專利文獻5算是第一個應用葡萄糖氧化酶於米飯之物 性改良的例子。而在專利文獻6中，是藉由葡萄糖氧化酶 來減少米飯中的葡萄糖量，以製造減重飯之方法，而在專 利文獻7中，則記載了添加葡萄糖氧化酶與葡萄糖來製造 調理包米飯，以在葡萄糖中置入溶存氧而防止米飯中因脂 質酸化所致的劣化之方法，但任一種均沒有關於物性改良 之記載。有關葡萄糖氧化酶對麵包之使用雖有多數的報告 ，且已知有提昇麵團安定性等效果，但麵包與米飯是全然 -6- 201201710 不同的食品，口感也有很大的差異’葡萄糖氧化酶對麵包 的添加效果與對米飯食品的添加效果不同。 在倂用轉麩醯胺酶、葡萄糖苷酶、葡萄糖氧化酶等 3酵素之上述的市售酵素製劑之使用方法方面，通常多爲 在米的浸漬液使其溶解並煮飯之方法，但位在大規模的煮 飯工廠時，因重視作業性，係採用在別的液體槽調整酵素 製劑的高濃度水:容液並將酵素水溶液以自動泵浦添加到米 中進行煮飯的方法，酵素製劑的高濃度水溶液係可在保持 於液體槽內2 4小時左右。 本發明者們發現，含有轉麩醯胺酶、α-葡萄糖苷酶、 葡萄糖氧化酶之上述市售製劑的高濃度溶液在24小時左 右保持於液體槽內時，各酵素的活性會降低，無法發揮充 分的改質效果等新的課題。例如，使上述市售製劑的20% 水溶液在25°C保存24小時時，發現轉麩醯胺酶、葡萄糖 氧化酶有90%以上、α-葡萄糖苷酶也有20%以上會失去活 性。甚至發現，不僅是3酵素倂用的情況下，連在轉麩醯 胺酶與α-葡萄糖苷酶、或是轉麩醯胺酶與葡萄糖氧化酶 之2酵素倂用的情況中，高濃度溶液被保持24小時左右 時，各酵素的活性便會降低。 酵素製劑的安定性低，意指口感改善效果不一致、限 制使用者的使用方法。例如，當酵素製劑水溶液不可能長 時間保存的情況下，用於大規模生產米飯食品時，必須要 有別的設備投資、人員配置等對策。 酵素的安定化方法方面，已知有在抗壞血酸氧化酵素 201201710 的純化步驟、製劑化步驟中添加可溶性澱粉之方法（專利 文獻8)、於肉軟化酵素中添加增黏劑、蛋白、聚丙三醇 脂肪酸酯之方法（專利文獻9)、於磷酸酶、醣苷酶中添 加亞拉伯膠、植物性蛋白之方法（專利文獻10)、於聚 甘露糖酶中添加來自咖啡的材料之方法（專利文獻11) 等。又，已知會因氧而導致活性降低之轉麩醯胺酶的安定 化方法方面，雖在專利文獻12中，揭示有轉麩醯胺酶與 (a)有機酸、其鹼金屬鹽或者其酯、（b)無機酸或者其 鹽、（c)聚苯酚、（d)硫醇或（e)糖醇等物質的其中 之一倂用之方法，或與由（a')有機酸、其鹼金屬鹽及其 酯、無機酸及其鹽、（c)聚苯酚、（d)硫醇及（ e)糖醇等5種物質選出之2種以上的物質倂用之方法， 但專利文獻1 3中係有類似其添加劑的添加效果不充分的 記載，並揭示有使用蛋白部分水解物之方法。專利文獻 12中有關轉麩醯胺酶與酸性物質及鹼性物質之倂用並無 記載，亦無有關其他酵素之效果的揭示或教示。酵素係因 種類而爲機能、特徵全然不同者，各方法只不過是對特定 酵素具有效果而已。意即，可安定化所有酵素的技術未知 ，又，同時達成轉麩醯胺酶、α-葡萄糖苷酶、葡萄糖氧化 酶之安定化的方法也未知。 [先前技術文獻] [專利文獻] [專利文獻 1]W02005/096839 201201710 [專利文獻2]特開平9-206.006號公報 [專利文獻3]專利33 1008 1號 [專利文獻4]特開2009-022267號公報 [專利文獻 5]W0201 0/035858 [專利文獻6]專利37 1 8495號 [專利文獻7】專利2808060號 [專利文獻8:丨特開平5-244948號公報 [專利文獻9]特開平10-1 36942號公報 [專利文獻1(>]特表2007-5 19408號公報 [專利文獻1]]特開2007-275065號公報 [專利文獻Π ]特開平4-2071 94號公報 [專利文獻 13]W096/1 1264 【發明內容】 [發明所欲解決之課題] 本發明係有鑑於上述情事而完成者，本發明之目的在 於提供一可改善物性及食味的食品之製造方法及食品改質 用之酵素製劑。特別是在於提供一僅以α ·葡萄糖苷酶、 轉麩醯胺酶之單獨使用或兩酵素的倂用並無法獲得的口感 ，例如具有「Q彈感」、「膨潤感」或是「粒感」、「啪 啦感」之米飯食品的製造方法。更具體而言，本發明之目 的在於提供一即使是使含有轉麩醯胺酶與葡萄糖氧化酶或 α -葡萄糖苷酶之2酵素’或是含有轉魅醯胺酶、α -葡萄糖 苷酶、葡萄糖氧化酶等3酵素之溶液保持24小時左右的 201201710 情況下，仍可保持各酵素活性之方法。 [解決課題之方法] 發明者們專致於檢討的結果發現，藉由在轉麩醯胺酶 與葡萄糖氧化酶或α-葡萄糖苷酶等2酵素、或是藉由在 轉麩醯胺酶、葡萄糖苷酶、葡萄糖氧化酶等3酵素之外 再使用磷酸鹽、碳酸鹽、有機酸、胺基酸，係可解決上述 課題而完成本發明。意即，本發明係包含以下之發明。 (1) 一種食品之製造方法，其特徵係使用（Α)轉麩醯 胺酶與葡萄糖氧化酶及/或α-葡萄糖苷酶、（Β)由磷酸、 磷酸鹽、有機酸、胺基酸所成之群選出的至少1種酸性物 質與（C)由磷酸鹽、碳酸鹽、檸檬酸鹽、鹼性胺基酸、 氧化銘所成之群選出的至少1種驗性物質β (2) 如（1)記載之方法，其中，酸性物質係蘋果酸或檸 檬酸’鹼性物質係磷酸氫二鈉或磷酸三鈉或碳酸鈉。 (3) —種食品之製造方法，其特徵係使用（α)轉麩醯 胺酶與葡萄糖氧化酶及/或α -葡萄糖苷酶與（c)驗性胺基 酸。 (4 )如（3 )記載之製造方法，其中，鹼性胺基酸係組胺 酸。 (5)—種食品之製造方法’其特徵係調製含有（Α)轉 魅醯fe:酶及葡萄糖氧化酶或α_葡萄糖苷酶、（Β)酸性物 質與（C)鹼性物質之溶液，或調製含有（Α)轉麩醯胺 酶及葡甸糖氧化酶或α -葡萄糖苷酶與鹼性胺基酸之 10- 201201710 溶液並使用。 (6) —種食品之製造方法，其特徵係調製含有 麩醯胺酶及葡萄糖氧化酶及α-葡萄糖苷酶、（B 質與（C)鹼性物質之溶液，或調製含有（a) 酶及葡萄糖氧化酶及α -葡萄糖苷酶及（c)鹼性 溶液並使用。 (7) 如（5)或（6)記載之方法，其中，酸性 係該溶液之0.02〜20重量％、鹼性物質的量係〇. 量％，且該溶液的pH係5.0〜8.0。 (8) 如（1)〜（7)中任一記載之方法，其中， 飯食品。 (9 )如（6 )記載之方法，其中，食品係米飯食 麩醯胺酶的量係毎lg原料生米爲0.05〜12U、α-酶的量係每lg原料生米爲15〜1 50,000U、葡萄 的量係每lg原料生米爲0.03~210Ue (10)如（6)或（9)記載之方法，其中，葡萄 的量係每1U轉麩醯胺酶爲0.003〜10,000U、每1 糖苷酶爲〇·〇〇〇〇〇3~34υ、α-葡萄糖苷酶的量係每 醯胺酶爲0.15〜2O0,OOOU。 (1 1 ) 一種酵素製劑，其係含有（A )轉麩醯胺 糖氧化酶及/或α-葡萄糖苷酶、（Β)由磷酸、磷 機酸、胺基酸所成之群選出的至少1種酸性物f 由磷酸鹽、碳酸鹽 '檸檬酸鹽、鹼性胺基酸、氧 之群選出的至少1種鹼性物質作爲有效成分。 ‘（A :丨轉 )酸性物 轉慈醯胺 胺基酸之 物質的量 02〜50重 食品係米 品，且轉 葡萄糖苷 糖氧化酶 糖氧化酶 U α-葡萄 1U轉麩 酶與葡萄 酸鹽、有 [( C) 化鈣所成 -11 - 201201710 (12) —種酵素製劑’其係含有（a)轉麩醯胺酶與葡萄 糖氧化酶及/或α-葡萄糖苷酶與（C)鹼性胺基酸作爲有效 成分。 (13) —種酵素製劑，其係含有（Α)轉麩醯胺酶及葡萄 糖氧化酶及α -葡萄糖苷酶、（Β)由磷酸、憐酸鹽、有機 酸、胺基酸所成之群選出的至少1種酸性物質與（C)由 磷酸鹽、碳酸鹽、檸檬酸鹽、鹼性胺基酸、氧化鈣所成之 群選出的至少1種鹼性物質作爲有效成分之酵素製劑，或 是含有（Α)轉麩醯胺酶及葡萄糖氧化酶及/或α-葡萄糖 苷酶與（C)鹼性胺基酸作爲有效成分之酵素製劑，其中 ，葡萄糖氧化酶的含量係每 1U 轉麩醯胺酶爲 0.003〜1 0,000U、每 lUa-葡萄糖苷酶爲 0.000003-34U。 [發明之效果] 根據本發明，即使是使含轉麩醯胺酶與葡萄糖氧化酶 及/或α-葡萄糖苷酶之酵素溶液保持24小時左右的情況下 ，亦可獲得保持各酵素活性良好之食品。特別是得以獲得 僅以α-葡萄糖苷酶、轉麩醯胺酶之單獨使用或兩酵素倂 用所無法得到的口感，例如具有「Q彈感」、「膨潤感」 或是「粒感」、「啪啦感」的米飯食品。 【實施方式】 [實施發明之形態] 以下就本發明詳細說明。本發明所致的食品之製造方 -12- 201201710 法及食品改質用之酵素製劑中，係使用（A )轉麩醯胺酶 與葡萄糖氧化酶及/或α-葡萄糖苷酶、（B)磷酸、磷酸鹽 、有機酸' 酸性胺基酸等的酸性物質與（C)磷酸鹽、碳 酸鹽、檸檬酸鹽、鹼性胺基酸、氧化鈣等的鹼性物質，或 是，使用（A )轉麩醯胺酶與葡萄糖氧化酶及/或α-葡萄 糖苷酶與（C )鹼性胺基酸。 本發明之葡萄糖氧化酶係一催化使葡萄糖、氧、水作 爲基質而與葡萄塘酸生成過氧化氫之反應的氧化酵素。藉 由此反應所生成的過氧化氫，係藉由氧化蛋白中的SH基 來促進SS鍵結（二硫鍵結）生成，且於蛋白中作出交聯 構造。已知葡萄糖氧化酶係有來自微生物、來自植物等種 種起源者，但本發明中所用的酵素若爲具有此活性的酵素 即可，也不管其起源爲何。又，即使是重組酵素亦可。以 「Sumizyme PGO」所稱之商品名係新日本化學工業（股 )所販售之來自微生物的葡萄糖氧化酶是爲一例。此外， 雖然有市售混合有過氧化氫酶的葡萄糖氧化酶製劑，但若 有葡萄糖氧化酶活性，即使是與其他酵素的混合物亦可。 葡萄糖氧化酶的酵素活性，係以葡萄糖爲基質，在氧 存在下使葡萄糖氧化酶作用來生成過氧化氫，且對生成之 過氧化氫在胺安替比林（aminoantipyrine)及苯酣存在下 使過氧化酶作用而生成的醌亞胺色素之所呈色調，以波長 5 00nm測定進行定量。定義1分鐘氧化Ιμιηοΐ葡萄糖所必 要的酵素量爲1U :酵素活性單位unit)。 本發明之轉麩醯胺酶係指具有催化使蛋白質或胜肽中 -13- 201201710 的麩醯胺酸殘基作爲供與體、離胺酸殘基作爲受容體之醯 基轉移反應的活性之酵素，已知有來自哺乳動物者、來自 魚類者、來自微生物者等種種起源者。本發明所用的酵素 若是真有此活性的酵素即可，其起源方面任一者均可。又 ，即使是重組酵素亦可。味之素（股）以「ACTIVA」TG 所稱之商品名市售之來自放線菌的轉麩醯胺酶係爲一例》 轉麩醯胺酶的酵素活性，係以苄基氧基羰基-L-麩醯 胺醯基甘胺酸與羥基胺作爲基質進行反應，將生成之羥胺 酸在三氯醋酸存在下使其形成鐵錯合物後，測定525nm 之吸光度，並由檢量線求取羥胺酸之量且算出活性。定義 在37°C、pH6.0在1分鐘內生成Ιμιηοΐ羥胺酸的酵素量爲 1U (酵素活性單位unit)。 本發明之α-葡萄糖苷酶係將非還原末端α-1，4-葡萄糖 苷鍵結水解，且生成α_葡萄糖之酵素。α-葡萄糖苷酶之中 ，係以對α-1，6鍵結勝過α-1，4鍵結之糖轉移活性的轉葡 萄糖苷酶爲佳。此外，以轉葡萄糖苷酶L「ΑΜΑΝΟ」所 稱之商品名由天野Enzyme (股）所市售之酵素係爲α-葡 萄糖苷酶的一例。 α-葡萄糖苷酶的酵素活性，係於ImM α-甲基-D-葡萄 糖苷1ml中加入0.02 Μ醋酸緩衝液（pH5.0)lml，且添加 酵素溶液0.5 ml，使其於40°C作用60分鐘後時，定義在 反應液2.5ml中生成1μ8葡萄糖之酵素量爲1U(酵素活 性單位u n i t )。 本發明之酸性物質係指溶解於蒸餾水時，pH爲酸性 -14- 201201710 者，亦指無機酸、有機酸、胺基酸、該等的酸性鹽。從對 食品之使用實績、對食品之味道的影響、溶解性、緩衝能 來看，係以磷酸二氫鉀、磷酸二氫鈉、蘋果酸、檸檬酸、 甘胺酸爲佳，又以蘋果酸、檸檬酸更佳。酸性物質的量係 以（A )轉麩醯胺酶、α-葡萄糖苷酶、葡萄糖氧化酶、（ Β)酸性物質及（C)鹼性物質之混合溶液的〇.〇2〜20重量 %爲佳、〇.i~io li量％更佳、1〜5重量％又更佳。此外，使 用組胺酸等鹼性胺基酸時，即使不倂用酸性物質亦可。 本發明之鹼性物質係使溶解於蒸餾水時pH爲鹼性者 ，指無機鹽、有機酸鹽、胺基酸鹽、鹼性胺基酸。從對食 品之使用實績、對米飯食品之味道的影響、溶解性、緩衝 能來看，係以磷酸水素二鉀、磷酸氫二鈉、磷酸三鈉、碳 酸鉀、碳酸鈉、離胺酸、精胺酸、組胺酸爲佳，又以磷酸 氫二鈉、磷酸三鈉、碳酸鈉、組胺酸更佳。鹼性物質的量 係以（A)轉麩醯胺酶、α-葡萄糖苷酶、葡萄糖氧化酶、 (Β)酸性物質、（C)鹼性物質之混合溶液的0.02~50重 量％爲佳、〇.1~30重量％更佳、2~9重量％又更佳。此外， 使用組胺酸等鹼性胺基酸時，即使不倂用酸性物質亦可。 本發明中，去除單獨使用鹼性胺基酸的情況，必須使 用酸性物質與鹼性物質雙方時，係以使該等溶解於蒸餾水 時的溶液pH爲5.0〜8、較佳爲6.0〜7.4、更佳爲6.5~7.4 之範圍適當地組合即可。例如，在蘋果酸或檸檬酸與磷酸 氫二鈉之組合時，溶液中的濃度以酸性物質1 %、鹼性物 質9%來摻合即可，而在蘋果酸或檸檬酸與檸檬酸三鈉之 -15- 201201710 組合時，溶液中的濃度以酸性物質2.5%、鹼性物質7.5% 來摻合即可。 本發明之食品方面，可舉出米飯食品、麵類、麵包、 水產加工品及水產品 '畜肉加工品及肉、乳製品、豆製品 、野菜、果物、零食點心等。米飯食品方面，可舉出煮飯 米（白飯）、醋飯（壽司飯）、赤飯、燴飯、炒飯、燉飯 、糯米小豆飯、粥、義大利什錦飯、飯團、壽司、便當等 。又包含此等的冷凍品、無菌包裝品、調理包品、乾燥品 、罐裝品。麵類方面，可舉出烏龍麵、炒麵、蕎麥麵、中 華麵、通心粉等。又包含此等的冷凍品、低溫品、調理包 品、乾燥品。麵包類方面，可舉出調理麵包、點心麵包、 三明治、吐司、米粉麵包、黑麵包等。又包含此等的冷凍 品、乾燥品。 可爲本發明之米飯食品原料的米，任何品種的米皆可 ，不論是軟質米、硬質米、新米、舊米都無所謂。又，低 質梗米或低質梗米亦可。再者，低蛋白米（蛋白調整米） 等經酸或酵素處理過的加工米也沒關係。 本發明之米飯食品的製造方法中，也可以不調製混合 了（A)轉麩醯胺酶、葡萄糖苷酶、葡萄糖氧化酶、（ Β)酸性物質、（C)鹼性物質之溶液，而可使其添加作 用於生米或煮飯米，但解決本發明之課題的重點，係以使 該混合溶液添加作用於生米或煮飯米中爲其特徵。當然， 不調製溶液而使此等添加作用也可以，使其添加作用的方 法，不管是在煮飯中的任何階段使其作用都無所謂，即使 -16- 201201710 是煮飯後也沒關係。意即，也可在爲了吸水而浸漬米的浸 漬液中添加（A)〜（C)，在浸漬後、煮飯前添加也沒關 係。又，煮飯後散灑在煮飯米上使其作用也可以。在蒸米 生產線上，也可於蒸的步驟之前或後散灑酵素使其作用。 本發明中，使其作用於米之葡萄糖氧化酶的添加量， 對原料生米lg而言，酵素活性係以0.001U以上、較佳爲 0.00卜5 00U、更佳爲0.03〜21 0U之範圍爲適。使葡萄糖氧 化酶作用於米的效果，可顯著地賦予米飯食品「Q彈感」 或「彈力」，特別是「Q彈感」，是添加轉麩醯胺酶或（X-葡萄糖苷酶所無法得到的口感。雖然轉麩醯胺酶與α-葡 萄糖苷酶的倂用可獲得一定的「彈力」賦予效果，但若爲 了獲得更強的「彈力」而增加轉麩醯胺酶的比率的話，會 有抑制α-葡萄糖苷酶的「膨潤感」賦予機能之傾向。但 是，藉由葡萄糖氧化酶的使用，係可在不過度抑制α·葡 萄糖苷酶的機能下賦予強「彈力」。另一方面，當葡萄糖 氧化酶添加500U以上時，會因「彈力」過強而造成像橡 膠似的不自然口感，喜好程度會降低。 本發明中，對原料生米lg而言，當葡萄糖氧化酶的 添加量係以酵素活性爲0.0 0 1 U以上、較佳爲〇 . 0 0 1〜5 0 0 U 、更佳爲0.03〜21 0U的情況下，使其作用於米之轉麩醯胺 酶的添加量係對原料生米lg而言以酵素活性爲0.0001 U 以上、較佳爲0.000 1〜120U、更佳爲0.05〜12U之範圍爲 適。再者’每1U葡萄糖氧化酶添加量理想上係以轉麩醯 胺酶爲0.003〜10,〇〇〇U、較佳爲0.1〜900U來添加轉麩醯胺 -17- 201201710 酶爲宜。 本發明中，對原料生米lg而言，使其作用於米之α_ 葡萄糖苷酶的添加量係以酵素活性爲0.03U以上、較佳爲 0.03〜300,000U、更佳爲15〜1 50,000U之範圍爲適。每1U α-葡萄糖苷酶的量，其添加之轉麩醯胺酶以 0.15〜200,000U爲佳。再者，每1U葡萄糖氧化酶添加量 係以 α-葡萄糖苷酶爲 0.000003〜34U 、較佳爲 0.000006〜3U來添加α-葡萄糖苷酶爲宜。 反覆而言，使轉麩醯胺酶與α-葡萄糖苷酶及/或葡萄 糖氧化酶作用於米來製造米飯食品時各酵素的添加量比， 以酵素活性（U數）來計，每1U葡萄糖氧化酶其轉麩醯 胺酶以0_003〜10,000U、較佳爲0_1〜9 00U、及/或每1U葡 萄糖氧化酶其α-葡萄糖苷酶以0.000003~34U、較佳爲 0.000006〜3U爲適。各酵素的添加量比位在上述範圍時， 製造後即刻的品質（膨潤感、Q彈感、粒感、鬆動性等物 性）良好，並可製造能夠抑制因經時所導致品質劣化之米 飯食品。 各酵素的反應時間若爲酵素作用於基質物質的可能時 間則無特別限制，可爲非常短的時間或相反地使其長時間 作用亦可，現實上的作用時間係以5分〜24小時爲佳。又 ，關於反應溫度，若是可保持酵素活性的範圍任何溫度都 無所謂，現實上，係以在0~80°C使其作用爲佳。意即，經 過一般的煮飯步驟可得充分的反應時間。 除了（A)轉麩醯胺酶、α-葡萄糖苷酶、葡萄糖氧化 -18- 201201710 酶、（B)酸性物質、（C)鹼性物質之外，係 加混合糊精、澱粉、加工澱粉、還原麥芽糖等的 畜肉精等的調味料、植物蛋白、麩質、卵白、明 白等的蛋白質、蛋白水解物、蛋白部分分解物、 檸檬酸鹽、聚合磷酸鹽等的螯合劑、麩胺基硫、 等的還原劑、褐藻酸、鹼水、油脂、色素、酸味 、過氧化氫酶等的酵素等其他的食品添加物等， 飯食品改質用之酵素製劑。本發明之酵素製劑可 、膏狀、顆粒狀、粉末狀的任何形態。又，酵素 酵素的摻合量雖爲大於0%小於100%，但以每1 氧化酶的含量其轉麩醯胺酶爲0.003〜1 0,000U 0.1〜900U、及/或每1U葡萄糖氧化酶的含量其 苷酶爲 0.000003〜34U、較佳爲 0.000006~3U爲 物質、鹼性物質的量理想上是使酵素製劑溶解於 餾水之溶液的pH爲5.0~8.0、較佳爲6.0〜7.4 6.5〜7.4。酵素製劑中酸性物質的量以0.001〜99 佳、0.1~80重量％更佳、1~50重量部又更佳。惟 組胺酸等的鹼性胺基酸作爲鹼性物質時，雖可倂 質，但不併用也沒關係。酵素製劑中鹼性物: 0.001~99重量％爲佳、0.1〜80重量％更佳、1~50 更佳。 以下列舉實驗例、實施例以更加詳細地說明 但本發明並不僅只受限於此等的實施例》 可藉由添 賦形劑、 膠、酪蛋 乳化劑、 半胱胺酸 料、香料 而獲得米 爲液體狀 製劑中各 u葡萄糖 、較佳爲 α -葡萄糖 適。酸性 5倍量蒸 、更佳爲 重量％爲 ，在使用 用酸性物 Ϊ的量以 重量％又 本發明。 -19- 201201710 [實驗例1]201201710 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a method for producing a food such as rice food using transglutaminase, glucose oxidase, and/or α-glucosidase, and a food modification method. Enzyme preparation. [Prior Art] Most foods are composed of various components such as starch, protein, sugar, and lipid, and these complexities create a taste of food. Among them, starch or protein has a great influence on the mouthfeel, especially the temporal change of starch is particularly important. According to Patent Document 1, in the case of a starch-containing food property improving agent, it is possible to obtain a soft, viscous, and not easily deteriorated over time by adding a glucosidase of α-glucosidase to rice during cooking. Cooking rice. Although excellent results are seen, there is room for improvement in terms of the looseness of the rice grains or the improvement of the physical properties. In this way, it is difficult to achieve an improvement in the mouthfeel immediately after cooking, and the excellent mouthfeel can be maintained for a long period of time. Regarding the use of transglutaminase for rice 'in Patent Document 2', a method for producing rice cooking rice is disclosed, in which rice is added to the cooking rice by adding transglutaminase and Partially hydrolyzed protein, less sugar, sugar alcohol to cook rice, to make the rice no longer lose its flavor even after long-term storage after cooking, especially for the cooking rice, only the transglutaminase At the time, although the chewyness was observed, compared with the rice cooked rice to which the transglutaminase and the partial protein hydrolyzate of the wheat protein-5-201201710 were added, the viscosity was lacking and the throat was inferior. Further, in Patent Document 3, a method of preventing deterioration of starch caused by multi-water rice storage at low temperature or low-temperature circulation by adding transglutaminase is described, but general rice cooking rice and rice water in rice are generally used. The taste is completely different. In Patent Document 4, it is described that an enzyme transglutaminase and a-glucosidase which are effective for improving the physical properties of proteins can produce a graininess or looseness which is not obtained by a single glucosidase, and The rice that can maintain the taste after a long time. Although the effect on the taste and the improvement of the change over time can be seen to be quite high, on the taste side, due to the increase in graininess, the Q-sense of the Japanese preference and the feeling of swelling are slightly weakened. . In order to solve this problem, Patent Document 5 discloses a technique for using three enzymes such as transglutaminase, α-glucosidase, and glucose oxidase, and commercially available three enzymes for food property improvement. The enzyme preparation "ACTIVA®" super rice (manufactured by Ajinomoto Co., Ltd.). This commercially available product is mainly used as a physical property improver for rice, and is fully modified. Patent Document 5 is the first example of the application of glucose oxidase to the improvement of physical properties of rice. Further, in Patent Document 6, a method of reducing the amount of glucose in rice by glucose oxidase to produce a weight loss rice is described. In Patent Document 7, it is described that glucose oxidase and glucose are added to produce a conditioned rice. In the case where the dissolved oxygen is placed in the glucose to prevent deterioration due to lipid acidification in the rice, there is no description about the physical property improvement. Although there are many reports on the use of glucose oxidase on bread, and it is known to improve the stability of the dough, but the bread and rice are completely different foods - 6-201201710, the taste is also very different 'glucose oxidase pair The effect of adding bread is different from the effect of adding rice food. In the method of using the above commercially available enzyme preparations such as transglutaminase, glucosidase, glucose oxidase and the like, it is usually a method of dissolving and cooking rice in an immersion liquid of rice, but In the large-scale rice cooking factory, due to the importance of workability, the high-concentration water of the enzyme preparation is adjusted in another liquid tank: the liquid solution and the aqueous solution of the enzyme are automatically pumped into the rice for cooking, and the enzyme is used. The high-concentration aqueous solution of the preparation can be kept in the liquid tank for about 24 hours. The present inventors have found that when a high-concentration solution containing the above-mentioned commercially available preparation of transglutaminase, α-glucosidase, and glucose oxidase is held in a liquid tank for about 24 hours, the activity of each enzyme is lowered, and it is impossible to We will play a new topic such as full improvement. For example, when a 20% aqueous solution of the above-mentioned commercially available preparation is stored at 25 ° C for 24 hours, it is found that 90% or more of the transglutaminase and the glucose oxidase, and 20% or more of the α-glucosidase lose activity. It has even been found that in the case of the use of 3 enzymes, in the case of transglutaminase and α-glucosidase, or in the case of transglutaminase and glucose oxidase 2, high concentration solution When kept for about 24 hours, the activity of each enzyme is lowered. The low stability of the enzyme preparation means that the effect of improving the mouthfeel is inconsistent and restricts the use of the user. For example, when an aqueous solution of an enzyme preparation cannot be stored for a long period of time, when it is used for mass production of rice food, it is necessary to have other equipment investment, staffing, and the like. In the method for the stabilization of the enzyme, a method of adding soluble starch to the purification step and the formulation step of ascorbate oxidase 201201710 is known (Patent Document 8), and a tackifier, protein, and polyglycerol fat are added to the meat softening enzyme. Method for acid ester (Patent Document 9), method for adding a arazyme and a plant protein to a phosphatase or a glycosidase (Patent Document 10), and a method for adding a material derived from coffee to a polymannanase (Patent Document) 11) Wait. Further, in the method of stabilizing the transglutaminase which causes a decrease in activity due to oxygen, Patent Document 12 discloses a transglutaminase and (a) an organic acid, an alkali metal salt thereof or an ester thereof. And (b) a method of using one of inorganic acid or a salt thereof, (c) polyphenol, (d) mercaptan or (e) sugar alcohol, or with (a') an organic acid or a base thereof A method in which two or more kinds of substances selected from the group consisting of a metal salt, an ester thereof, an inorganic acid and a salt thereof, (c) a polyphenol, (d) a mercaptan, and (e) a sugar alcohol are used, but Patent Document 13 The middle system has a description that the addition effect of the additive is insufficient, and a method of using the partial hydrolyzate of the protein is disclosed. Patent Document 12 does not describe the use of transglutaminase with acidic substances and alkaline substances, nor does it disclose or teach about the effects of other enzymes. Enzymes are completely different in function and characteristics due to their types. Each method is only effective for specific enzymes. That is, the technique for stabilizing all enzymes is unknown, and the method for achieving stability of transglutaminase, α-glucosidase, and glucose oxidase is also unknown. [Patent Document 1] [Patent Document 1] WO2005/096839 201201710 [Patent Document 2] JP-A-9-206.006 [Patent Document 3] Patent No. 33 1008 No. 1 [Patent Document 4] Special Opening 2009-022267 [Patent Document 5] W0201 0/035858 [Patent Document 6] Patent No. 37 1 8495 [Patent Document 7] Patent No. 2808060 [Patent Document 8: Japanese Patent Laid-Open No. Hei 5-244948 (Patent Document 9) Japanese Laid-Open Patent Publication No. 2007-275065 [Patent Document No. 2007-275065] [Patent Document Π] Japanese Patent Publication No. 4-2071 No. 94 [Patent Document] 13] W096/1 1264 [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a food manufacturing method and food modification which can improve physical properties and taste. An enzyme preparation for use, in particular, a mouthfeel which is not available only by α-glucosidase, transglutaminase alone or two enzymes, such as "Q-sense" and "swelling" Or the "rice" and "sweet" rice food system More specifically, the object of the present invention is to provide a 2 enzyme which contains transglutaminase and glucose oxidase or α-glucosidase or contains a transaminase or α-glucoside. The solution of enzymes, glucose oxidase and other 3 enzymes can maintain the activity of each enzyme in the case of 201201710 for about 24 hours. [Method of solving the problem] The inventors focused on the results of the review and found that by turning the bran Phosphatase and 2 enzymes such as glucose oxidase or α-glucosidase, or phosphate, carbonate, and organic acid in addition to 3 enzymes such as transglutaminase, glucosidase, and glucose oxidase The present invention can be achieved by solving the above problems. The present invention relates to the following invention. (1) A method for producing a food, which is characterized in that (醯) transglutaminase and glucose oxidation are used. An enzyme and/or an α-glucosidase, at least one acidic substance selected from the group consisting of phosphoric acid, a phosphate, an organic acid, and an amino acid, and (C) a phosphate, a carbonate, a citrate Basic amino acid, At least one type of test substance selected by the group of the group of the oxidized group. (2) The method according to (1), wherein the acidic substance is malic acid or citric acid 'alkaline substance is disodium hydrogen phosphate or trisodium phosphate or Sodium carbonate. (3) A method for producing a food, which comprises (α) transglutaminase with glucose oxidase and/or α-glucosidase and (c) an amino acid. (4) The production method according to (3), wherein the basic amino acid is histidine. (5) A method for producing a food product, characterized in that it contains a solution containing (酶) 转fe: enzyme, glucose oxidase or α_glucosidase, (Β) acidic substance and (C) basic substance, Or use a solution containing (Α) transglutaminase and glucose oxidase or α-glucosidase and basic amino acid 10-201201710 and use. (6) A method for producing a food, which comprises preparing a solution containing branamine, glucose oxidase and α-glucosidase, (B and (C) basic substances, or preparing (a) enzyme And a method according to (5) or (6), wherein the acid is 0.02 to 20% by weight of the solution, and the alkalinity is used. The amount of the substance is 5% by weight, and the pH of the solution is 5.0 to 8.0. (8) The method according to any one of (1) to (7), wherein the rice food is (9) as described in (6) The method, wherein the amount of the food-based rice bran glutamate is 0.05 lg raw rice is 0.05~12U, the amount of α-enzyme is 15~1 50,000U per lg raw rice, and the amount of grapes is lg The raw material raw rice is 0.03 to 210 Ue. (10) The method according to (6) or (9), wherein the amount of the grape is 0.003 to 10,000 U per 1 U of transglutaminase, and the perglycosidase is 〇·〇〇. The amount of 〇〇〇3~34υ and α-glucosidase is 0.15~2O0, OOOU per guanylase. (1 1 ) An enzyme preparation containing (A) transglutamin oxidase and/or Alpha-glucose At least one acid f selected from the group consisting of phosphoric acid, phosphoric acid, and amino acid, and at least one selected from the group consisting of phosphate, carbonate 'citrate, basic amino acid, and oxygen. One kind of alkaline substance is used as an active ingredient. The amount of the substance ('A: 丨)) acidic substance transferred to the citronamine acid is 02~50, and the food is rice, and the glucoside sugar oxidase is oxidized. - Grape 1U transglutaminase and gluconate, [[C] Calcium -11 - 201201710 (12) - an enzyme preparation" containing (a) transglutaminase and glucose oxidase and / or Α-glucosidase and (C) basic amino acid as an active ingredient. (13) An enzyme preparation containing (Α) transglutaminase, glucose oxidase and α-glucosidase, (Β a group of at least one acidic substance selected from the group consisting of phosphoric acid, a diacid salt, an organic acid, and an amino acid, and (C) a phosphate, a carbonate, a citrate, a basic amino acid, and a calcium oxide. An enzyme preparation selected from the group consisting of at least one basic substance as an active ingredient, or containing (Α) transglutaminase and glucose oxidation And / or α-glucosidase and (C) basic amino acid as an active ingredient enzyme preparation, wherein the glucose oxidase content is 0.003~1 0,000 U per 1 U of transglutaminase per lUa-glucose The glucosidase is 0.000003-34 U. [Effect of the Invention] According to the present invention, even when the enzyme solution containing the transglutaminase and the glucose oxidase and/or the α-glucosidase is kept for about 24 hours, A food that maintains good activity of each enzyme is obtained. In particular, it is possible to obtain a mouthfeel which cannot be obtained by using only α-glucosidase, transglutaminase alone or two enzymes, for example, "Q-sense", "swelling" or "granularity", Rice food with "sweet feeling". [Embodiment] [Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The method for producing foods according to the present invention is the use of (A) transglutaminase and glucose oxidase and/or α-glucosidase, (B) in the enzyme preparation for food and food modification. Acidic substance such as phosphoric acid, phosphate, organic acid 'acidic acid acid, and (C) alkaline substance such as phosphate, carbonate, citrate, basic amino acid, calcium oxide, etc., or used (A Transgenic glutaminase with glucose oxidase and/or alpha-glucosidase and (C) basic amino acid. The glucose oxidase of the present invention is an oxidase which catalyzes the reaction of glucose, oxygen and water as a substrate to form hydrogen peroxide with grape pond acid. Hydrogen peroxide generated by this reaction promotes SS bond (disulfide bond) formation by oxidizing the SH group in the protein, and makes a crosslinked structure in the protein. It is known that glucose oxidase is derived from various origins such as microorganisms and plants, but the enzyme used in the present invention is an enzyme having such activity, regardless of its origin. Also, even recombinant enzymes can be used. The name of the product called "Sumizyme PGO" is a microbial glucose oxidase sold by Shin-Nippon Chemical Industry Co., Ltd. as an example. Further, although a glucose oxidase preparation in which a catalase is mixed is commercially available, if it has glucose oxidase activity, it may be a mixture with other enzymes. The enzyme activity of glucose oxidase is based on glucose, which causes glucose oxidase to form hydrogen peroxide in the presence of oxygen, and the hydrogen peroxide formed in the presence of amine antipyrine and benzoquinone The color tone of the quinone imine dye produced by the action of peroxidase was quantified by measurement at a wavelength of 500 nm. The amount of enzyme necessary to define 1 minute of oxidized Ιμιηοΐ glucose is 1U: enzyme activity unit unit). The transglutaminase of the present invention refers to an activity of a thiol transfer reaction which catalyzes the use of a brasinic acid residue of -13-00101710 in a protein or a peptide as a donor and an lysine residue as a acceptor. Enzymes are known to originate from mammals, fishermen, and microbes. The enzyme used in the present invention may be any enzyme which has such activity, and any of its origins may be used. Also, even recombinant enzymes can be used. Ajinomoto (share) is a transglutaminase derived from actinomycetes sold under the trade name "ACTIVA" TG. The enzyme activity of transglutaminase is benzyloxycarbonyl-L. - branamine mercaptoglycine and hydroxylamine as a substrate, the resulting hydroxylamine is formed into an iron complex in the presence of trichloroacetic acid, the absorbance at 525 nm is measured, and the hydroxylamine is determined from the calibration curve. The amount of acid is calculated and the activity is calculated. Definition The amount of enzyme that produces Ιμηηοΐhydroxylamine in 1 minute at 37 ° C and pH 6.0 is 1 U (enzyme activity unit unit). The α-glucosidase of the present invention hydrolyzes a non-reducing terminal α-1,4-glucoside bond and produces an α-glucose enzyme. Among the α-glucosidases, a transglucosidase having an α-1,6 bond which is superior to the α-1,4 bond sugar transfer activity is preferred. Further, an enzyme commercially available from Amano Enzyme (trade name), which is referred to as a transglucosidase L "ΑΜΑΝΟ", is an example of an α-glucosidase. The enzyme activity of α-glucosidase is 1 ml of 1 mM α-methyl-D-glucoside, 1 ml of 0.02 Μ acetic acid buffer (pH 5.0), and 0.5 ml of enzyme solution is added to make it act at 40 ° C. After 60 minutes, the amount of the enzyme which produced 1 μg of glucose in 2.5 ml of the reaction solution was defined as 1 U (enzyme activity unit unit). The acidic substance of the present invention means a pH of -14 to 201201710 when dissolved in distilled water, and also refers to an inorganic acid, an organic acid, an amino acid, or the like. From the viewpoint of the use of food, the influence on the taste of food, solubility, and buffering energy, potassium dihydrogen phosphate, sodium dihydrogen phosphate, malic acid, citric acid, glycine acid, and malic acid are preferred. Citric acid is better. The amount of the acidic substance is 〜. 2 to 20% by weight of the mixed solution of (A) transglutaminase, α-glucosidase, glucose oxidase, (Β) acidic substance and (C) basic substance. Good, 〇.i~io li% is better, 1~5 wt% is better. Further, when a basic amino acid such as histidine is used, an acidic substance may not be used. The basic substance of the present invention is an inorganic salt, an organic acid salt, an amino acid salt or a basic amino acid, which is a pH which is alkaline when dissolved in distilled water. From the use of food, the influence on the taste of rice food, solubility, buffering energy, it is potassium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium carbonate, sodium carbonate, lysine, fine Amino acid and histidine are preferred, and disodium hydrogen phosphate, trisodium phosphate, sodium carbonate and histidine are more preferred. The amount of the alkaline substance is preferably 0.02 to 50% by weight of the mixed solution of (A) transglutaminase, α-glucosidase, glucose oxidase, (Β) acidic substance, and (C) basic substance. 〇. 1~30% by weight is better, 2~9% by weight is better. Further, when a basic amino acid such as histidine is used, an acidic substance may not be used. In the present invention, when the basic amino acid is used alone, it is necessary to use both the acidic substance and the alkaline substance, and the pH of the solution when dissolved in distilled water is 5.0 to 8, preferably 6.0 to 7.4. More preferably, the range of 6.5 to 7.4 can be appropriately combined. For example, in the combination of malic acid or citric acid and disodium hydrogen phosphate, the concentration in the solution can be blended with 1% of acidic substance and 9% of basic substance, and in malic acid or citric acid and trisodium citrate. -15-201201710 When combined, the concentration in the solution can be blended with 2.5% acidic substance and 7.5% alkaline substance. Examples of the food of the present invention include rice food, noodles, bread, processed fish products, and aquatic products, processed meat products, meat, dairy products, soy products, wild vegetables, fruit, snacks, and the like. For rice food, rice, rice, vinegar rice, sushi rice, risotto rice, fried rice, stewed rice, glutinous rice, rice, porridge, Italian rice, rice balls, sushi, lunch, etc. Also included are such frozen products, aseptic packages, conditioning packages, dried products, and canned products. For the noodles, there are noodles, fried noodles, soba noodles, Chinese noodles, and macaroni. These include frozen products, low-temperature products, conditioning packages, and dried products. Examples of the bread include conditioning bread, snack bread, sandwiches, toast, rice flour bread, and black bread. Also included are such frozen and dried products. It can be the rice of the rice food raw material of the present invention, and any variety of rice can be used, and it does not matter whether it is soft rice, hard rice, new rice or old rice. Also, low quality stalked rice or low quality stalked rice can be used. Furthermore, it is also possible to process rice treated with acid or enzyme such as low protein rice (protein-adjusted rice). In the method for producing a rice food of the present invention, a solution of (A) transglutaminase, glucosidase, glucose oxidase, (Β) acidic substance, or (C) basic substance may be prepared without mixing. It is added to rice or rice, but the main point of solving the problem of the present invention is to add the mixed solution to rice or rice. Of course, it is also possible to add these effects without modulating the solution, and it does not matter whether it is applied at any stage of cooking, even if -16-201201710 is after cooking. That is, it is also possible to add (A) to (C) to the immersion liquid for immersing rice for water absorption, and it is not necessary to add it after immersion or before cooking. Moreover, it is also possible to spread the rice on the rice after cooking. In the steamed rice production line, the enzyme can also be sprinkled before or after the steaming step. In the present invention, the amount of the glucose oxidase to be added to the rice is 0.001 U or more, preferably 0.00 500 Å, more preferably 0.03 to 21 0 U. Suitable. The effect of glucose oxidase on rice can significantly impart "Q-sense" or "elasticity" to rice food, especially "Q-sense", which is added by transglutaminase or (X-glucosidase) The resulting mouthfeel. Although the use of transglutaminase and α-glucosidase can achieve a certain "elastic" effect, if the ratio of transglutaminase is increased in order to obtain a stronger "elasticity", There is a tendency to inhibit the "swelling sensation" of α-glucosidase, but the use of glucose oxidase can impart strong "elasticity" without excessive inhibition of α-glucosidase. On the other hand, when the glucose oxidase is added at 500 U or more, the rubbery-like unnatural taste is caused by the "elasticity" being too strong, and the degree of preference is lowered. In the present invention, when the raw material lg is used, when glucose oxidase is used The amount of addition is such that the enzyme activity is 0.00 1 U or more, preferably 〇. 0 0 1 to 5 0 0 U, more preferably 0.03 to 21 0 U, so that it acts on the transglutaminase of rice The amount added is for the raw rice lg The activity of the element is 0.0001 U or more, preferably 0.000 1 to 120 U, more preferably 0.05 to 12 U. Further, the amount of glucose oxidase per 1 U is desirably 0.003 to 10, and the transglutaminase is 0.003 to 10, 〇〇〇U, preferably 0.1 to 900 U, is preferably added to the transglutamin-17-201201710 enzyme. In the present invention, the raw rice lg is added to the amount of α-glucosidase of rice. The enzyme activity is preferably 0.03 U or more, preferably 0.03 to 300,000 U, more preferably 15 to 1 50,000 U. The amount of the transglutaminase added is 0.15 per 1 U of the α-glucosidase. Preferably, the amount of glucose peroxidase per 1 U is preferably α-glucosidase by adding α-glucosidase to 0.000003 to 34 U, preferably 0.000006 to 3 U. When branase and α-glucosidase and/or glucose oxidase act on rice to produce rice food, the ratio of each enzyme added is calculated by enzyme activity (U number), and per 1U glucose oxidase is converted to bran The aminase is 0-003~10,000 U, preferably 0_1~9 00 U, and/or per 1 U glucose oxidase α- The glycosidase is preferably 0.000003 to 34 U, preferably 0.000006 to 3 U. When the amount of each enzyme added is in the above range, the quality immediately after manufacture (physical properties such as swelling feeling, Q feel, graininess, and looseness) It is good and can produce rice food which can suppress deterioration of quality due to the passage of time. The reaction time of each enzyme is not particularly limited as long as the reaction time of the enzyme acts on the matrix substance, and it can be made for a very short time or vice versa. Time can also be used, and the actual action time is preferably 5 minutes to 24 hours. Further, regarding the reaction temperature, any temperature which can maintain the activity of the enzyme does not matter, and in reality, it is preferable to make it work at 0 to 80 °C. That is, a sufficient reaction time can be obtained by a general rice cooking step. In addition to (A) transglutaminase, α-glucosidase, glucose oxidation-18-201201710 enzyme, (B) acidic substance, (C) alkaline substance, mixed dextrin, starch, processed starch, A chelating agent such as a seasoning material such as animal meat, such as maltose, a vegetable protein, a gluten, a protein, a protein, a protein hydrolyzate, a protein partial decomposition product, a citrate, a polymeric phosphate, or the like, and a glutamine-based sulfur, Other food additives such as reducing agents, alginic acid, alkaline water, oils and fats, pigments, sourness, and enzymes such as catalase, etc., are enzyme preparations for the upgrading of rice foods. The enzyme preparation of the present invention may be in any form of a paste, a granule or a powder. Further, although the amount of the enzyme enzyme is more than 0% and less than 100%, the transglutaminase is 0.003 to 10,000 U 0.1 to 900 U per 1 oxidase, and/or per 1 U of glucose oxidase. The content of the glycosidase is 0.000003 to 34 U, preferably 0.000006 to 3 U, and the amount of the alkaline substance is preferably such that the pH of the solution in which the enzyme preparation is dissolved in the distilled water is 5.0 to 8.0, preferably 6.0 to 7.4 6.5. 7.4. The amount of the acidic substance in the enzyme preparation is preferably 0.001 to 99, more preferably 0.1 to 80% by weight, still more preferably 1 to 50 parts by weight. When a basic amino acid such as histamine is used as a basic substance, it may be enamel, but it may not be used in combination. The alkaline substance in the enzyme preparation is preferably 0.001 to 99% by weight, more preferably 0.1 to 80% by weight, even more preferably 1 to 50%. The following examples and examples are given to illustrate in more detail, but the present invention is not limited only to the examples, and may be added by excipients, gums, casein emulsifiers, cysteine, perfumes. The obtained rice is a liquid preparation, and each of the u glucose, preferably α-glucose, is suitable. The acidity is 5 times the amount of steam, more preferably the weight %, and the amount of the acidic substance is used in the weight %. -19- 201201710 [Experimental Example 1]
使由轉麩醯胺酶（以下簡稱爲TG) 、α-葡萄糖苷酶 (以下簡稱爲AG)、葡萄糖氧化酶（以下簡稱爲GO)、 糊精所成的米飯用酵素製劑（製劑每l〇〇g含有TG6.2g、 7，3 78U、AG4.74g、2, 940,000U、G031.3g、65，73 0U )溶解於超純水，調製20%溶液。溶液中各酵素的濃度係 AG0.95%、TG1.24%、G06.26%。TG 使用味之素公司製「 ACTIVA」TG ( 1，190U/g ) 、AG 使用天野 Enzyme 公司 製α-葡萄糖苷酶「AMANO」（ 620,000U/g) 、GO使用新 日本化學工業公司製「Sumizyme PGO j ( 2，100U/g )) 。測定將調製之酵素溶液保存在25 t時的各酵素殘存活性 ，如圖1所示，各酵素的活性會降低，特別是GO、TG在 24小時後的酵素活性幾乎無殘存。又，調製溶液中溶解 有各酵素濃度爲AG3.20%、TG2.00%之溶液，測定保存後 各酵素的殘存活性，其結果如圖2所示，且調製溶解有各 酵素濃度爲TG 1.24%、G06.26%之溶液，測定保存後各酵 素的殘存活性，其結果如圖3所示。各酵素濃度同樣地調 製僅溶解各酵素之溶液，測定保存後各酵素的殘存活性， 如表1所示，未見除了 GO以外的活性降低。特別是，圖 1~3中所示的現象，係在TG與GO或AG之2酵素或是 TG、AG、GO之3酵素的混合溶液中表現的，似乎是因某 種相互作用所致。 -20- 201201710 [表1] 摆 绩濃度 保i 字時間(小時)與殘存活性 濃度(％) 活性値(u/g) 0 3 6 24 TG 1.24¾ 13.6 100.0% 95.4% 94.2% 100.0% AG 0.95% t.2 100.0% 96.1% 100.2% 96.4¾ GO 6.26% 125.2 100.0% 23.0¾ 18.2» 4.1% [實驗例2] 生米「北海道KIRARA397」300g以自來水洗米，自 來水浸漬1小時。浸漬米濾掉水後’放入電鍋^ IH呷-煮 飯器NJ-HS06-S」（三菱電機公司製），對生米加入1.5 倍自來水。此外，所謂1 ·5倍加水’係指浸漬時的生米吸 水量與浸漬後的加水量之合計爲生米3 0 0 g之1 · 5倍量爲 450g之加水。其中’以表2所示之慘合來添加AG、G(〕、 T G並使其溶解，以上述電鍋煮飯。將所得予以冷凍之冷 凍米飯在-20°C保存1週後，以微波回溫進行官能評價。 官能評價除了就軟硬、Q彈感、保水感、膨潤感、黏性、 啪啦感、彈力、粒感等8項目進行之外’也將白飯之口感 平衡的喜好程度以◎、〇、△、X之記號表示。◎是「非常 佳」、〇是「佳」、△是「稍佳」、X是「不佳」之意思 。令評價人數爲人。此外’表中的3.4 E +2或5·6Ε-6 係爲指數之表示，各意指3.4X10的2次方、5.6x10的-6 次方。 -21 - 201201710 [表2] 試驗區 1 2 3 4 5 6 7 8 9 ag添加量[υ/g生米） 0 0.003 0.03 15 38 45 50 75 88 TG添加fi(U/g生米） 0 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 GO*加量(U/g生米） 0 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 GO/AG0J 比） 0 3.4B-02 3.4E+01 5.6Ε-02 2.2Ε-02 1.9Ε-02 1.7Ε-02 1.1Ε-02 9.6Ε-03 GO/TG(U 比） 0 3.2ΒΌΟ 3.2圧州0 3.2Ε+00 3.2Ε+00 3.2Ε+00 3.2Ε+00 3.2E-KJ0 3.2Ε+00 官能評價結果 X X Λ 〇 © ◎ ◎ ◎ ◎ 試驗區 10 11 12 13 14 15 16 17 18 AG添加SU/g生米） 95 100 5000 150000 300000 375000 70.8 70.8 70.8 TG添加受(U/g生米） 0.26 0.26 0.26 0.26 0.26 0.26 0.00005 0.0001 0.05 GO添加量(U/g生米） 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 GO/AG0J 比） 8.8E-03 8.4E-03 1.7Ε-04 5.6Ε-06 2.8Ε-08 2.2Ε-06 1.2Ε-02 1.2Ε-02 1.2Ε-02 GOJG(U 比） 3.2E-KJ0 3.2&-00 3.2Ε+00 3.2Ε+00 3.2Ε-ΚΙ0 3.2Ε·Κ)0 1.8Ε+04 9.1Ε+03 1.8Ε+01 官能評價結果 ◎ ◎ 0 〇 Δ X X Δ Ο 試驗區 19 20 21 22 23 24 25 26 27 AGS5M«U/s 生米〉 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.8 TG添加fi(U/E生米） 0.14 0.16 0.18 0.23 0.32 0.35 0.37 0.41 11.5 GO通加曼(U/R生米〉 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 GO/AG(U 比） 1.2E-02 1.2E-02 1.2Ε-02 1.2Ε-02 1.2Ε-02 1.2Ε-02 1.2Ε-02 1.2Ε-02 1.2Ε-02 GO/TG(U 比〉 6.1E+00 5.2Ef〇0 4.6Ε+00 3.7Ε+00 2.6Ε+00 2.4Ε+00 2.3Ε-ΚΚ) 2.0Ε+00 7.3Ε-02 官能評價結果 © ◎ ◎ ◎ ◎ ◎ ◎ ◎ Ο 試驗區 28 29 30 31 32 33 34 35 36 AG活加《U/β生米〉 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.8 tgs加e(u/g生米） 115 230 0.26 0.26 0.26 0.26 0.26 0.26 0.26 GOS5加登(U/s生米） 0.84 0.84 0.0001 0.001 0.03 0.42 0.50 0.59 0.67 GO/AG0J 比） 1.2E-02 1.2E-02 1.2Ε-06 1.2Ε-05 3.6Ε-04 5.9Ε-03 7.1Ε-03 8.3Ε-03 9.5Ε-03 GO/TG(U 比） 7.3E-03 3.76-03 3.2Ε-04 3.2Ε-03 9.7Ε-02 1.6Ε+00 1.9Ε+00 2.3E-MD0 2>6Ε+00 官能評價結果 Δ X X Δ 〇 ◎ ◎ ◎ ◎ 試驗區 37 38 39 40 41 42 43 44 AG添加au/g生米〉 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.7 TG添加受(U/g生米） 0.26 0.26 0.2Θ 0.26 0.26 0.26 0.26 0.17 GO添加量(U/g生米） 1.18 1.26 1.34 1.68 210 504 3360 1.68 GO/AGOJ 比） 1.7E-02 1.8E-02 1.9Ε-02 2.4Ε-02 3.0Ε+00 7.1Ε+00 4.7E-KJ1 2.4Ε-02 GO/TGOI 比） 4.5E+00 4.8 &Ό0 5.2Ε+00 6.5Ε+00 8.1Ε+02 1.9Ε·Κ)3 1.3Ε+04 9.7Ε+00 官能評價結果 ◎ ◎ ◎ ◎ 〇 △ X ◎ 如表2所示可確認，併用3酵素時的AG、TG、GO 各自的添加量在某一定範圍內時，係會因添加而有較佳的 效果。又，在G0/AG比（U比）、GO/TG比（U比）中 ，亦可確認在某一定之範圍內會有較佳的效果。AG係在 每 lg生米爲 〇.〇3〜3 00,000U時有稍佳的效果、在 15~150,000U時發揮了較佳的效果。TG係在每lg生米爲 0.000 1〜115U時有稍佳的效果、0.05〜11.5U時發揮了較佳 的效果。GO係在每lg生米爲0.001〜5 04U時有稍佳的效 -22- 201201710 果、0.03〜210U時發揮了較佳的效果。又，對AG1U而言 ，GO量方面在 0.000003〜34U時有稍佳的效果、 0.000006〜3U時發揮了較佳的效果。對TG1U而言，GO 量方面在〇.〇〇3~9130U時有稍佳的效果、o.i〜8〇7U時發 揮了較佳的效果。整理以上的値可知，對米飯食品添加 AG及 TG及 GO時，AG的添加量係每lg生米以 0.03~3 00,0O0U爲佳、15〜1 50,000U更佳。TG的添加量係 每lg生米以〇·〇〇〇1〜120U爲佳、0.05〜12U更佳。GO的 添加量係每lg生米以〇.〇〇l~500U爲佳' 0.03〜210U更佳 。又顯示出，對AG1U而言，GO量係以0.000003〜34U爲 佳、0.000006〜3VJ更佳，且對TG1U而言，GO量係以 0.003〜1 0,000U爲佳、0.1〜900U更佳。如上所述以上述範 圍內之條件倂用3酵素，係可在不犧牲「軟硬」「Q彈感 」「保水感」「膨潤感」「黏性」「啪啦感」「粒感」之 任一項目下，兼具平衡地賦予此等性質。特別是因同時賦 予至今仍難以達戌之稱爲「軟硬」「粒感」等口感與「Q 彈感」「膨潤感」等口感，而得以實現較佳之口感。 [實施例1] 使用在實驗例1中所用之AG、TG、GO ’調製表3所 示摻合之酵素製劑，調製了與實驗例1同樣2 0%溶液。此 外，糊精係使用松谷化學公司製的「Pinedex#l」。測定 酵素製劑溶液在25 °C、24小時保存後之各酵素的殘存活 性。調製後即刻的活性値爲1 〇〇時，求取24小時後之酵 -23- 201201710 素活性殘存率，並將結果顯示於表3。 [表3】An enzyme preparation for rice prepared by transglutaminase (hereinafter abbreviated as TG), α-glucosidase (hereinafter abbreviated as AG), glucose oxidase (hereinafter abbreviated as GO), or dextrin (preparation per 〇) 〇g contains TG6.2g, 7,378U, AG4.74g, 2, 940,000U, G031.3g, 65,73 0U) dissolved in ultrapure water to prepare a 20% solution. The concentration of each enzyme in the solution was AG 0.95%, TG 1.24%, and G62.6%. TG uses "ACTIVA" TG (1,190 U/g) manufactured by Ajinomoto Co., Ltd., AG uses α-glucosidase "AMANO" (620,000 U/g) manufactured by Amano Enzyme, and "Sumizyme" manufactured by Nippon Chemical Industry Co., Ltd. PGO j (2,100U/g )). Determine the viability of each enzyme when the prepared enzyme solution is stored at 25 t. As shown in Figure 1, the activity of each enzyme will decrease, especially after 24 hours of GO and TG. There is almost no residual activity of the enzyme. Further, a solution of each enzyme concentration of AG3.20% and TG2.00% is dissolved in the preparation solution, and the residual activity of each enzyme after storage is measured, and the result is shown in Fig. 2, and the preparation is dissolved. There are solutions in which the concentration of each enzyme is TG 1.24% and G6.2.6%, and the residual viability of each enzyme after storage is measured, and the results are shown in Fig. 3. Each enzyme concentration is similarly prepared by dissolving only the solution of each enzyme, and measuring each after storage. The residual activity of the enzyme, as shown in Table 1, showed no decrease in activity other than GO. In particular, the phenomenon shown in Figures 1-3 was based on TG and GO or AG 2 enzymes or TG, AG, GO. Of the 3 enzymes in the mixed solution, it seems to be due to some interaction -20- 201201710 [Table 1] Performance concentration i-time (hours) and residual viability (%) Activity 値 (u/g) 0 3 6 24 TG 1.243⁄4 13.6 100.0% 95.4% 94.2% 100.0 % AG 0.95% t.2 100.0% 96.1% 100.2% 96.43⁄4 GO 6.26% 125.2 100.0% 23.03⁄4 18.2» 4.1% [Experimental Example 2] 300g of raw rice "Hokkaido KIRARA397" was washed with tap water and immersed in tap water for 1 hour. After the water was immersed in the immersed rice, it was placed in an electric cooker, IH呷-cooker NJ-HS06-S (manufactured by Mitsubishi Electric Corporation), and 1.5 times tap water was added to the raw rice. In addition, the term "1.5 times the amount of water added" means that the total amount of water absorbed by the raw rice and the amount of water added after the immersion is 1⁄5 times the amount of raw rice, and the amount of water added is 450 g. Among them, AG, G(], TG were added and dissolved in the mixture shown in Table 2, and the rice was cooked in the above-mentioned electric pot. The frozen rice which was obtained by freezing was stored at -20 ° C for 1 week, and microwave was used. The sensitization was evaluated by the temperature evaluation. In addition to the 8 items including softness and hardness, Q-sense, water retention, swelling, viscosity, squeakiness, elasticity, and graininess, the degree of preference for the taste of the rice was also balanced. It is indicated by the symbol of ◎, 〇, △, X. ◎ is "very good", 〇 is "good", △ is "slightly better", and X is "poor". The number of evaluations is human. The 3.4 E +2 or 5·6Ε-6 in the system is expressed as an index, which means 3.4X10 to the 2nd power and 5.6x10 to the -6th power. -21 - 201201710 [Table 2] Test area 1 2 3 4 5 6 7 8 9 ag added amount [υ/g raw rice) 0 0.003 0.03 15 38 45 50 75 88 TG added fi (U/g raw rice) 0 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 GO* addition amount (U/ g raw rice) 0 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 GO/AG0J ratio) 0 3.4B-02 3.4E+01 5.6Ε-02 2.2Ε-02 1.9Ε-02 1.7Ε-02 1.1Ε-02 9.6Ε- 03 GO/TG (U ratio) 0 3.2ΒΌΟ 3.2圧State 0 3.2Ε+00 3.2Ε+00 3.2Ε+00 3.2Ε+00 3.2E-KJ0 3.2Ε+00 Functional evaluation result XX Λ 〇© ◎ ◎ ◎ ◎ Test area 10 11 12 13 14 15 16 17 18 AG added SU/g raw rice) 95 100 5000 150000 300000 375000 70.8 70.8 70.8 TG addition (U/g raw rice) 0.26 0.26 0.26 0.26 0.26 0.26 0.00005 0.0001 0.05 GO addition amount (U/g raw rice) 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 GO/AG0J ratio) 8.8E-03 8.4E-03 1.7Ε-04 5.6Ε-06 2.8Ε-08 2.2Ε-06 1.2Ε-02 1.2Ε-02 1.2Ε-02 GOJG(U ratio) 3.2 E-KJ0 3.2&-00 3.2Ε+00 3.2Ε+00 3.2Ε-ΚΙ0 3.2Ε·Κ)0 1.8Ε+04 9.1Ε+03 1.8Ε+01 Functional evaluation result ◎ ◎ 0 〇Δ XX Δ Ο test Area 19 20 21 22 23 24 25 26 27 AGS5M «U/s raw rice> 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.8 TG added fi (U/E raw rice) 0.14 0.16 0.18 0.23 0.32 0.35 0.37 0.41 11.5 GO Tongjiaman (U/R raw rice) 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 GO/AG (U ratio) 1.2E-02 1.2E-02 1.2Ε-02 1.2Ε-02 1.2Ε-02 1.2Ε-02 1.2Ε- 02 1.2Ε-02 1.2Ε-02 GO/TG(U ratio > 6.1E+00 5.2Ef〇0 4.6Ε+00 3.7 +00 2.6Ε+00 2.4Ε+00 2.3Ε-ΚΚ) 2.0Ε+00 7.3Ε-02 Functional evaluation result © ◎ ◎ ◎ ◎ ◎ ◎ ◎ Ο Test area 28 29 30 31 32 33 34 35 36 AG live plus U/β raw rice> 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.8 tgs plus e (u/g raw rice) 115 230 0.26 0.26 0.26 0.26 0.26 0.26 0.26 GOS5 Garden (U/s raw rice) 0.84 0.84 0.0001 0.001 0.03 0.42 0.50 0.59 0.67 GO/AG0J ratio) 1.2E-02 1.2E-02 1.2Ε-06 1.2Ε-05 3.6Ε-04 5.9Ε-03 7.1Ε-03 8.3Ε-03 9.5Ε-03 GO/TG(U ratio) 7.3E-03 3.76-03 3.2Ε-04 3.2Ε-03 9.7Ε-02 1.6Ε+00 1.9Ε+00 2.3E-MD0 2>6Ε+00 Functional evaluation result Δ XX Δ 〇◎ ◎ ◎ ◎ Test area 37 38 39 40 41 42 43 44 AG Add au/g raw rice> 70.8 70.8 70.8 70.8 70.8 70.8 70.8 70.7 TG addition (U/g raw rice) 0.26 0.26 0.2Θ 0.26 0.26 0.26 0.26 0.17 GO addition amount (U/g raw m) 1.18 1.26 1.34 1.68 210 504 3360 1.68 GO/AGOJ ratio) 1.7E-02 1.8E-02 1.9Ε-02 2.4Ε-02 3.0Ε+00 7.1Ε+00 4.7E-KJ1 2.4Ε-02 GO/TGOI Ratio) 4.5E+00 4.8 &Ό0 5.2Ε+00 6.5Ε+00 8.1Ε+02 1.9Ε·Κ)3 1.3Ε+04 9. 7Ε+00 Functional evaluation result ◎ ◎ ◎ ◎ 〇 △ X ◎ As shown in Table 2, it can be confirmed that when the addition amount of AG, TG, and GO in the case of using 3 enzymes is within a certain range, it is added by Good results. Further, in the G0/AG ratio (U ratio) and the GO/TG ratio (U ratio), it is also confirmed that a better effect is obtained within a certain range. The AG system has a slightly better effect when it is 〇.〇3~3 00,000U per lg of raw rice, and has a better effect at 15~150,000U. The TG system has a better effect when it is 0.000 1 to 115 U per lg of raw rice, and has a better effect when it is 0.05 to 11.5 U. The GO system has a slightly better effect when it is 0.001 to 5 04 U per lg of raw rice. -22-201201710, 0.03 to 210 U, which exerts a better effect. Further, for the AG1U, the GO amount has a slightly better effect at 0.000003 to 34 U, and a better effect is obtained at 0.000006 to 3 U. For TG1U, the amount of GO has a slightly better effect when it is 〇.〇〇3~9130U, and it has a better effect when it is o.i~8〇7U. According to the above, when adding AG, TG and GO to rice food, the addition amount of AG is preferably 0.03~3 00, 0O0U and 15~1 50,000U per lg of raw rice. The amount of TG added is preferably 〜·〇〇〇1 to 120 U per lg of raw rice, and more preferably 0.05 to 12 U. The addition amount of GO is preferably 0.0. 〇〇l~500U per lg of raw rice is better than 0.03~210U. Further, it is shown that the GO amount is preferably 0.000003 to 34 U and 0.000006 to 3 VJ for the AG1U, and the GO amount is preferably 0.003 to 10,000 U and more preferably 0.1 to 900 U for the TG1U. As described above, the use of 3 enzymes in the above-mentioned range is possible without sacrificing "soft and hard", "Q-sense", "water retention", "swelling", "stickiness", "sweetness" and "granularity". Under any project, these properties are balanced. In particular, it has been able to achieve a better taste by giving it a taste such as "soft and hard" and "granular" which are still difficult to achieve at the same time, and the taste of "Q-sense" and "swelling". [Example 1] Using the AG, TG, and GO' used in Experimental Example 1, the enzyme preparation blended as shown in Table 3 was prepared, and the same 20% solution as in Experimental Example 1 was prepared. In addition, "dinedex #l" manufactured by Matsutani Chemical Co., Ltd. was used as the dextrin. The residual activity of each enzyme after storage of the enzyme preparation solution at 25 ° C for 24 hours was measured. When the active enthalpy immediately after the preparation was 1 ,, the residual activity of the fermentation -23-201201710 after 24 hours was obtained, and the results are shown in Table 3. [table 3】
如表3所示，藉由在TG、GO、AG3酵素中以規定量 摻合特定的酸性物質及/或鹼性物質，可確認酵素溶液即 使在保持24小時後，各酵素的活性係可保持。 [實施例2] 調製表3所示之摻合酵素製劑，而調製與實施例1同 樣20%溶液，且保存在251、24小時。在生米「越光」 3 80g中加入.自來水5 80g，經1小時浸漬後，添加24小時 保存後的酵素製劑溶液3.8g (酵素製劑爲〇.76g)，且對 原料米lg而言，係使酵素製劑爲0.002g、GO爲1.3U、 TG爲0.1U、AG爲61.1U、酸性物質與鹼性物質的合計量 爲O.OOlg，以電鍋「IH呷-電鍋NJ-HS06-S」（三菱電機 公司製）煮飯。煮熟的米以真空冷卻機「食品用急速冷卻 機CMJ-40」（三浦PROTECH公司製）冷卻至25t以下 。所得之煮飯米（白飯）移至密封性高的容器中，以伸縮 性保鮮膜覆蓋，在20°C之恆溫槽保管24小時後，微波回 -24- 201201710 溫而以經訓練之品評員進行官能評價，並將其結果顯示於 表4。官能評價係用以確認對在W0200 5/096 839中所確認 對米之效果在本素材是否顯示出相加•相乘的效果。此外 ，官能評價在對照區方面所設定於煮飯前使GO、TG，AG 、酸性物質、鹼性物質與各試料等量添加，且與以同樣操 作製成的白飯比較，使物性同等且對味覺完全無影響者爲 ◎、物性同等且對味覺幾乎沒差別者爲〇、呈現出異味者 爲X。 [表4] 1 酵素製劑中各_料之慘合(％) I 『Will GO TG AG i mmm 鹼性物質 I msm mm 評價 31.3 6.2 4.7 — 0 一 0 EMS· 對照 31.3 6.2 4.7 檸樣酸憮水） 7.5 瞵酸三鈉 17.5 EMi· © 31.3 6.2 4.7 磷酸二通鉀 15 搬氫二鉀 35 mmm 7.8 100 ο 31.3 6.2 4.7 磷酸二通鉀 10 磷酸氫二鈉 40 EMM 7.8 100 ο 31.3 6.2 4.7 磷酸二讎 20 播酸三鈉 30 7.8 100 ο 31.3 6.2 4.7 磷酸二m鈉(無水） 10 磷酸氤二鉀 40 EH· 7.8 100 ο 31,3 6.2 4.7 磷酸二氫鈉嘸水） 7.5 裔酸氫二鈉 42.5 IMM 7.8 100 C)~ 31.3 6.2 4.7 磷酸二鈕鈉(無水） 22.5 磷酸三鈉 27.5 EH· 7.8 100 0 31.3 6.2 4.7 DL蘋果酸 5 磷酸氫二鉀 45 EH· 7.8 100 ο 31.3 6.2 4.7 DL蘋果瞍 5 满酸氤二鈉 45 IM· 7.8 100 (§) 31.3 6.2 4.7 DLmmm 12.5 磷酸三鈉 37.5 糊精 7.8 100 <§» 31.3 6.2 4.7 檸檬酸(無水） 5 屬酸氫二鉀 45 糊精 7.8 100 ο 31.3 6.2 4.7 嬙檬酸(無水） 5 磷酸氫二鈉 45 糊精 7.8 100 ◎ 31.3 6.2 4.7 1檸S酸(無水) 12.5 職三鈉 37.5 样精 7.8 100 ◎ 31.3 6.2 4.7 檸橡酸(獅 22.5 w酸鈉 27,5 7.8 100 ◎ 〇 ©一 31.3 6.2 4.7 櫸檬酸憮水） 5 彌酸 ! 15 _精 37.8 100 31.3 6.2 4.7 一 0 遞酸 10 精 47.8 100 如表4所示：藉由於TG、GO、AG3酵素中，以規定 量摻合特定的酸性物質及/或鹼性物質，係使酵素溶液即 使在保持24小時後，仍可確認與煮飯前添加了 3酵素之 對照品具有同等的口感、食味。特別是以規定量使用作爲 酸性物質之蘋果酸、檸檬酸' 作爲鹼性物質之磷酸氫二鈉 、磷酸三鈉、碳酸鈉、組胺酸時，對煮飯米的味覺完全沒 有影響。 -25- 201201710 [實施例3] 使用實驗例1中所用之TG，以及AG或GO之二酵素 調製表5所示之摻合酵素製劑，且調製與實驗例1同樣 2 0%溶液。此外，糊精係使用松谷化學公司製的「 Pinedex#l」。酵素製劑溶液在25°C、24小時保存後測定 各酵素的殘存活性。使調製後即刻的活性値爲100時，求 取24小時後的酵素活性殘存率，並將結果顯示於表5中 [«51 _ 1 1 TG IASJ IGO 1 賦形爾 合計丨 pH mmm AG GO -Ϊ0 ~ίδ 0 一 0 — —糊梢 1 741 1001 7.0 60 85 10 16 0 悪 黻酸(無水） 3 鼸三纳 7 mm 1 641 1001 7.0 99 100 _ 10 16 0 嫩 4.5 5.5 7.0 100 95 _ 6.2 0 31.3 — 0 — 0 1 7.0 10 7 6.2 0 31.3 糊敵無水》 3 磷酸三鈉 7 ϋιι 52.5 100 7.0 99 • 90 6.2 0 31.3 9mm 4.5 5.5 糊糈 52.5 100 7.0 100 - 95 如表5所示可確認，藉由在TG與AG或GO等之二 酵素中，以規定量摻合特定的酸性物質及/或鹼性物質， 即使是將酵素溶液保持24小時後，各酵素的活性仍可保 持。 [實施例4] 調製如表5所示之摻合的酵素製劑，且調製與實施例 1同樣20%溶液後，以25 °C、24小時保存。在生米「越光 」3 8 0g中加入自來水580g且浸漬1小時後，添加24小 時保存後的酵素製劑溶液3.8g (酵素製劑爲0.76g)，且 對原料米lg而言，使酵素製劑爲0.002g、TG爲0.2U、 AG爲208.0U、或TG爲0.1U、GO爲1.3U、而酸性物質 與鹼性物質的合計量爲0.001 g，以電鍋「IH呷-電鍋NJ- -26- 201201710 HS06-S j (三菱電機公司製）煮飯》將煮飯米以真空冷卻 機「食品用急速冷卻機CMJ-40」（三浦PROTECH公司 製）冷卻至25°C以下。將所得之煮飯米（白飯）移至密封 性高的容器中，以伸縮性保鮮膜覆蓋，於20°C恆溫槽保管 24小時後，微波回溫而以受過訓練之品評員進行官能評 價，並將其結果顯示於表6。官能評價係用以確認對在 W0 2005/096839中所確認對米之效果在本素材是否顯示出 相加•相乘的效果。此外，官能評價在對照區方面所設定 於煮飯前使TG、AG、GO、酸性物質、鹼性物質與各試料 等量添加，且與以同樣操作製成的白飯比較，使物性同等 且對味覺完全無影響者爲◎、物性同等且對味覺幾乎沒差 別者爲〇、呈現出異味者爲X。 [*6] 酵素製劑中各原料之摻合(％) ~%w 評價 TG AG GO 酸件物晳 驗性物質 賦形劑 合計 10 16 0 一 0 一 0 糊棺 42.7 100 對照區 10 16 0 檸檬酸(無羽 3 磷酸二鈉 7 糊稩 64 100 ◎ 10 16 0 棒樣醏 4.5 碳酸鈉 5.5 _糈 64 100 ◎ 1 _赛製劑中各原料之摻合(％) ' 1 rwi 評價 爾屜 TG AG GO 1 賦形劑 1 6.2 0 31.3 — 0 — 0 糊精. 42.7 hm 6.2 0 31.3 摊酸(無水） 3 磷寧三鈉 7 螭精 64 100 @ 6.2 0 31.3 挚黷 4.5 mmm 5.5 52.5 100 ◎ 如圖2、圖3所示，除了 GO，在TG、AG單體之酵 素表現安定。但是，TG與AG或GO之二酵素倂用時， TG、AG之酵素活性可確認其失活。另一方面，如表6所 示，藉由在TG與AG或GO之二酵素中以規定量摻合特 定的酸性物質及/¾鹼性物質，即使在酵素溶液保持24小 時後，仍可確認與在煮飯前添加二酵素之對照品具有同等 的口感、食味。特別是，以規定量使用作爲酸性物質之檸 -27- 201201710 檬酸、作爲鹼性物質之磷酸三鈉、碳酸鈉時，對煮飯米之 味覺完全沒有影響。 [產業上的可利用性] 藉由本發明，因可使食品之品質特別是米飯食品之品 質向上提昇，而在食品領域上極爲有用。 【圖式簡單說明】 [圖1]表示實驗例1之含轉麩醯胺酶、α-葡萄糖苷酶 、葡萄糖氧化酶的溶液中各酵素安定性之比較圖》 [圖2]表示實驗例1之含轉麩醯胺酶、α-葡萄糖苷酶 的溶液中各酵素安定性之比較圖。 [圖3]表示實驗例1之含轉麩醯胺酶、葡萄糖氧化酶 的溶液中各酵素的安定性之比較圖。 -28-As shown in Table 3, by mixing a specific acidic substance and/or a basic substance in a predetermined amount in TG, GO, and AG3 enzymes, it was confirmed that the activity of each enzyme can be maintained even after the enzyme solution is maintained for 24 hours. . [Example 2] The blended enzyme preparation shown in Table 3 was prepared, and the same 20% solution as in Example 1 was prepared and stored at 251 and 24 hours. 380 g of tap water was added to the raw rice "Koshihikari" 3 80 g, and after immersion for 1 hour, 3.8 g of the enzyme preparation solution after storage for 24 hours (the enzyme preparation was 〇.76 g) was added, and for the raw material lg, The enzyme preparation is 0.002g, the GO is 1.3U, the TG is 0.1U, the AG is 61.1U, and the total amount of the acidic substance and the alkaline substance is O.OOlg, and the electric kettle "IH呷-electric cooker NJ-HS06- S" (made by Mitsubishi Electric Corporation) to cook rice. The cooked rice was cooled to 25 t or less with a vacuum cooler "Food Cooling Cooler CMJ-40" (manufactured by Miura PROTECH Co., Ltd.). The rice boiled rice (white rice) is transferred to a container with high sealing property, covered with a stretchable plastic wrap, and stored in a thermostat at 20 ° C for 24 hours, then microwaved back to -24-201201710 and trained as a quality reviewer. The sensory evaluation was performed, and the results are shown in Table 4. The sensory evaluation is used to confirm whether the effect of the rice confirmed in W0200 5/096 839 shows the effect of addition/multiplication in the material. In addition, the functional evaluation was set in the control area before the cooking, and GO, TG, AG, acidic substance, and alkaline substance were added in the same amount as each sample, and the physical properties were equivalent and compared with the rice prepared in the same manner. Those whose taste is completely unaffected are ◎, the physical properties are the same, and those who have almost no difference in taste are 〇, and those who exhibit odor are X. [Table 4] 1 Miscellaneous (%) in the enzyme preparation I "Will GO TG AG i mmm alkaline substance I msm mm evaluation 31.3 6.2 4.7 - 0 - 0 EMS · Control 31.3 6.2 4.7 Lime-like acid water 7.5 Trisodium citrate 17.5 EMi· © 31.3 6.2 4.7 Potassium dihydrogen phosphate 15 Transfer of dipotassium hydrogen phosphate 35 mmm 7.8 100 ο 31.3 6.2 4.7 Potassium dihydrogen phosphate 10 Disodium hydrogen phosphate 40 EMM 7.8 100 ο 31.3 6.2 4.7 Diterpene phosphate 20 Solubilized acid trisodium 30 7.8 100 ο 31.3 6.2 4.7 Diammonium phosphate (anhydrous) 10 Potassium dipotassium phosphate 40 EH· 7.8 100 ο 31,3 6.2 4.7 Sodium dihydrogen phosphate 呒 water 7.5 Acidic acid disodium 42.5 IMM 7.8 100 C)~ 31.3 6.2 4.7 sodium hexaphosphate (anhydrous) 22.5 trisodium phosphate 27.5 EH· 7.8 100 0 31.3 6.2 4.7 DL malic acid 5 dipotassium hydrogen phosphate 45 EH· 7.8 100 ο 31.3 6.2 4.7 DL apple 瞍 5 full Acid bismuth disodium 45 IM· 7.8 100 (§) 31.3 6.2 4.7 DLmmm 12.5 Trisodium phosphate 37.5 Dextrin 7.8 100 <§» 31.3 6.2 4.7 Citric acid (anhydrous) 5 Hydrogen dipotassium 45 Dextrin 7.8 100 ο 31.3 6.2 4.7 citric acid (anhydrous) 5 disodium hydrogen phosphate 45 dextrin 7.8 100 ◎ 31.3 6.2 4.7 1 lemon S acid (none 12.5 occupational trisodium 37.5 sample 7.8 100 ◎ 31.3 6.2 4.7 citrate rubber (lion 22.5 w sodium 27,5 7.8 100 ◎ 〇©31.3 6.2 4.7 citric acid water) 5 acid! 15 _ fine 37.8 100 31.3 6.2 4.7 0-1 Acidic acid 10 Fine 47.8 100 As shown in Table 4: By adding specific acidic substances and/or alkaline substances in a prescribed amount in TG, GO, and AG3 enzymes, the enzyme solution is maintained even though After 24 hours, it was confirmed that the taste of the 3 enzymes added before cooking was the same as the taste and taste. In particular, when malic acid or citric acid as an acidic substance is used as a basic substance, disodium hydrogen phosphate, trisodium phosphate, sodium carbonate or histidine is used in a predetermined amount, the taste of rice cooked rice is not affected at all. -25-201201710 [Example 3] The blended enzyme preparation shown in Table 5 was prepared using the TG used in Experimental Example 1, and the AG or GO dienzyme, and the same 20% solution as in Experimental Example 1 was prepared. Further, "dextdex #l" manufactured by Matsutani Chemical Co., Ltd. was used as the dextrin. The enzyme preparation solution was stored at 25 ° C for 24 hours, and the residual viability of each enzyme was measured. When the activity enthalpy immediately after the preparation was 100, the residual activity of the enzyme activity after 24 hours was obtained, and the results are shown in Table 5 [«51 _ 1 1 TG IASJ IGO 1 形 形 合 丨 丨 pH mmm AG GO - Ϊ0 ~ίδ 0 - 0 - Paste 1 741 1001 7.0 60 85 10 16 0 Tannic acid (anhydrous) 3 鼸 three nanometers 7 mm 1 641 1001 7.0 99 100 _ 10 16 0 tender 4.5 5.5 7.0 100 95 _ 6.2 0 31.3 — 0 — 0 1 7.0 10 7 6.2 0 31.3 Paste anhydrous” 3 Trisodium phosphate 7 ϋιι 52.5 100 7.0 99 • 90 6.2 0 31.3 9mm 4.5 5.5 Paste 52.5 100 7.0 100 - 95 As shown in Table 5, By mixing a specific acidic substance and/or a basic substance in a predetermined amount in two enzymes such as TG and AG or GO, the activity of each enzyme can be maintained even after the enzyme solution is kept for 24 hours. [Example 4] The blended enzyme preparation shown in Table 5 was prepared, and the same 20% solution as in Example 1 was prepared, and then stored at 25 ° C for 24 hours. After adding 580 g of tap water to the raw rice "Koshihikari" 380 g and immersing for 1 hour, 3.8 g of the enzyme preparation solution after storage for 24 hours (0.76 g of the enzyme preparation) was added, and for the raw material lg, the enzyme preparation was made. It is 0.002g, TG is 0.2U, AG is 208.0U, or TG is 0.1U, GO is 1.3U, and the total amount of acidic substance and alkaline substance is 0.001g, and electric kettle "IH呷-electric cooker NJ- -26- 201201710 HS06-S j (Mitsubishi Electric Co., Ltd.) "cooking rice" is cooled to 25 ° C or less with a vacuum cooler "Food Cooling Machine CMJ-40" (manufactured by Miura PROTECH Co., Ltd.). The rice cooked rice (white rice) was transferred to a container having a high sealing property, covered with a stretchable plastic wrap, and stored in a thermostat at 20 ° C for 24 hours, and then microwaved to be warmed up and evaluated by a trained reviewer. The results are shown in Table 6. The sensory evaluation is used to confirm whether the effect of the rice confirmed in W0 2005/096839 shows the effect of addition/multiplication in the material. In addition, the functional evaluation was set in the control area before the cooking, and TG, AG, GO, acidic substance, alkaline substance, and each sample were added in the same amount, and the physical properties were equivalent and the same as the white rice prepared in the same manner. Those whose taste is completely unaffected are ◎, the physical properties are the same, and those who have almost no difference in taste are 〇, and those who exhibit odor are X. [*6] Blending of each raw material in the enzyme preparation (%) ~%w Evaluation TG AG GO Acidic substance test substance Excipient total 10 16 0 0 0 0 Paste 42.7 100 Control area 10 16 0 Lemon Acid (no feather 3 phosphate disodium 7 paste 64 100 ◎ 10 16 0 stick 醏 4.5 sodium carbonate 5.5 _ 糈 64 100 ◎ 1 _ mixing of raw materials in the preparation (%) ' 1 rwi Evaluation TG AG GO 1 Excipient 1 6.2 0 31.3 — 0 — 0 Dextrin. 42.7 hm 6.2 0 31.3 Acid (anhydrous) 3 Phosphate Trisodium 7 Qujing 64 100 @ 6.2 0 31.3 挚黩4.5 mmm 5.5 52.5 100 ◎ 2. As shown in Fig. 3, in addition to GO, the enzymes in TG and AG alone are stable. However, when TG is used with AG or GO, the enzyme activity of TG and AG can confirm its inactivation. As shown in Table 6, by blending specific acidic substances and /3⁄4 alkaline substances in a predetermined amount in TG and AG or GO two enzymes, even after the enzyme solution is kept for 24 hours, it can be confirmed and cooked. The reference substance added with two enzymes before meals has the same taste and taste. In particular, it is used as a acidic substance in a prescribed amount. -27-201201710 Acid, as a basic substance, trisodium phosphate, sodium carbonate, has no effect on the taste of rice. [Industrial Applicability] By the present invention, the quality of food, especially the quality of rice food, can be improved. It is very useful in the food field. [Simplified illustration] [Fig. 1] Comparison of the stability of each enzyme in the solution containing the transglutaminase, α-glucosidase, and glucose oxidase of Experimental Example 1. Fig. 2 is a graph showing the comparison of the stability of each enzyme in the solution containing the transglutaminase and the α-glucosidase of Experimental Example 1. [Fig. 3] shows the transglutaminase containing the test example 1. Comparison of the stability of each enzyme in the solution of glucose oxidase. -28-