JP4173334B2 - β-maltose hydrous crystal-containing powder, its production method and use - Google Patents
β-maltose hydrous crystal-containing powder, its production method and use Download PDFInfo
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Description
【0001】
【発明の属する技術分野】
本発明は、β−マルトース含水結晶含有粉末とその製造方法並びに用途に関し、更に詳細には、噴霧方式で粉末化され、水系媒体への溶解性に優れ、取扱い容易なβ−マルトース含水結晶含有粉末とその製造方法並びに当該粉末を水系媒体に溶解、含有せしめた飲食物、化粧品、医薬品など各種組成物への用途に関する。
【0002】
【従来の技術】
従来、甘味料として砂糖が大量に消費されてきた。しかしながら、砂糖は甘味が強すぎることから最近の嗜好に合わず、また、虫歯の主な誘発物質であるなどの欠点を有している。
【0003】
近年、砂糖の欠点を解消するために、各種糖質を利用することが提案され、とりわけ、澱粉から製造されるマルトースについては、砂糖と比較して甘味が低い、虫歯誘発の懸念が少ない、風味が良好である、などの特徴を有しており、現在では、食品級のβ−マルトース含水結晶含有粉末が、(株)林原商事から登録商標「サンマルト」及び「サンマルトS」として市販され、その消費量の更なる拡大が期待できる。
【0004】
β−マルトース含水結晶含有粉末は、通常、マルトース含有溶液を原料として、分蜜方式、切削方式又は噴霧方式により製造されている。
【0005】
これらのうち、分蜜方式は、原料のマルトース含有溶液を濃縮し、β−マルトース含水結晶が種晶として共存する状態下で、撹拌しつつ徐冷してβ−マルトース含水結晶を晶出させたマスキットとし、これを遠心分離などにより、結晶と蜜とに分離し、結晶部分を採取、乾燥する粉末の製造方法である。この方式は、きわめて高純度の結晶粉末が得られるものの、蜜を副生する分、β−マルトース含水結晶粉末の収率が低い欠点がある。
【0006】
これに対して、切削方式や噴霧方式は、通常、原料のマルトース含有溶液を濃縮し、これをマスキットにした後、切削方式においては全量を固化、熟成させて切削、乾燥して粉末を採取するか、噴霧方式においてはマスキットを噴霧乾燥させたものを熟成し採取する、粉末の製造方法である。これらの方式は、マルトースの純度を高めることはできないものの全量を粉末化でき、蜜を副生することもなく、工業的に有利である。
【0007】
詳細には、切削方式については、通常、マルトース含有溶液を濃縮し、種晶としてβ−マルトース含水結晶を加えてβ−マルトース含水結晶を部分的に晶出させマスキットとしたのち、全量をブロック状に固化、熟成させて、これを切削、乾燥、篩別して、安定なβ−マルトース含水結晶含有粉末を製造するものであるが、この切削方式によって工業的に生産された製品は、(株)林原商事より商標登録「サンマルト」として販売されている。この切削方式によれば、原料マルトースの全量を粉末化することができ、工業的に有利であるものの、この切削方式には、マスキットをブロック状に固化、熟成させるのに5乃至15日間もの長い期間を要するのみならず、その後の切削、乾燥、篩別に繁雑な工程を必要とする欠点がある。
【0008】
一方、噴霧方式については、従来、マルトース含有溶液を濃縮し、種晶としてβ−マルトース含水結晶を加えてβ−マルトース含水結晶を部分的に晶出させマスキットとしたのち、これを噴霧乾燥して粉末化し、熟成させて、β−マルトース含水結晶含有粉末を製造する方法が知られていた(特公昭54−3937、特公昭54−27325)。この噴霧方式は、マスキットを固化、熟成させる長い期間を必要とせず工業的には最も有利であるものの、それでも、その製造に3乃至4日間もの期間を要し、噴霧方式でスムーズに連続的に粉末を製造することが困難であった。
【0009】
その後、これを改善するために、マルトース以外の糖質、具体的には、グルコース、マルトトリオース及びグルコース重合度4以上のオリゴ糖などの含量をできる限り低減させて、無水物換算で、マルトース含量約95w/w%(以下、本明細書では、特段の断りがない限り、w/w%を単に%と略称する。)以上とした極めて高純度のマルトース含有溶液を用いることにより、噴霧方式でβ−マルトース含水結晶含有粉末を比較的短時間で製造する方法が確立され、(株)林原商事より登録商標「サンマルトS」として販売されるに至った。しかしながら、本発明者等が初めて見いだした知見によれば、この噴霧方式によって得られるβ−マルトース含水結晶含有粉末は、意外にも、水系媒体への溶解性が必ずしも満足できるものでなく、この溶解性を更に向上させる必要性のあることが判明した。
【0010】
【発明が解決しようとする課題】
本発明は、本発明者等が新たに見いだした上記噴霧方式の欠点を解決するためになされたもので、工業的に有利で、且つ安価に実施できる噴霧方式を採用し、水系媒体への溶解性に優れ、取扱い容易なβ−マルトース含水結晶含有粉末とその製造方法並びに用途を提供することを課題とするものである。
【0011】
【課題を解決するための手段】
本発明者等は、上記の課題を解決するために、噴霧方式で粉末化されるβ−マルトース含水結晶含有粉末の各種物性について研究し、とりわけ、原料のマルトース含有溶液の糖組成と得られる粉末の各種物性との関係に着目して、鋭意研究を重ねた。即ち、各種糖組成のマルトース含有溶液から調製したマスキットを、噴霧方式で粉末とし、まず、比較的低湿度で高温の雰囲気に保ち、次いで、比較的高湿度で低温の雰囲気に保って得られるβ−マルトース含水結晶含有粉末を採取し、この粉末の吸湿性、固着性、溶解性、α−アノマー含量、結晶化度などの諸性質について詳細に調べた。
【0012】
その結果、▲1▼、噴霧方式で粉末化され、無水物換算で、マルトース86%以上93%未満およびグルコース2%以上含有し、結晶化度が62%以上72%未満であるβ−マルトース含水結晶含有粉末が、水系媒体への溶解性に優れ、且つ、取扱い容易な粉末であることを見いだし、当該粉末の製造方法として、▲2▼、無水物換算で、マルトース86%以上93%未満およびグルコース2%以上を含有している溶液を、β−マルトース含水結晶を晶出させたマスキットとし、次いで噴霧方式で粉末とし、更に、比較的低湿度で高温の雰囲気に保って、マルトース中のα−アノマー高含有粉末とし、その後、比較的高湿度で低温の雰囲気に保って、噴霧された粉末のマルトース中のα−アノマー含量を7%以上14%未満に低減せしめ、得られる結晶化度が62%以上72%未満の粉末を採取することを特徴とするβ−マルトース含水結晶含有粉末の製造方法を確立し、併せて、▲3▼、前記の▲1▼、又は▲2▼の製造方法で得られるβ−マルトース含水結晶含有粉末を水系媒体に溶解、含有せしめた組成物を確立して本発明を完成した。
【0013】
【発明の実施の形態】
本発明のβ−マルトース含水結晶含有粉末の原料に用いるマルトース含有溶液としては、噴霧方式で粉末化され、無水物換算で、マルトース86%以上93%未満およびグルコース2%以上を含有し、結晶化度が62%以上72%未満であるβ−マルトース含水結晶含有粉末ができるものであればよく、そのようなマルトース含有溶液の製造方法としては、例えば、特公昭54−3937号公報、特公昭56−28153号公報、特公昭57−3356号公報、特許第2518646号公報などに開示されるように、各種の澱粉を加熱、糊化したのちにα−アミラーゼ(EC.3.2.1.1)を作用させるか、酸または機械力により、できるだけ低い加水分解率に液化し、次いで、β−アミラーゼ(EC.3.2.1.2)と澱粉枝切り酵素(プルラナーゼEC.3.2.1.41またはイソアミラーゼEC.3.2.1.68のいずれか)を作用させて糖化して製造する方法がある。
【0014】
本発明でいう、無水物換算で、マルトース86%以上93%未満及びグルコース2%以上を含有する溶液は、前述のように澱粉から製造され、通常、他の糖質としてマルトトリオース及びグルコース重合度4以上のオリゴ糖などを含有している。このマルトトリオース及びグルコース重合度4以上のオリゴ糖は、マルトース含有溶液からβ−マルトース含水結晶の晶出を阻害し易いのでできるだけこの含量を低減させることが望ましく、とりわけ、マルトトリオースについては、その含量を、無水物換算で、2%未満にするのが好適である。
【0015】
マルトトリオース及びグルコース重合度4以上のオリゴ糖の含量を低減させる方法としては、例えば、特公昭56−28154号公報、特許第2696530号公報などに開示されているように、マルトトリオースまたはグルコース重合度4以上のオリゴ糖に比較的よく作用し、それらを分解してグルコースやマルトースなどを生成する酵素を作用させることで、マルトトリオースまたはグルコース重合度4以上のオリゴ糖の含量を減少させるとともにマルトースの含量を増加させることができる。また、UF膜や逆浸透膜、活性炭などを用いてマルトトリオースまたはグルコース重合度4以上のオリゴ糖を分離、除去することも、更に、特公昭62−51120号公報、特公平5−79316号公報などに開示されているように、イオン交換樹脂を用いるクロマト分離法を用いてマルトトリオースまたはそれ以上のオリゴ糖を分離、除去することもできる。
【0016】
本発明の特徴の一つは、次に述べる各工程を組み合わせる一連の製造方法を採用し、マルトースの晶出速度を高めることにより、無水物換算で、マルトース含量が86%以上93%未満、換言すれば、グルコース、マルトトリオース及びグルコース重合度4以上のオリゴ糖などのマルトース以外の糖質を7%以上14%未満と比較的多量共存含有しているにもかかわらず、噴霧方式で、溶解性に優れ、且つ、取扱いの容易なβ−マルトース含水結晶含有粉末が容易に、比較的短時間に製造できることである。
【0017】
即ち、一連の製造方法は、(a)、本発明に用いる糖組成のマルトース含有溶液をマスキットとし、次いで、(b)、噴霧方式、望ましくは、高圧ノズルや回転円盤を用いた噴霧乾燥法により粉末とし、望ましくは、水分10%未満、更に望ましくは、約5乃至9%の粉末とし、更に、これに含まれるマルトースの晶出速度を高めるために、(c)、これを比較的低湿度で高温の雰囲気、望ましくは、相対湿度(RH)40%未満、更に望ましくは20%未満で、望ましくは、75℃を越え、更に望ましくは80乃至110℃の雰囲気に1乃至4時間程度保って、マルトース異性体であるα−アノマーの高含有粉末、望ましくは、マルトース中のα−アノマー含量が35%以上の粉末とし、その後、(d)、比較的高湿度で低温の雰囲気、望ましくは、相対湿度(RH)70%を越え、更に望ましくは80%以上で、望ましくは、50℃未満、更に望ましくは20乃至45℃の雰囲気に5乃至10時間程度保って、そのマルトース中のα−アノマー含量を7%以上14%未満に低減せしめ、(e)、得られる結晶化度が62%以上72%未満のβ−マルトース含水結晶含有粉末を採取することにより達成される。
【0018】
以下、前記各工程について、更に詳細に説明する。前記工程(a)においては、マルトース含有溶液を濃縮し、望ましくは、水分15乃至30%の濃縮液とし、これに種晶としてβ−マルトース含水結晶の適量、通常は0.1乃至5%程度を共存させて徐冷、攪拌しつつマスキットを製造する。この際、β−マルトース含水結晶の晶出率(以下、本明細書では、特段の断りがない限り、晶出率とは、マスキットを結晶と蜜とに分別し、(結晶無水物重量/マスキットの無水物重量)×100の値をいう。)が高くなればなる程、マスキットの粘度が上昇する。
【0019】
また、前記工程(b)においては、本発明者等は、β−マルトース含水結晶を含む高粘度のマスキットを実質的に晶出率を低下させない範囲内で加熱、昇温させてその粘度を低下させることにより、噴霧方式でβ−マルトース含水結晶含有粉末が容易に製造できるという知見を得た。すなわち、本発明者等は、マスキットを加熱、昇温すると、粘度は温度の上昇とともに直ちに低下するものの、生成した結晶は多少温度が上昇しても短時間では溶解することはなく、晶出率の低下は殆ど見られないことを見出し、実質的に晶出率を低下させることなく、マスキットを昇温することでマスキットの粘度を、望ましくは、50,000cp(以下、本明細書では、特段の断りがない限り、粘度cpとはBH型回転粘度計を使用し、No.7のローターを用い、4rpmで回転させて測定したときの値をいう。)以下にすれば、噴霧処理の操作が容易となり、しかも、その乾燥効率を良くできることが明らかとなった。
【0020】
昇温の方法は特に限定されない。例えば、マスキットが入った助晶機のジャケットに温水を流す、助晶機内に直接蒸気を加える、助晶機から送液ポンプの間で熱交換機を使用して加温するなど公知の方式が適宜採用できる。昇温の程度は、マスキットの粘度が噴霧できる程度、具体的には、50,000cp以下、望ましくは、40,000cp以下となればよく、通常、2乃至15℃、望ましくは、2乃至10℃の範囲で晶出率の低下を起こさない程度になるべく短時間に行うのが好適である。
【0021】
前記工程(c)においては、粉末をα−マルトース無水結晶の少量と接触させてマルトース中のα−アノマーへの異性化を促進する方法を採用することも有利に実施できる。マルトース異性体としては、α−アノマーとβ−アノマーが存在する。結晶の形態としては、α−マルトース無水結晶、β−マルトース含水結晶、β−マルトース無水結晶並びにα−マルトースとβ−マルトースが一定の割合で共存するα、βコンプレックス結晶が知られている。
【0022】
マルトース中のα−アノマーを7%以上14%未満含有するとは、マルトース中のα−アノマーの含量を意味し、その形態が非晶質であるか結晶質であるかは問わない。一般的に、マルトース中のα−アノマーの含量が14%以上の場合は、非晶質のマルトースが多いか、又は、α−マルトース無水結晶を含有していることを意味し、逆に、マルトース中のα−アノマーの含量が7%未満の場合は、残りはβ−マルトースであるのでβ−マルトース含水又は無水結晶の含量が高いことを意味している。
【0023】
更に、前記工程(d)においては、5乃至10時間程度保ってマルトース中のα−アノマー含量を7%以上14%未満に低減せしめた後、必要ならば、更に乾燥工程を加えることも有利に実施できる。
【0024】
前記工程(e)においては、得られるβ−マルトース含水結晶含有粉末が、粒度分布試験(澱粉糖関連工業分析法、1991年発行、(株)食品化学新聞社発売に118頁記載の粒度分布の測定方法に準じて、JIS・Z8801のふるいを用い、試料50gを15分間篩って測定した)において、比較的粒度の大きな粉末を多量含有しており、通常、106μmを越す粉末を60%以上含んでおり、多くの場合、150μmを越え300μm以下の粉末を40%以上含んでいる。また、この150μmを越え300μm以下の粉末は、しばしば噴霧乾燥機内を落下する途中、または熟成から乾燥終了に至る工程で、複数個の粒子が付着、凝集して生成した凝集物を含んでいる。
【0025】
この様にして得られる本発明のβ−マルトース含水結晶含有粉末は、水系媒体への溶解性に優れ、しかも、保存安定性、流動性良好で、取扱い容易な粉末である。
【0026】
本発明でいう水系媒体とは、β−マルトース含水結晶含有粉末を溶解、含有させることのできる水または水分を多く含む液状、ペースト状、半固状物又は固状物を意味する。とりわけ、粘性を有する水系媒体としては、例えば、糖類、澱粉、脂肪、蛋白質、ポリフェノール及び乳化剤などを含むものであって、具体的には、例えば、求肥、餅菓子などに用いられる糊化澱粉、小麦粉から調製された生地、ドウ、麺などや、生あん、魚肉、畜肉などの擂潰食肉、液卵、乳クリーム、発酵乳、ピーナッツペースト、果実パルプ、野菜パルプ、糖類シロップ、抽出液濃縮物などがある。
【0027】
本発明のβ−マルトース含水結晶含有粉末は、前述の粘性を持つ水系媒体への溶解性に優れ、これに利用されることはもとより、粘度の低い水系媒体への用途にも有利に利用できる。また、良質で上品な甘味を有すると共に、虫歯の原因の一つであるデキストランの生成を阻害する作用を有しており、虫歯を起こしにくい甘味料としても好適に利用される。
【0028】
また、本発明のβ−マルトース含水結晶含有粉末は、プルラン、ヒドロキシエチルスターチ、ポリビニルピロリドンなどの公知の結合剤と併用して、錠剤の糖衣剤としても有利に用いることができる。更に、本発明のβ−マルトース含水結晶含有粉末は、浸透圧調節性、賦形性、照り付与性、保湿性、粘性、糖質晶出防止性、糊化澱粉の老化防止性などの有用な性質をも兼備している。
【0029】
従って、本発明のβ−マルトース含水結晶含有粉末は、甘味料、呈味改良剤、風味改良剤、品質改良剤、安定剤、賦形剤などとして、食品、飼料、餌料、化粧品、医薬品、嗜好品などの各種組成物に有利に用いることができる。
【0030】
本発明のβ−マルトース含水結晶含有粉末の具体的な用途としては、各種物品の甘味付けのための調味料としても用いることができる。必要に応じて、例えば、粉飴、ブドウ糖、フラクトース、ラクトスクロース、蔗糖、トレハロース、異性化糖、蜂蜜、メープルシュガー、イソマルトオリゴ糖、ガラクトオリゴ糖、フラクトオリゴ糖、ソルビトール、マルチトール、ラクチトール、ジヒドロカルコン、ステビオシド、α−グリコシルステビオシド、レバウディオシド、グリチルリチン、L−アスパルチル−L−フェニルアラニンメチルエステル、スクラロース、アセスルファムK、サッカリン、グリシン、アラニンなどのような他の甘味料の1種又は2種以上と併用することも、必要ならば、デキストリン、澱粉、砂糖、乳糖などの増量剤の1種又は2種以上と併用することも随意である。
【0031】
又、本発明のβ−マルトース含水結晶含有粉末は、そのままで、又は必要に応じて、適宜の増量剤、賦形剤、結合剤、甘味料などの1種又は2種以上と併用して、顆粒、球状、短棒状、板状、立方体状、錠剤状、フィルム状又はシート状などの各種形状に成型して用いることも随意である。
【0032】
更に、本発明のβ−マルトース含水結晶含有粉末の甘味は、酸味、塩から味、渋味、旨味、苦味などの他の呈味を有する各種物質とよく調和し、各種飲食物の甘味付け、呈味改良に、又品質改良を目的として用いることができる。具体的には、例えば、アミノ酸、ペプチド類、醤油、粉末醤油、味噌、粉末味噌、もろみ、ひしお、ふりかけ、マヨネーズ、ドレッシング、食酢、三杯酢、粉末すし酢、中華の素、天つゆ、麺つゆ、ソース、ケチャップ、焼肉のタレ、カレールウ、シチューの素、スープの素、ダシの素、核酸系調味料、複合調味料、みりん、新みりん、テーブルシュガー、コーヒーシュガーなど各種調味料として有利に利用できる。又、例えば、せんべい、あられ、おこし、餅類、まんじゅう、ういろう、あん類、羊羮、水羊羮、錦玉、ゼリー、カステラ、飴玉などの各種和菓子、パン、ビスケット、クラッカー、クッキー、パイ、プリン、バタークリーム、カスタードクリーム、シュークリーム、ワッフル、スポンジケーキ、ドーナツ、チョコレート、チューインガム、キャラメル、キャンディーなどの洋菓子、アイスクリーム、シャーベットなどの氷菓、果実のシロップ漬、氷蜜などのシロップ類、フラワーペースト、ピーナッツペースト、フルーツペースト、スプレッドなどのペースト類、ジャム、マーマレード、シロップ漬、糖果などの果実、野菜の加工食品類、福神漬、べったら漬、千枚漬、らっきょう漬などの漬物類、たくあん漬の素、白菜漬の素などの漬物の素類、ハム、ソーセージなどの畜肉製品類、魚肉ハム、魚肉ソーセージ、かまぼこ、ちくわ、天ぷらなどの魚肉製品、ウニ、イカの塩辛、酢こんぶ、さきするめ、ふぐみりん干しなどの各種珍味類、のり、山菜、するめ、小魚、貝などで製造されるつくだ煮類、煮豆、ポテトサラダ、こんぶ巻などの惣菜食品、ヨーグルト、チーズなどの乳製品、魚肉、畜肉、果実、野菜のビン詰、缶詰類、清酒、合成酒、リキュール、洋酒などの酒類、コーヒー、紅茶、ココア、ジュース、炭酸飲料、乳酸飲料、乳酸菌飲料などの清涼飲料水、プリンミックス、ホットケーキミックス、即席しるこ、即席スープなどの即席食品、更には、離乳食、治療食、ドリンク剤、ペプチド食品、冷凍食品、健康食品などの各種飲食物に有利に利用できる。
【0033】
更に、家畜、家禽、その他蜜蜂、蚕、魚などの飼育動物用の飼料、餌料などの嗜好性を向上させる目的で使用することもできる。その他、タバコ、練歯磨、口紅、リップクリーム、内服液、錠剤、トローチ、肝油ドロップ、口中清涼剤、口中香剤、うがい剤などの各種固形物用甘味剤として、又はそれらの呈味改良剤、矯味剤、品質改良剤、安定剤などとして有利に利用できる。
【0034】
本発明のβ−マルトース含水結晶含有粉末は、品質改良剤及び/又は安定剤として、有効成分、活性成分又は生理活性物質を含む健康食品、医薬品などに配合することにより、安定で高品質の液状、ペースト状又は固状の健康食品や医薬品を得ることができる。前記有効成分や生理活性物質としては、例えば、インターフェロン−α、インターフェロン−β、インターフェロン−γ、TNF−α、TNF−β、マクロファージ遊走阻止因子、コロニー刺激因子、トランスファーファクター、インターロイキンなどのリンホカイン、インシュリン、成長ホルモン、プロラクチン、エリトロポエチン、卵細胞刺激ホルモンなどのホルモン、BCGワクチン、日本脳炎ワクチン、はしかワクチン、ポリオ生ワクチン、痘苗、破傷風トキソイド、ハブ抗毒素、ヒト免疫グロブリンなどの生物製剤、ペニシリン、エリスロマイシン、クロラムフェニコール、テトラサイクリン、ストレプトマイシン、硫酸カナマイシンなどの抗生物質、チアミン、リボフラビン、L−アスコルビン酸、α−グリコシルアスコルビン酸、肝油、カロチノイド、エルゴステロール、トコフェロール、ルチン、α−グリコシルルチン、ナリンジン、α−グリコシルナリンジン、ヘスペリジン、α−グリコシルヘスペリジンなどのビタミン類、リパーゼ、エラスターゼ、ウロキナーゼ、プロテアーゼ、β−アミラーゼ、イソアミラーゼ、グルカナーゼ、ラクターゼなどの酵素、薬用人参エキス、笹エキス、梅エキス、松エキス、スッポンエキス、クロレラエキス、アロエエキス、プロポリスエキスなどのエキス類、ウイルス、乳酸菌、酵母などの生菌、ローヤルゼリーなどを例示することができる。
【0035】
以上述べた各種組成物に、本発明のβ−マルトース含水結晶含有粉末を含有させる方法は、これらの組成物が完成するまでの工程で含有させればよく、例えば、混和、溶解、融解、浸漬、浸透、散布、塗布、被覆、噴霧、注入、晶出、固化など公知の方法が適宜選ばれる。その量は、通常、前記組成物重量当たり、1%以上、好ましくは、2%以上、より好ましくは、5乃至99%配合するのが好適である。
【0036】
以下、本発明を具体的な実験を用いて詳しく説明する。
【0037】
【実験】
〈各種β−マルトース結晶含有粉末の物性に及ぼす原料糖組成の影響〉
噴霧方式による、各種β−マルトース結晶含有粉末の物性に及ぼす原料糖組成の影響を調べた。試験用粉末は、糖組成の異なる各種の原料マルトース含有溶液を調製し、これを噴霧方式でβ−マルトース含水結晶含有粉末としたものを用いた。マルトース含有溶液は、市販の精製マルトース((株)林原商事販売 登録商標「サンマルトS」)、又は、この精製マルトースにグルコース(和光純薬(株)販売 試薬特級)、マルトトリオース、マルトテトラオース及び/又はマルトペンタオース(いずれも(株)林原生物化学研究所製造 試薬)を加えて各種組成のマルトース含有溶液を調製した。
【0038】
噴霧方式によるβ−マルトース含水結晶含有粉末の調製は次の通り行った。即ち、原料のマルトース含有溶液を水分25%に濃縮したのち助晶機に移し、種晶としてβ−マルトース含水結晶を1%加え、ゆっくり攪拌しながら、温度を徐々に30℃まで低下させ、12乃至18時間かけてβ−マルトース含水結晶を部分的に晶出させ、マスキットを得た。マスキットの晶出率は36乃至43%であった。助晶を終了した後、マスキットの粘度が50,000cpを超えるものについては、高圧ポンプで送液する前に加温し、晶出率を実質的に低減させることなく約45,000cpに粘度を下げるとともに、加圧ノズルを用いて噴霧した。噴霧時の乾燥用熱風の温度は75℃、熱風の送風方式は噴霧乾燥機内で垂直下降流、送風空気量は噴霧乾燥機内から取出した時の乾燥粉末の水分が約8.5%となるように調節した。
【0039】
得られた粉末は、直ちに、種晶としてα−マルトース無水結晶0.2%と混合接触せしめ、温度90℃、相対湿度(RH)20%の恒温恒湿機内で2時間保存し、次いで、30℃、相対湿度(RH)80%の恒温恒湿機内で5時間保持し、熟成を行ってβ−マルトース含水結晶含有粉末を得た。この粉末を、次に述べる各種物性試験に供した。
【0040】
物性試験には、対照として、精製マルトース((株)林原商事販売 登録商標「サンマルトS」)、試薬β−マルトース含水結晶((株)林原生物化学研究所製造 商品名「マルトースHHH」)及びα−マルトース無水結晶((株)林原商事販売 登録商標「ファイントース」)を用いた。
【0041】
物性試験は次のような方法で行った。
A.糖組成分析は、KS−801カラム(昭和電工製)またはCH04SSカラム(MCI製)を用いた液体クロマトグラフィーを行い、クロマトグラムの面積比より糖組成を求めた。
【0042】
B.吸湿性試験は、アルミカップに入れた試料の蓋をしないで、RH75.2%(飽和塩化ナトリウム水溶液で平衡化)に調整したデシケーター内に入れ、25℃で3日間放置したのち、重量変化を測定し、元のサンプルに対する重量増加の割合(%)を求め、吸湿性とした。
【0043】
C.固着性は、吸湿性試験で3日間放置後取り出したアルミカップ内の試料の状態を肉眼観察し、試料が試験前と比べて吸湿したことにより固まっておれば、固着性有りとした。
【0044】
D.溶解性試験は、(i)水に対する溶解性試験としては、25℃の脱イオン水5mlをプラスチック製試験管に入れ、これに各種糖組成のマルトース結晶含有粉末1gを一度に加え、粉末が完全に水中に沈んだ状態で密栓し、これを50℃の恒温槽中で保持し、粉末の溶解状態を20分毎に肉眼観察した。評価は、粉末が完全溶解し、透明になるまでに要する時間(分)を求めた。評価の基準は、粉末が溶けて見えなくなるまでの時間が短いものほど溶解性に優れると判断した。
【0045】
(ii)デキストリン含有溶液に対する溶解性試験としては、粘性を有する濃度17%のデキストリン((株)松谷化学工業製造 商品名「パインデックス#1」)水溶液5mlをプラスチック製試験管に入れ、これに各種糖組成のマルトース結晶含有粉末1gを前記(i)の水に対する溶解性試験の場合と同様に加え、粉末が完全に水中に沈んだ状態で密栓し、これを50℃の恒温槽中で保持し、粉末の状態を肉眼観察した。評価の基準は前記(i)の水に対する溶解性試験の場合と同様とした。
【0046】
E.マルトース異性体の分析は、試料を無水ピリジンに溶解後、TMS化処理を行って、2%OV−17 クロモソルブW(AW−DMCS)を用いたガスクロマトグラフィーを行い、クロマトグラムの面積比よりα、β−アノマー比を求めた。
【0047】
F.粉末の結晶化度の測定は、X線回折装置ガイガーフレックスRDA−IIB(Cu、Kα線使用)(理学電気(株)製)を用いて、粉末X線回折図形に基づくルーランド(Ruland)の方法(アクタ クリスタログラフィカ:Acta Crystallographica、第14巻、第1180頁、1961年)により求めた。測定した粉末のうち、代表的な粉末X線回折図形を図1乃至図5に示した。
【0048】
原料のマルトース含有溶液の糖組成及び得られた各粉末の吸湿性、固着性、溶解性、α−アノマー含量、結晶化度についての試験結果は、各種マルトース結晶含有粉末の物性として表1にまとめた。
【0049】
【表1】
【0050】
表1から明らかなように、試験No.3乃至6の噴霧方式で得られた、無水物換算で、マルトース86%以上93%未満及びグルコース2%以上を含有し、他の糖質として、マルトトリオース及びグルコース重合度4以上のオリゴ糖を含有し、マルトース異性体としてマルトース中のα−アノマーを7%以上14%未満含有する結晶化度が62%以上72%未満のβ−マルトース含水結晶含有粉末は、吸湿性が低く、固着性が見られず保存安定性良好、取扱い容易で、しかも、水及び粘性を有するデキストリン含有溶液などの水系媒体への溶解性に優れていることが判明した。これに対して、試験No.1及び2のマルトース含量が82.4%及び84.2%と低く、マルトース異性体としてマルトース中のα−アノマー含量が14%を越える結晶化度が62%未満の噴霧方式で得られたβ−マルトース含水結晶含有粉末は、水系媒体への溶解性に優れているものの吸湿性が高く、固着性を示し、保存安定性に劣る不安定な粉末であった。
【0051】
一方、試験No.1のマルトース含量が94.1%と高く、マルトース異性体としてマルトース中のα−アノマー含量が7%以下と少なく、結晶化度が72%を越える噴霧方式で得られたβ−マルトース含水結晶含有粉末は、吸湿性が少なく、固着性がないものの、水系媒体への溶解性に劣る粉末であった。
【0052】
なお、対照として用いた試験No.8の「サンマルトS」は、噴霧方式で得られた粉末である。しかしながら、マルトース純度が95.0%、結晶化度74.5%といずれも高く、吸湿性がほとんどなく、固着性も全くないものの、水系媒体への溶解性に劣るものであった。また、試験No.9の「マルトースHHH」は、マスキットを分蜜して得られた結晶粉末である。本粉末はきわめて高純度のマルトースであって、マルトース純度が99.6%、結晶化度も82.6%と高く、吸湿性がほとんどなく、固着性も全く示さないものの、水系媒体への溶解性に劣るものであった。更に、試験No.10の「ファイントース」は、他の試料と異なって、α−マルトース無水結晶粉末である。本粉末はマルトース中のα−アノマー含量が高く、粉末が示す性質はβ−マルトース含水結晶を主とする他の粉末とは大きく異なっており、結晶化度の違いにかかわらず、吸湿性が高く、固着性も激しく、保存安定性に劣る不安定な粉末であり、その上、水系媒体への溶解性に劣るものであった。
【0053】
以上の結果から、噴霧方式によるβ−マルトース結晶含有粉末の製造においては、無水物換算で、マルトース86%以上93%未満及びグルコース2%以上を含有している溶液を原料とし、本発明の一連の製造方法に従って製造すると、水系媒体への溶解性に優れ、取扱いの容易なβ−マルトース結晶含有粉末を得ることができることが判明した。
【0054】
従って、本発明を採用することにより得られる、無水物換算で、マルトース86%以上93%未満及びグルコース2%以上を含有し、結晶化度が62%以上72%未満であるβ−マルトース結晶含有粉末は、水系媒体への溶解性に優れ、取扱い容易で、しかも高収率に製造できるのに加え、これまでと比較して、水系媒体に溶解して使用するときの作業時間を大幅に短縮することができ、産業上もきわめて価値の高いものといえる。
【0055】
以下に、具体的な実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらの実施例によって限定されるものではない。
【0056】
【実施例A−1−a】
<マルトース含有溶液の調製>
馬鈴薯澱粉1重量部と水4重量部との懸濁液に市販の細菌液化型α−アミラーゼ(スピターゼHS 長瀬産業(株)製)を加え90℃に昇温し、加熱糊化したのち、直ちに130℃に加熱して酵素反応を止め、DE1.8の液化液を得た。この澱粉液化液を55℃まで急冷し、澱粉枝切り酵素(シュードモナス菌を培養して調製したイソアミラーゼ)を澱粉1g当たり100単位および大豆由来のβ−アミラーゼ(商品名#1500 長瀬産業(株)製)を澱粉1g当たり50単位、更に、マルトゲナーゼ(ノボ ノルディスク(株)製)を糖質1g当たり10単位加えpH5.0に保って40時間糖化した。これを、常法に従って、活性炭処理による脱色、イオン交換樹脂処理による脱塩を行って精製し、減圧濃縮してマルトース含有溶液を得た。マルトース含有溶液の糖組成は、グルコース3.8%、マルトース92.5%、マルトトリオース1.1%、マルトテトラオース以上2.6%であった。
【0057】
【実施例A−1−b】
<β−マルトース含水結晶含有粉末の調製>
実施例A−1−aで得られたマルトース含有溶液を水分29%に濃縮したのち助晶缶に移し、種晶としてβ−マルトース含水結晶を1%加え、ゆっくり攪拌しながら、マスキットの温度を徐々に29℃まで低下させ、12時間かけてβ−マルトース含水結晶を部分的に晶出させた。マスキットの晶出率は37%となった。助晶終了後のマスキットを高圧ポンプで送液し、回転円盤を用いて噴霧乾燥機内に噴霧した。このときの乾燥用熱風の温度は70℃、熱風の送風は噴霧乾燥機内で垂直下降並流、送風空気量は噴霧乾燥機内から取出し時の乾燥粉末の水分が7.5%となるように調節した。
【0058】
この粉末を直ちにα−マルトース無水結晶0.2%と混合接触させ、温度85℃、相対湿度(RH)20%で3時間保持し、次いで、30℃、相対湿度(RH)80%で5時間保持し熟成を行って、結晶化度が71.4%、水分6.1%のβ−マルトース含水結晶含有粉末を、原料の馬鈴薯澱粉に対し、無水物換算で、収率96%で得た。本粉末は、無水物換算で、マルトース92.5%とともに、グルコース3.8%、マルトトリオース1.1%及びグルコース重合度4以上のオリゴ糖2.6%を含有し、しかも、マルトース異性体としてマルトース中のα−アノマーを7.8%含有しているもので、水系媒体への溶解性に優れていた。しかも、25℃、相対湿度(RH)75.2%の条件下で保存してもほとんど吸湿性を示さず、保存安定性に優れ、流動性良好で、取扱い容易な粉末であった。また、本粉末の粒度分布を測定した結果、粒子中に微粒子が凝集した粉末を含み、150μm以上300μm以下の粒子が41%含まれていた。
【0059】
また、本粉末は、甘味料、呈味改良剤、品質改良剤、安定剤、変色防止剤、増量剤、賦形剤、結合剤などとして、とりわけ、水系媒体への溶解性に優れているので、例えば、水のみならず、ペースト状、半固状物などに溶解、含有せしめて、飲食物、嗜好物、飼料、餌料、化粧品、医薬品などの各種組成物に有利に利用できる。更に、そのままで、または必要に応じて、増量剤、賦形剤、結合剤などと混合して、顆粒、球状、短棒状、板状、立方体、錠剤など各種形状に成形して使用することも随意である。
【0060】
【実施例A−2−a】
<マルトース含有溶液の調製>
コーンスターチ1重量部と水3重量部との懸濁液に市販の細菌液化型α−アミラーゼ(スピターゼHS 長瀬産業(株)製)を加え90℃に昇温し、加熱糊化したのち直ちに130℃に加熱して酵素反応を止め、DE2.5の液化液を得た。この澱粉液化液を55℃まで急冷し、澱粉枝切り酵素(シュードモナス菌を培養して調製したイソアミラーゼ)を澱粉1g当たり50単位および大豆由来のβ−アミラーゼ(商品名#1500 長瀬産業(株)製)を同じく20単位加えpH5.0に保って40時間糖化し、マルトース含量が固形物当たり84.6%の高純度マルトース含有糖化液を得た。マルトース含有糖化液の糖組成は、グルコース3.5%、マルトース84.6%、マルトトリオース8.2%、マルトテトラオース以上3.7%であった。
【0061】
この糖化液に、更に、タカアミラーゼAを糖質1g当たり50単位加えpH5.5に保って、更に20時間、酵素反応を進めた。これを常法に従って、活性炭処理による脱色、イオン交換樹脂処理による脱塩を行い精製し、減圧濃縮してマルトース含有溶液を得た。マルトース含有溶液の糖組成は、グルコース5.6%、マルトース91.2%、マルトトリオース1.3%、マルトテトラオース以上1.9%であった。
【0062】
【実施例A−2−b】
<β−マルトース含水結晶含有粉末の調製>
実施例A−2−aで得られたマルトース含有溶液を水分26%に濃縮したのち助晶機に移し、種晶としてβ−マルトース含水結晶を1%加え、ゆっくり攪拌しながら、マスキットの温度を徐々に30℃まで低下させ、14時間かけてβ−マルトース含水結晶を部分的に晶出させた。マスキットの晶出率は41%であった。助晶終了後のマスキットを高圧ポンプで送液し、回転円盤を用いて噴霧乾燥機内に噴霧した。乾燥用の熱風の温度は75℃、熱風の送風は噴霧乾燥機内で垂直下降並流、送風空気量は噴霧乾燥機内から取出し時の乾燥粉末の水分が8.5%となるように調節した。
【0063】
この粉末を直ちにα−マルトース無水結晶0.2%と混合接触させ、温度90℃、相対湿度(RH)25%で2時間保持し、次いで、30℃、相対湿度(RH)80%で5時間保持し熟成を行って、結晶化度70.4%、水分6.1%のβ−マルトース含水結晶含有粉末を、原料のコーンスターチに対し、無水物換算で、収率95%で得た。本粉末は、無水物換算で、マルトース91.2%とともに、グルコース5.6%、マルトトリオース1.3%及びグルコース重合度4以上のオリゴ糖1.9%を含有し、しかも、マルトース異性体としてマルトース中のα−アノマーを9.2%含有しているもので、水系媒体への溶解性に優れていた。しかも、25℃、相対湿度(RH)75.2%の条件下で保存してもほとんど吸湿性を示さず、保存安定性に優れ、流動性良好で、取扱い容易な粉末であった。また、本粉末の粒度分布を測定した結果、粒子中に微粒子が凝集した粉末を含み、150μm以上300μm以下の粒子が47%含まれていた。
【0064】
また、本粉末は、甘味料、呈味改良剤、品質改良剤、安定剤、変色防止剤、増量剤、賦形剤、結合剤などとして、とりわけ、水系媒体への溶解性に優れているので、例えば、水のみならず、ペースト状、半固状物などに溶解、含有せしめて、飲食物、嗜好物、飼料、餌料、化粧品、医薬品などの各種組成物に有利に利用できる。更に、そのままで、または必要に応じて、増量剤、賦形剤、結合剤などと混合して、顆粒、球状、短棒状、板状、立方体、錠剤など各種形状に成形して使用することも随意である。
【0065】
【実施例A−3−a】
<マルトース含有溶液の調製>
コーンスターチ3重量部と水7重量部との懸濁液に市販の細菌液化型α−アミラーゼ(スピターゼHS 長瀬産業(株)製)を加え90℃に昇温し、加熱糊化したのち直ちに130℃に加熱して酵素反応を止め、DE4.3の液化液を得た。この澱粉液化液を55℃まで急冷して澱粉枝切り酵素(シュードモナス菌を培養して調製したイソアミラーゼ)を澱粉1g当たり50単位、大豆由来のβ−アミラーゼ(商品名#1500 長瀬産業(株)製)を同じく20単位を加えpH5.0に保って40時間糖化し、マルトース含量が固形物当たり84.6%の糖化液を得た。これを、常法に従って、活性炭処理による脱色、イオン交換樹脂処理による脱塩を行って精製し、減圧濃縮して糖濃度45%のマルトース含有溶液を得て、分画原料とした。
【0066】
分画に用いた分画用樹脂は、アルカリ金属型強酸性カチオン交換樹脂(東京有機化学工業(株)製 商品名アンバーライトXT−1007Na+型、架橋度6%)を使用し、内径5.4cmのジャケット付ステンレス製カラムに水懸濁液で充填し、糖質溶液が直列に流れるようにカラム2本を連結して樹脂層全長を10mとした。
【0067】
カラム内温度を55℃に維持しつつ、原料の糖質溶液を樹脂に対して5v/v%加え、これに55℃の温水をSV0.3で流して分画し、マルトトリオース高含有画分を分離、除去して、マルトースを高含有しているとともに他にオリゴ用などを含有しているマルトース高含有画分を採取した。次いで、常法に従って、活性炭処理による脱色、イオン交換樹脂処理による脱塩を行って精製し、減圧濃縮してマルトース含有溶液を得た。このマルトース含有溶液の糖組成は、グルコース6.0%、マルトース90.1%、マルトトリオース0.8%、マルトテトラオース以上3.1%であった。
【0068】
【実施例A−3−b】
<β−マルトース含水結晶含有粉末の調製>
実施例A−3−aで得られたマルトース含有溶液を水分24%に濃縮したのち助晶機に移し、種晶としてβ−マルトース含水結晶を1%加え、ゆっくり攪拌しながら、マスキットの温度を徐々に29℃まで低下させ、15時間かけてβ−マルトース含水結晶を部分的に晶出させた。晶出率は40%であった。助晶終了後のマスキットは粘度が高いため、高圧ポンプで送液時に加温し、晶出率を低減させることなく、約40,000cpに粘度を下げるとともに、加圧ノズルを用いて噴霧乾燥機内に噴霧した。このときの乾燥用熱風の温度は75℃とし、熱風の送風は噴霧乾燥機内で垂直下降並流とし、送風空気量は噴霧乾燥機内から取出し時の乾燥粉末の水分が9.0%となるように調節した。
【0069】
この粉末を直ちにα−マルトース無水結晶0.2%と混合接触させ、温度85℃、相対湿度(RH)20%で2時間保持し、次いで、35℃、相対湿度(RH)75%で5時間保持し熟成を行って、結晶化度が69.0%、水分6.4%のβ−マルトース含水結晶含有粉末を、原料コーンスターチに対して、無水物換算で、収率89%で得た。本粉末は、無水物換算で、マルトース90.1%とともに、グルコース6.0%、マルトトリオース0.8%及びグルコース重合度4以上のオリゴ糖3.1%を含有し、しかも、マルトース異性体としてマルトース中のα−アノマーを9.9%含有しているもので、水系媒体への溶解性に優れていた。しかも、25℃、相対湿度(RH)75.2%の条件下で保存してもほとんど吸湿性を示さず、保存安定性にも優れ、流動性良好で、取扱い容易な粉末である。また、本粉末の粒度分布を測定した結果、粒子中に微粒子が凝集した粉末を含み、150μm以上300μm以下の粒子が51%含まれていた。
【0070】
また、本粉末は、甘味料、呈味改良剤、品質改良剤、安定剤、変色防止剤、増量剤、賦形剤、結合剤などとして、とりわけ、水系媒体への溶解性に優れているので、例えば、水のみならず、ペースト状、半固状物などに溶解、含有せしめて、飲食物、嗜好物、飼料、餌料、化粧品、医薬品などの各種組成物に有利に利用できる。更に、そのままで、または必要に応じて、増量剤、賦形剤、結合剤などと混合して、顆粒、球状、短棒状、板状、立方体、錠剤など各種形状に成形して使用することも随意である。
【0071】
【実施例A−4−a】
<マルトース含有溶液の調製>
コーンスターチ1重量部と水2重量部との懸濁液に市販の細菌液化型α−アミラーゼ(スピターゼHS 長瀬産業(株)製)を加え90℃に昇温し、加熱糊化したのち直ちに130℃に加熱して酵素反応を止め、DE4.3の液化液を得た。この澱粉液化液を55℃まで急冷して澱粉枝切り酵素(シュードモナス菌を培養して調製したイソアミラーゼ)を澱粉1g当たり50単位、大豆由来のβ−アミラーゼ(商品名#1500 長瀬産業(株)製)を同じく10単位加え、pH5.0に保って40時間糖化し、マルトース含量が固形物当たり74.1%の糖化液を得た。これを、常法に従って、活性炭処理による脱色、イオン交換樹脂処理による脱塩を行って精製し、減圧濃縮して糖濃度45%のマルトース含有溶液を得て、分画原料とした。
【0072】
分画に用いた分画用樹脂は、アルカリ金属型強酸性カチオン交換樹脂(東京有機化学工業(株)製 商品名アンバーライトXT−1007Na+型、架橋度6%)を使用し、内径5.4cmのジャケット付ステンレス製カラムに水懸濁液で充填し、糖質溶液が直列に流れるようにカラム2本を連結して樹脂層全長を10mとした。
【0073】
カラム内温度を55℃に維持しつつ、原料の糖質溶液を樹脂に対して5v/v%加え、これに55℃の温水をSV0.3で流して分画し、マルトトリオース高含有画分を分離、除去して、マルトースを高含有しているとともに他にオリゴ用などを含有しているマルトース高含有画分を採取した。次いで、常法に従って、活性炭処理による脱色、イオン交換樹脂処理による脱塩を行って精製し、減圧濃縮してマルトース含有溶液を得た。マルトース含有溶液の糖組成は、グルコース9.8%、マルトース87.4%、マルトトリオース1.0%、マルトテトラオース以上1.8%であった。
【0074】
【実施例A−4−b】
<β−マルトース含水結晶含有粉末の調製>
実施例A−4−aで得られたマルトース含有溶液を水分20%に濃縮したのち助晶機に移し、種晶としてβ−マルトース含水結晶を1%加え、ゆっくり攪拌しながら、マスキットの温度を徐々に32℃まで低下させ、16時間かけてβ−マルトース含水結晶を部分的に晶出させた。晶出率は39%となった。助晶終了後のマスキットは粘度が高いために、高圧ポンプで送液時に加温し、晶出率を低減させることなく、約45,000cp以下に粘度を下げるとともに、回転円盤を用いて噴霧乾燥機内に噴霧した。このときの乾燥用熱風の温度は90℃とし、熱風の送風は噴霧乾燥機内で垂直下降並流とし、送風空気量は噴霧乾燥機内から取出し時の乾燥粉末の水分が9.5%となるように調節した。
【0075】
この粉末を直ちにα−マルトース無水結晶0.2%と混合接触させ、温度90℃、相対湿度(RH)20%で3時間保持し、次いで、30℃、相対湿度(RH)80%で5時間保持し熟成を行って、結晶化度が64.6%、水分6.8%のβ−マルトース含水結晶含有粉末を、原料のコーンスターチに対し、無水物換算で、収率80%で得た。本粉末は、無水物換算で、マルトース87.4%とともに、グルコース9.8%、マルトトリオース1.0%及びグルコース重合度4以上のオリゴ糖1.8%を含有し、しかも、マルトース異性体としてマルトース中のα−アノマーを12.7%含有しているもので、水系媒体への溶解性に優れていた。しかも、25℃、相対湿度(RH)75.2%の条件下で保存してもほとんど吸湿性を示さず、保存安定性に優れ、流動性良好で、取扱い容易な粉末であった。また、本粉末の粒度分布を測定した結果、粒子中に微粒子が凝集した粉末を含み、150μm以上300μm以下の粒子が53%含まれていた。
【0076】
また、本粉末は、甘味料、呈味改良剤、品質改良剤、安定剤、変色防止剤、増量剤、賦形剤、結合剤などとして、とりわけ、水系媒体への溶解性に優れているので、例えば、水のみならず、ペースト状、半固状物などに溶解、含有せしめて、飲食物、嗜好物、飼料、餌料、化粧品、医薬品などの各種組成物に有利に利用できる。更に、そのままで、または必要に応じて、増量剤、賦形剤、結合剤などと混合して、顆粒、球状、短棒状、板状、立方体、錠剤など各種形状に成形して使用することも随意である。
【0077】
【実施例B−1】
<甘味料>
実施例A−1−bの方法で得たβ−マルトース含水結晶含有粉末0.5重量部、ソルビトール無水結晶0.5重量部、α−グリコシルステビオシド(東洋精糖(株)販売登録商標「αGスイート」)0.01重量部及びL−アスパルチル−L−フェニルアラニンメチルエステル(味の素(株)社販売 登録商標「アスパルテーム」)0.01重量部を均一に混合し、顆粒成型機にかけて、顆粒状甘味料を得た。本品は、甘味の質が優れ、蔗糖の約2倍の甘味度を有し、実質的に低カロリーである。本甘味料は、それに配合した高甘味度甘味物の分解もなく、安定性に優れており、低カロリー甘味料として、カロリー摂取を制限している肥満者、糖尿病者などのための低カロリー飲食物などに対する甘味付けに好適である。また、本甘味料は、虫歯誘発菌による酸の生成が少なく、不溶性グルカンの生成も少ないことより、虫歯を抑制する飲食物などに対する甘味付けにも好適である。
【0078】
【実施例B−2】
<ハードキャンディー>
蔗糖50重量部と実施例A−2−bの方法で得たβ−マルトース含水結晶含有粉末50重量部を水100重量部に溶解、加熱混合し、次いで減圧下で水分2%未満になるまで加熱濃縮し、これにクエン酸0.6重量部及び適量のレモン香料と着色料とを混和し、常法に従って成形し、製品を得た。本品は歯切れ、色調、呈味、風味とも良好で、蔗糖の晶出も起こさず、吸湿性少なく、ダレも起こさない安定で高品質のハードキャンディーである。
【0079】
【実施例B−3】
<チューインガム>
ガムベース3重量部を柔らかくなる程度に加熱溶融し、これに無水結晶マルチトール((株)林原商事販売 登録商標「マビット」)2重量部、キシリトール2重量部、実施例A−3−bの方法で得たβ−マルトース含水結晶含有粉末2重量部、及び含水結晶トレハロース((株)林原商事販売 登録商標「トレハ」)1重量部を加え、更に適量の香料と着色料とを混合し、常法に従って、ロールにより練り合わせ、成形、包装して製品を得た。本品は、テクスチャー、呈味、風味良好で、低う蝕性、低カロリーのチューインガムとして好適である。
【0080】
【実施例B−4】
<加糖練乳>
原乳100重量部に実施例A−4−bの方法で得たβ−マルトース含水結晶含有粉末2重量部及び蔗糖2重量部を溶解し、プレートヒーターで加熱殺菌し、次いで濃度70%に濃縮し、無菌状態で缶詰して製品を得た。本品は、温和な甘味で風味も良く、フルーツ、コーヒー、ココア、紅茶などの調味用に有利に利用できる。
【0081】
【実施例B−5】
<乳酸菌飲料>
脱脂粉乳175重量部、実施例A−2−bの方法で得たβ−マルトース含水結晶含有粉末60重量部及びラクトスクロース高含有粉末(株式会社林原商事販売、登録商標『乳果オリゴ』)50重量部を水1,150重量部に溶解し、65℃で30分間殺菌し、40℃に冷却後、これに、常法に従って、乳酸菌のスターターを30重量部植菌し、37℃で8時間培養して乳酸菌飲料を得た。本品は、風味良好で、オリゴ糖を含有し、乳酸菌を安定に保つだけでなく、ビフィズス菌増殖促進作用、整腸作用を有する乳酸菌飲料として好適である。
【0082】
【実施例B−6】
<粉末ジュース>
噴霧乾燥により製造したオレンジ果汁粉末33重量部に対して、実施例A−4−bの方法で得たβ−マルトース含水結晶含有粉末50重量部、無水結晶マルチトール((株)林原商事販売 登録商標「マビット」)10重量部、無水クエン酸0.65重量部、リンゴ酸0.1重量部、アスコルビン酸2−グルコシド結晶粉末((株)林原商事販売)0.2重量部、クエン酸ソーダ0.1重量部、プルラン((株)林原商事販売 PF−20)0.5重量部及び粉末香料の適量をよく混合攪拌し、粉砕し微粉末にして、これを流動層造粒機に仕込み、排風温度40℃とし、これに実施例A−4−bの方法で得たβ−マルトース含水結晶含有粉末を水に溶解した70%溶液をバインダーとして適量スプレーし、30分間造粒し、計量、包装して製品を得た。本品は、果汁含有率約30%の粉末ジュースである。又、本品は、異味、異臭がなく、高品質のジュースとして商品価値の高いものである。
【0083】
【実施例B−7】
<コーヒー飲料>
焙煎したコーヒー豆100重量部を粉砕し、これに熱水1,000重量部を用いて抽出し、抽出液860重量部を得た。本液450重量部に実施例A−1−bの方法で得たβ−マルトース含水結晶含有粉末90重量部及び適量の重曹を含む水400重量部を加え、均一に混合して中性pHのコーヒー飲料を調製し、次いで、これを常法に従って、缶に充填し、120℃、30分間加熱殺菌して缶入りコーヒー飲料を製造した。本品は、香り、味ともに良好な高品質のコーヒー飲料である。また、本品を自動販売機に入れ、60℃で1ヶ月間保持した後も、その良好な風味をよく維持していた。また、本品は、夏場向けに冷却して保存しても、香り、味ともに良好な高品質のコーヒー飲料である。
【0084】
【実施例B−8】
<カスタードクリーム>
コーンスターチ100重量部、実施例A−2−bの方法で得たβ−マルトース含水結晶含有粉末50重量部、含水結晶トレハロース((株)林原商事販売 登録商標「トレハ」)60重量部、砂糖40重量部、及び食塩1重量部を充分に混合し、鶏卵280重量部を加えて攪拌し、これに沸騰した牛乳1,000重量部を徐々に加え、更に火にかけて攪拌を続け、コーンスターチが完全に糊化して全体が半透明になった時に火を止め、これを冷却して適量のバニラ香料を加え、計量、充填、包装して製品を得た。本品は、なめらかな光沢を有し、風味良好で、澱粉の老化も抑制され、高品質のカスタードクリームである。
【0085】
【実施例B−9】
<ういろうの素>
米粉90重量部に、コーンスターチ20重量部、無水結晶マルチトール((株)林原商事販売 登録商標「マビット」)70重量部、実施例A−1−bの方法で得たβ−マルトース含水結晶含有粉末50重量部、及びプルラン((株)林原商事販売 PF−20)4重量部を均一に混合してういろうの素を製造した。ういろうの素と適量の抹茶と水とを混練し、これを容器に入れて60分間蒸し上げて抹茶ういろうを製造した。本品は、照り、口当たりも良好で、風味も良い。又、澱粉の老化も抑制され、日持ちも良く、低カロリーのういろうとしても好適である。
【0086】
【実施例B−10】
<求肥>
餅粉4重量部を水6重量部で溶いて、木枠に濡れ布巾を敷いたものに流し込み、これを100℃で20分間蒸した後、これに実施例A−1−bの方法で得たβ−マルトース含水結晶含有粉末2重量部及び砂糖2重量部を加えて十分にこねた後に成形し、求肥を得た。本品は、風味良好であり、しかも糊化した餅米澱粉の老化が抑制され、その賞味期間を大幅に延長することができる。
【0087】
【実施例B−11】
<あん>
原料あずき10重量部に、常法に従って、水を加えて煮沸し、渋切り、あく抜きし、水溶性夾雑物を除去して、あずきつぶあん約21重量部を得た。この生あんに砂糖14重量部、実施例A−3−bの方法で得たβ−マルトース含水結晶含有粉末3重量部及び水7重量部を加えて煮沸し、これに少量のサラダオイルを加えてつぶあんを壊さないように練り上げ、製品のあんを約35重量部得た。本品は、色焼け、離水もなく安定で、舌触り、風味良好で、あんパン、まんじゅう、団子、最中、氷菓などの製菓材料として好適である。
【0088】
【実施例B−12】
<パン>
小麦粉100重量部、イースト2重量部、砂糖5重量部、実施例A−1−bの方法で得たβ−マルトース含水結晶含有粉末5重量部および無機フード0.1重量部を、常法に従って、水でこね、中種を26℃で2時間発酵させ、その後30分間熟成、焼き上げた。本品は、色相、すだちとも良好で、適度な弾力、温和な甘味を有する高品質のパンである。
【0089】
【実施例B−13】
<アイシング>
実施例A−2−bの方法で得たβ−マルトース含水結晶含有粉末10重量部に乳化剤(シュガーエステル)1.2重量部を加熱混合し、次いで、含水結晶トレハロース((株)林原商事販売 登録商標「トレハ」)107重量部を混合し、更に45℃に保ちながら、油脂7.5重量部を混合してアイシングを製造した。本品は、トレハロース微結晶を含有し、成形性良好でべたつきもなく、経日変化の少ないアイシングである。
【0090】
【実施例B−14】
<ボンボン>
実施例A−3−bの方法で得たβ−マルトース含水結晶含有粉末3重量部、含水結晶トレハロース((株)林原商事販売 登録商標「トレハ」)300重量部及び水115重量部を混合し、加熱してBx70まで煮詰め、品温を80℃まで冷却し、ブランディー40重量部を混合した後、常法に従って成形してボンボンを得た。本品は、トレハロースの微結晶を含有し、ブランディー風味豊かで、経日変化の少ない高品質のボンボンである。
【0091】
【実施例B−15】
<ハム>
豚もも肉1,000重量部に食塩15重量部および硝酸カリウム3重量部を均一にすり込んで、冷室に1昼夜堆積する。これを水500重量部、食塩100重量部、硝酸カリウム3重量部、実施例A−4−bの方法で得たβ−マルトース含水結晶含有粉末40重量部および香辛料からなる塩漬液に冷室で7日間漬け込み、次いで、常法に従い、冷水で洗浄し、ひもで巻き締め、薫煙し、クッキングし、冷却、包装して製品を得た。本品は、色合いもよく、風味良好な高品質のハムである。
【0092】
【実施例B−16】
<佃煮>
砂取り、酸処理して角切りした昆布250重量部に醤油212重量部、アミノ酸液318重量部及び実施例A−3−bの方法で得たβ−マルトース含水結晶含有粉末35重量部及び砂糖20重量部を加えて煮込みつつ、更にグルタミン酸ソーダ12重量部、カラメル8重量部を加えて炊きあげ、昆布の佃煮を得た。本品は低う蝕性の佃煮である。また、味、香りだけでなく、色、艶ともに食欲をそそるものである。
【0093】
【実施例B−17】
<浴用剤>
ユズの皮ジュース1重量部に対して、実施例A−1−bの方法で得たβ−マルトース含水結晶含有粉末10重量部の割合で混合し、ユズの皮エキス含有粉末を得た。本粉末5重量部に、焼塩90重量部、含水結晶トレハロース((株)林原商事販売 登録商標「トレハ」)2重量部、無水ケイ酸1重量部及びα−グルコシル ヘスペリジン((株)林原商事販売、商品名αGヘスペリジン)0.5重量部、アスコルビン酸2−グルコシド結晶粉末((株)林原商事販売)2重量部を混合して浴用剤を製造した。本品は、ユズの香りも豊かで、入浴用の湯に100乃至10,000倍に希釈して利用すればよく、入浴後は、肌がしっとりしなめらかで、湯冷めしない高品質の浴用剤である。
【0094】
【実施例B−18】
<化粧用クリーム>
モノステアリン酸ポリオキシエチレングリコール2重量部、自己乳化型モノステアリン酸グリセリン5重量部、実施例A−1−bの方法で得たβ−マルトース含水結晶含有粉末5重量部、α−グルコシル ルチン(株式会社林原販売、登録商標「αGルチン」)1重量部、アスコルビン酸2−グルコシド結晶粉末((株)林原商事販売)1重量部流動パラフィン1重量部、トリオクタン酸グリセリン10重量部および防腐剤の適量を常法に従って加熱溶解し、これにL−乳酸2重量部、1,3−ブチレングリコール5重量部および精製水66重量部を加え、ホモゲナイザーにかけ乳化し、更に香料の適量を加えて撹拌混合し、化粧用クリームを製造した。本品は、抗酸化性を有し、安定性が高く、高品質の日焼け止め、美肌剤、色白剤などとして有利に利用できる。
【0095】
【実施例B−19】
<練歯磨>
第二リン酸カルシウム45重量部、ラウリル硫酸ナトリウム1.5重量部、グリセリン25重量部、ポリオキシエチレンソルビタンラウレート0.5重量部、実施例A−2−bの方法で得たβ−マルトース含水結晶含有粉末10重量部、サッカリン0.02重量部および防腐剤0.05重量部を水13重量部と混合して練歯磨を得た。本品は、界面活性剤の洗浄力を落とすことなく、嫌味を改良し、使用後感も良好である。
【0096】
【実施例B−20】
<流動食用固体製剤>
実施例A−3−bの方法で得たβ−マルトース含水結晶含有粉末100重量部、トレハロース含水結晶200重量部、マルトテトラオース高含有粉末200重量部、粉末卵黄270重量部、脱脂粉乳209重量部、塩化ナトリウム4.4重量部、塩化カリウム1.8重量部、硫酸マグネシウム4重量部、チアミン0.01重量部、アスコルビン酸ナトリウム0.1重量部、ビタミンEアセテート0.6重量部及びニコチン酸アミド0.04重量部からなる配合物を調製し、この配合物25グラムずつ防湿性ラミネート小袋に充填し、ヒートシールして製品を得た。本品は、β−マルトース含水結晶含有粉末及びトレハロース含水結晶により適度の甘味が付加され、整腸作用に優れた流動食である。1袋分を約150乃至300mlの水に溶解して流動食とし、経口的、又は鼻腔、胃、腸などへ経管的使用方法により利用され、生体へのエネルギー補給用に有利に利用できる。
【0097】
【実施例B−21】
<錠剤>
アスピリン50重量部に実施例A−4−bの方法で得たβ−マルトース含水結晶含有粉末14重量部、コーンスターチ4重量部を充分に混合した後、常法に従って打錠機により打錠して厚さ5.25mm、1錠680mgの錠剤を製造した。本品は、β−マルトース含水結晶含有粉末の賦形性を利用したもので、吸湿性がなく、物理的強度も充分にあり、しかも水中での崩壊はきわめて良好である。
【0098】
【実施例B−22】
<糖衣錠>
重量150mgの素錠を芯剤とし、これに実施例A−4−bの方法で得たβ−マルトース含水結晶含有粉末40重量部、プルラン((株)林原商事販売 PF−20)2重量部、水30重量部、タルク25重量部および酸化チタン3重量部からなる下掛け液を用いて錠剤重量が約230mgになるまで糖衣し、次いで、同じβ−マルトース含水結晶含有粉末65重量部、プルラン((株)林原商事販売 PF−20)1重量部および水34重量部からなる上掛け液を用いて、糖衣し、更に、ロウ液で艶出しして光沢のある外観の優れた糖衣錠を得た。本品は、耐衝撃性にも優れており、高品質を長期間維持する。
【0099】
【発明の効果】
以上の説明から明らかなように、本発明の噴霧方式で粉末化され、無水物換算で、マルトース86%以上93%未満及びグルコース2%以上を含有し、結晶化度が62%以上72%未満であるβ−マルトース含水結晶含有粉末は、マルトース異性体としてマルトース中のα−アノマーを7%以上14%未満含有し、水系媒体への溶解性に優れ、且つ、保存安定性に優れ、流動性良好で、取扱い容易な粉末である。また、これらのβ−マルトース含水結晶含有粉末は、グルコース、マルトトリオース及びグルコース重合度4以上のオリゴ糖などのマルトース以外の糖質を7%以上14%未満と比較的多量共存含有しているにもかかわらず、噴霧方式での製造が容易であり、連続的で、短時間に製造することもでき、粉末収率も高いことから、コストダウンを計ることも容易である。
【0100】
従って、本発明の確立は、水系媒体への溶解性に優れたβ−マルトース含水結晶含有粉末を容易に、低コストで製造できることから、澱粉糖製造業だけでなく、利用する側の人にとっても作業性の向上などが期待できるために好都合であり、該当する業界を初めとする産業界に与える工業的意義は極めて大きい。
【図面の簡単な説明】
【図1】 マルトース含量が、無水物換算で86.2%で結晶化度が62.1%を示すβ−マルトース含水結晶含有粉末の粉末X線回折図形。
【図2】 マルトース含量が、無水物換算で91.3%で結晶化度が70.8%を示すβ−マルトース含水結晶含有粉末の粉末X線回折図形。
【図3】 マルトース含量が、無水物換算で95.0%で結晶化度が74.5%を示す精製マルトース 登録商標「サンマルトS」の粉末X線回折図形。
【図4】 マルトース含量が、無水物換算で99.6%で結晶化度が82.6%を示す試薬β−マルトース含水結晶 商品名「マルトースHHH」の粉末X線回折図形。
【図5】 マルトース含量が、無水物換算で98.5%で結晶化度が76.3%を示すα−マルトース無水結晶 登録商標「ファイントース」の粉末X線回折図形。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a β-maltose hydrous crystal-containing powder and a method for producing the same, and more specifically, and more specifically, β-maltose hydrous crystal-containing powder that is powdered by a spray method, has excellent solubility in an aqueous medium, and is easy to handle. Further, the present invention relates to a method for producing the same and a use thereof for various compositions such as foods, drinks, cosmetics and pharmaceuticals in which the powder is dissolved and contained in an aqueous medium.
[0002]
[Prior art]
Conventionally, a large amount of sugar has been consumed as a sweetener. However, since sugar is too sweet, it does not meet recent tastes, and has the disadvantage that it is the main inducer of caries.
[0003]
In recent years, it has been proposed to use various sugars in order to eliminate the disadvantages of sugar. Especially, maltose produced from starch has lower sweetness compared to sugar, less concern about induction of tooth decay, and flavor. Currently, food-grade β-maltose hydrous crystal-containing powders are commercially available from Hayashibara Corporation as registered trademarks “San Mart” and “San Mart S”. Further expansion of consumption can be expected.
[0004]
The β-maltose hydrous crystal-containing powder is usually produced by a honey method, a cutting method, or a spray method using a maltose-containing solution as a raw material.
[0005]
Among these, the honey-concentration method concentrated the raw material maltose-containing solution and gradually cooled it with stirring under the condition that β-maltose hydrous crystals coexisted as seed crystals to crystallize β-maltose hydrous crystals. This is a method for producing a powder in which a mass kit is obtained, which is separated into crystals and nectar by centrifugation or the like, and the crystal portion is collected and dried. This method has a disadvantage that the yield of β-maltose hydrous crystal powder is low due to the fact that nectar is by-produced, although extremely high purity crystal powder can be obtained.
[0006]
On the other hand, in the cutting method and the spraying method, normally, the raw material maltose-containing solution is concentrated and made into a mass kit. Then, in the cutting method, the whole amount is solidified and aged, then cut and dried to collect the powder. Alternatively, the spray method is a powder production method in which a mass kit spray-dried is aged and collected. Although these methods cannot increase the purity of maltose, they can be pulverized in total, and do not produce nectar as a byproduct, which is industrially advantageous.
[0007]
Specifically, for the cutting method, normally, a maltose-containing solution is concentrated, β-maltose hydrated crystals are added as seed crystals, and β-maltose hydrated crystals are partially crystallized to form a mass kit, and then the entire amount is blocked. This product is solidified and aged, and is then cut, dried and sieved to produce a stable β-maltose hydrous crystal-containing powder. The product produced industrially by this cutting method is Hayashibara Corporation. It is sold as a registered trademark "San Mart" by Shoji. According to this cutting method, the entire amount of raw material maltose can be pulverized, which is industrially advantageous. However, this cutting method requires 5 to 15 days to solidify and age the mass kit in blocks. Not only does it require a period of time, it also has the disadvantage of requiring complicated processes for subsequent cutting, drying and sieving.
[0008]
On the other hand, for the spraying method, conventionally, a maltose-containing solution is concentrated, β-maltose hydrated crystals are added as seed crystals to partially crystallize β-maltose hydrated crystals to form a mass kit, which is then spray-dried. A method for producing β-maltose hydrous crystal-containing powder by pulverization and ripening has been known (Japanese Examined Patent Publication Nos. 54-3937 and 54-27325). This spray method is industrially most advantageous because it does not require a long period for solidifying and aging the mass kit, but it still takes 3 to 4 days for its production, and it is smoothly and continuously produced by the spray method. It was difficult to produce a powder.
[0009]
Thereafter, in order to improve this, the content of carbohydrates other than maltose, specifically, glucose, maltotriose and oligosaccharides having a glucose polymerization degree of 4 or more are reduced as much as possible to reduce maltose in terms of anhydride. By using an extremely high-purity maltose-containing solution having a content of about 95 w / w% or more (hereinafter, unless otherwise specified, w / w% is simply abbreviated as%). Has established a method for producing β-maltose hydrous crystal-containing powder in a relatively short time, and has been sold by Hayashibara Shoji Co., Ltd. as a registered trademark “Sanmaruto S”. However, according to the knowledge found by the present inventors for the first time, the β-maltose hydrous crystal-containing powder obtained by this spraying method is surprisingly not necessarily satisfactory in solubility in an aqueous medium. It has been found that there is a need to further improve the performance.
[0010]
[Problems to be solved by the invention]
The present invention has been made in order to solve the disadvantages of the above-mentioned spraying method newly found by the present inventors, and employs a spraying method that is industrially advantageous and can be carried out at low cost, and is dissolved in an aqueous medium. It is an object of the present invention to provide a β-maltose hydrous crystal-containing powder that is excellent in properties and easy to handle, a method for producing the same, and a use thereof.
[0011]
[Means for Solving the Problems]
In order to solve the above problems, the present inventors have studied various physical properties of β-maltose hydrous crystal-containing powders that are pulverized by a spray method, and in particular, the sugar composition of the raw material maltose-containing solution and the resulting powder Focusing on the relationship with various physical properties, we conducted extensive research. That is, a mass kit prepared from a maltose-containing solution of various sugar compositions is powdered by a spray method, first kept in a relatively high humidity and low temperature atmosphere, and then kept in a relatively high humidity and low temperature atmosphere. -Maltose hydrous crystal-containing powder was collected, and various properties such as hygroscopicity, adhesiveness, solubility, α-anomer content, crystallinity, etc. of this powder were examined in detail.
[0012]
As a result, (1), β-maltose hydrate containing powdered by a spray method, containing 86% to less than 93% maltose and 2% or more glucose in terms of anhydride, and having a crystallinity of 62% to less than 72%. It was found that the crystal-containing powder was excellent in solubility in an aqueous medium and easy to handle. As a method for producing the powder, (2), maltose 86% or more and less than 93% in terms of anhydride and A solution containing 2% or more of glucose is used as a mass kit in which β-maltose hydrous crystals are crystallized, then powdered by a spray method, and further maintained in a relatively low humidity and high temperature atmosphere to maintain α in maltose. A powder containing a high amount of anomer, and then kept in a relatively high humidity and low temperature atmosphere to reduce the α-anomer content in the maltose of the sprayed powder to 7% or more and less than 14%; A method for producing a β-maltose hydrous crystal-containing powder characterized by collecting a powder having a crystallinity of 62% or more and less than 72%, and in addition, (3), the above (1), or The present invention was completed by establishing a composition in which β-maltose hydrous crystal-containing powder obtained by the production method 2 was dissolved in an aqueous medium.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The maltose-containing solution used as a raw material for the β-maltose hydrous crystal-containing powder of the present invention is pulverized by a spray method and contains 86% to less than 93% maltose and 2% or more glucose in terms of anhydride. Any β-maltose hydrous crystal-containing powder having a degree of 62% or more and less than 72% can be used. Examples of methods for producing such a maltose-containing solution include Japanese Patent Publication No. 54-3937 and Japanese Patent Publication No. 56. As disclosed in Japanese Patent No. 28153, Japanese Patent Publication No. 57-3356, Japanese Patent No. 2518646, and the like, various starches are heated and gelatinized and then α-amylase (EC 3.2.1.1.1). ) Or by acid or mechanical force to liquefy to the lowest possible hydrolysis rate, and then β-amylase (EC 3.2.1.2) and starch debranching enzyme By the action of one) of the pullulanase EC.3.2.1.41 or isoamylase EC.3.2.1.68 there is a method for producing and saccharified.
[0014]
The solution containing maltose 86% or more and less than 93% and glucose 2% or more, as referred to in the present invention, is produced from starch as described above, and usually maltotriose and glucose polymerization as other carbohydrates. Contains oligosaccharides with a degree of 4 or more. Since this maltotriose and oligosaccharide having a glucose polymerization degree of 4 or more are liable to inhibit crystallization of β-maltose hydrous crystals from a maltose-containing solution, it is desirable to reduce this content as much as possible. Especially, for maltotriose, The content is preferably less than 2% in terms of anhydride.
[0015]
As a method for reducing the content of maltotriose and oligosaccharide having a glucose polymerization degree of 4 or more, for example, as disclosed in Japanese Patent Publication No. 56-28154, Japanese Patent No. 2696530, etc., maltotriose or glucose Reducing the content of maltotriose or oligosaccharides having a polymerization degree of glucose of 4 or more by acting on enzymes having a polymerization degree of 4 or more and acting on enzymes that decompose them to produce glucose or maltose. At the same time, the maltose content can be increased. In addition, it is also possible to separate and remove maltotriose or oligosaccharide having a glucose polymerization degree of 4 or more using a UF membrane, reverse osmosis membrane, activated carbon, or the like, as described in JP-B-62-51120 and JP-B-5-79316. As disclosed in publications and the like, maltotriose or higher oligosaccharides can also be separated and removed using a chromatographic separation method using an ion exchange resin.
[0016]
One of the features of the present invention is that a maltose content is 86% or more and less than 93% in terms of anhydride by adopting a series of production methods combining the following steps and increasing the crystallization rate of maltose. In this case, it is dissolved in a spray method despite the fact that carbohydrates other than maltose, such as glucose, maltotriose and oligosaccharides with a glucose polymerization degree of 4 or higher, are present in a relatively large amount of 7% to less than 14%. A β-maltose hydrous crystal-containing powder that is excellent in properties and easy to handle can be easily produced in a relatively short time.
[0017]
That is, a series of production methods are (a) using a maltose-containing solution of the sugar composition used in the present invention as a mass kit, and then (b) spraying, preferably by a spray drying method using a high-pressure nozzle or a rotating disk. In order to increase the crystallization rate of maltose contained in the powder, preferably (c), which has a relatively low humidity, the powder is preferably less than 10% moisture, more preferably about 5-9%. At a high temperature atmosphere, preferably less than 40% relative humidity (RH), more preferably less than 20%, preferably above 75 ° C., more preferably 80-110 ° C. for about 1 to 4 hours. , A powder containing a high content of α-anomer which is a maltose isomer, preferably a powder having a content of α-anomer in maltose of 35% or more, and (d) a relatively high humidity and low temperature atmosphere, desired Alternatively, the relative humidity (RH) exceeds 70%, more preferably 80% or more, preferably less than 50 ° C., more preferably 20 to 45 ° C. for about 5 to 10 hours. The α-anomer content is reduced to 7% or more and less than 14%, and (e) is achieved by collecting β-maltose hydrous crystal-containing powder having a crystallinity of 62% or more and less than 72%.
[0018]
Hereafter, each said process is demonstrated in detail. In the step (a), the maltose-containing solution is concentrated, desirably a concentrated solution having a water content of 15 to 30%, and an appropriate amount of β-maltose hydrous crystal as a seed crystal, usually about 0.1 to 5%. A mass kit is produced while gradually cooling and stirring together. At this time, the crystallization rate of β-maltose hydrous crystals (hereinafter, unless otherwise specified, the crystallization rate means that the mass kit is divided into crystals and nectar, and (crystal anhydride weight / mass kit). The weight of the anhydride)) x 100.) The higher the value of), the higher the viscosity of the mass kit.
[0019]
In the step (b), the present inventors reduced the viscosity by heating and raising the temperature of the high-viscosity mass kit containing β-maltose hydrous crystals within a range that does not substantially reduce the crystallization rate. As a result, it was found that a β-maltose hydrous crystal-containing powder can be easily produced by a spray method. That is, the inventors of the present invention, when the mass kit is heated and heated, the viscosity immediately decreases as the temperature increases, but the generated crystals do not dissolve in a short time even if the temperature rises somewhat, and the crystallization rate The viscosity of the mass kit is desirably increased by raising the temperature of the mass kit without substantially reducing the crystallization rate, and desirably the viscosity of the mass kit is 50,000 cp (hereinafter referred to as “special” in the present specification). Unless otherwise indicated, the viscosity cp means a value measured by rotating at 4 rpm using a No. 7 rotor using a BH rotational viscometer. It has become clear that the drying efficiency can be improved.
[0020]
The method for raising the temperature is not particularly limited. For example, known methods such as flowing warm water through a jacket of a crystallizer containing a mass kit, adding steam directly into the crystallizer, and heating using a heat exchanger between the crystallizer and the liquid feed pump are appropriately used. Can be adopted. The degree of temperature rise is such that the viscosity of the mass kit can be sprayed, specifically, 50,000 cp or less, preferably 40,000 cp or less, usually 2 to 15 ° C., preferably 2 to 10 ° C. It is preferable to carry out in as short a time as possible without causing a decrease in the crystallization rate.
[0021]
In the step (c), it is also possible to advantageously employ a method in which the powder is brought into contact with a small amount of anhydrous α-maltose crystals to promote isomerization to α-anomer in maltose. As maltose isomers, there are α-anomer and β-anomer. Known crystal forms include anhydrous α-maltose crystals, hydrous β-maltose crystals, anhydrous β-maltose crystals, and α and β complex crystals in which α-maltose and β-maltose coexist at a certain ratio.
[0022]
The content of α-anomer in maltose of 7% or more and less than 14% means the content of α-anomer in maltose, regardless of whether the form is amorphous or crystalline. In general, when the content of α-anomer in maltose is 14% or more, it means that there is a lot of amorphous maltose or α-maltose anhydrous crystals, and conversely, maltose. When the content of α-anomer is less than 7%, the rest is β-maltose, which means that the content of water containing β-maltose or anhydrous crystals is high.
[0023]
Further, in the step (d), after the α-anomer content in the maltose is reduced to 7% or more and less than 14% by keeping it for about 5 to 10 hours, it is advantageous to add a drying step if necessary. Can be implemented.
[0024]
In the step (e), the obtained β-maltose hydrous crystal-containing powder is subjected to a particle size distribution test (starch sugar related industrial analysis method, published in 1991, released by Food Chemical Newspaper Co., Ltd. on page 118). According to the measurement method, a sample of 50 g was measured for 15 minutes using a JIS / Z8801 sieve) and contained a large amount of powder having a relatively large particle size, and usually more than 60% of the powder exceeding 106 μm In many cases, it contains 40% or more of powders exceeding 150 μm and not more than 300 μm. In addition, the powder of more than 150 μm and less than 300 μm often contains agglomerates produced by adhering and agglomerating a plurality of particles in the course of dropping in the spray dryer or in the process from aging to completion of drying.
[0025]
The β-maltose hydrous crystal-containing powder of the present invention thus obtained is a powder that is excellent in solubility in an aqueous medium, has good storage stability and fluidity, and is easy to handle.
[0026]
The aqueous medium referred to in the present invention means a liquid, paste, semi-solid or solid containing a large amount of water or water that can dissolve and contain the β-maltose hydrous crystal-containing powder. In particular, the aqueous medium having viscosity includes, for example, sugars, starches, fats, proteins, polyphenols, emulsifiers, and the like. Specifically, for example, gelatinized starch used for fertilization, rice cake confectionery, etc. Dough, dough, noodles, etc. prepared from wheat flour, crushed meat such as raw bean paste, fish meat, livestock meat, liquid egg, milk cream, fermented milk, peanut paste, fruit pulp, vegetable pulp, sugar syrup, extract concentrate and so on.
[0027]
The β-maltose hydrous crystal-containing powder of the present invention is excellent in solubility in an aqueous medium having the above-mentioned viscosity, and can be advantageously used not only for this purpose but also for use in an aqueous medium having a low viscosity. In addition, it has good quality and elegant sweetness and has an action of inhibiting the production of dextran, which is one of the causes of dental caries, and is also suitably used as a sweetener that hardly causes caries.
[0028]
Moreover, the β-maltose hydrous crystal-containing powder of the present invention can be advantageously used as a sugar coating for tablets in combination with known binders such as pullulan, hydroxyethyl starch, and polyvinylpyrrolidone. Furthermore, the β-maltose hydrous crystal-containing powder of the present invention is useful for osmotic pressure controllability, shaping, irradiating properties, moisture retention, viscosity, sugar crystallization prevention properties, anti-aging properties of gelatinized starch, etc. It also has properties.
[0029]
Accordingly, the β-maltose hydrous crystal-containing powder of the present invention is used as a sweetener, a taste improver, a flavor improver, a quality improver, a stabilizer, an excipient, etc. as food, feed, feed, cosmetics, pharmaceuticals, tastes, etc. It can be advantageously used in various compositions such as products.
[0030]
As a specific use of the β-maltose hydrous crystal-containing powder of the present invention, it can be used as a seasoning for sweetening various articles. As needed, for example, powdered sugar, glucose, fructose, lactosucrose, sucrose, trehalose, isomerized sugar, honey, maple sugar, isomaltoligosaccharide, galactooligosaccharide, fructooligosaccharide, sorbitol, maltitol, lactitol, dihydrochalcone, Use in combination with one or more of other sweeteners such as stevioside, α-glycosyl stevioside, rebaudioside, glycyrrhizin, L-aspartyl-L-phenylalanine methyl ester, sucralose, acesulfame K, saccharin, glycine, alanine, etc. If necessary, it is also optional to use in combination with one or more fillers such as dextrin, starch, sugar and lactose.
[0031]
Further, the β-maltose hydrous crystal-containing powder of the present invention is used as it is or in combination with one or more of appropriate fillers, excipients, binders, sweeteners, etc. It is also optional to use in various shapes such as granules, spheres, short bars, plates, cubes, tablets, films or sheets.
[0032]
Furthermore, the sweetness of the β-maltose hydrous crystal-containing powder of the present invention is well harmonized with various substances having other tastes such as acidity, salt to taste, astringency, umami, bitterness, sweetening various foods, It can be used for improving taste and improving quality. Specifically, for example, amino acids, peptides, soy sauce, powdered soy sauce, miso, powdered miso, moromi, hashio, sprinkle, mayonnaise, dressing, vinegar, three cups of vinegar, powdered sushi vinegar, Chinese food, tentsuyu, noodle soup, sauce , Ketchup, grilled meat sauce, curry roux, stew element, soup element, dashi element, nucleic acid seasoning, compound seasoning, mirin, new mirin, table sugar, coffee sugar, etc. Also, for example, various Japanese sweets such as rice crackers, hail, rice cakes, rice cakes, manju, eel wax, bean jam, water sheep cake, brocade, jelly, castella, rice cake, bread, biscuits, crackers, cookies, pie , Pudding, butter cream, custard cream, cream puff, waffle, sponge cake, donut, chocolate, chewing gum, caramel, candy and other Western confectionery, ice cream, sorbet and other ice confectionery, fruit syrup pickled, syrup such as ice honey, flower Paste such as paste, peanut paste, fruit paste, spread, fruits such as jam, marmalade, syrup pickles, sugar cane, processed foods of vegetables, pickles such as Fukujin pickles, bedara pickles, thousand pickles, pickled pickles, takan pickles, Pickled Chinese cabbage Raw meat products such as ham, sausage, fish meat ham, fish sausage, fish products such as kamaboko, chikuwa, tempura, sea urchin, squid salted salt, vinegared konbu, suki-meme, dried fugurin, and paste , Wild vegetables such as wild vegetables, sushi, small fish, shellfish, boiled beans, potato salad, side dish foods such as kombu rolls, dairy products such as yogurt and cheese, fish meat, livestock meat, fruits, bottled vegetables, canned foods , Sake, synthetic sake, liqueur, liquor such as Western liquor, coffee, tea, cocoa, juice, carbonated beverages, lactic acid beverages, lactic acid beverages, lactic acid bacteria beverages and other soft drinks, pudding mix, hot cake mix, instant sushi, instant soup, etc. It can be advantageously used in foods, and various foods such as baby foods, therapeutic foods, drinks, peptide foods, frozen foods, and health foods.
[0033]
Furthermore, it can also be used for the purpose of improving the palatability of feed, feed, etc. for domestic animals, poultry, other bees, rabbits, fish and other domestic animals. In addition, as a sweetener for various solids such as tobacco, toothpaste, lipstick, lip balm, oral solution, tablet, troche, liver oil drop, mouth freshener, mouth fragrance, gargle, etc., or a taste improver thereof, It can be advantageously used as a corrigent, quality improver, stabilizer and the like.
[0034]
The β-maltose hydrous crystal-containing powder of the present invention is a stable, high-quality liquid by blending it into health foods, pharmaceuticals, etc. containing active ingredients, active ingredients or bioactive substances as quality improvers and / or stabilizers. A paste-like or solid health food or medicine can be obtained. Examples of the active ingredient and physiologically active substance include interferon-α, interferon-β, interferon-γ, TNF-α, TNF-β, macrophage migration inhibitory factor, colony stimulating factor, transfer factor, lymphokine such as interleukin, Hormones such as insulin, growth hormone, prolactin, erythropoietin, egg cell stimulating hormone, BCG vaccine, Japanese encephalitis vaccine, measles vaccine, polio vaccine, seedling, tetanus toxoid, hub antitoxin, human immunoglobulin and other biologics, penicillin, erythromycin , Chloramphenicol, tetracycline, Strept Antibiotics such as mycin and kanamycin sulfate, thiamine, riboflavin, L-ascorbic acid, α-glycosyl ascorbic acid, liver oil, carotenoid, ergosterol, tocopherol, rutin, α-glycosylrutin, naringin, α-glycosylnarindine, hesperidin, α -Vitamins such as glycosyl hesperidin, lipase, elastase, urokinase, protease, β-amylase, isoamylase, glucanase, lactase and other enzymes, ginseng extract, koji extract, plum extract, pine extract, supella extract, chlorella extract, aloe Examples include extracts such as extracts and propolis extracts, live bacteria such as viruses, lactic acid bacteria, and yeasts, royal jelly, and the like.
[0035]
The above-described method for adding the β-maltose hydrous crystal-containing powder of the present invention to the various compositions may be included in the process until these compositions are completed, for example, mixing, dissolution, melting, and immersion. Well-known methods such as permeation, spraying, coating, coating, spraying, pouring, crystallization and solidification are appropriately selected. The amount is usually 1% or more, preferably 2% or more, more preferably 5 to 99%, based on the weight of the composition.
[0036]
Hereinafter, the present invention will be described in detail using specific experiments.
[0037]
[Experiment]
<Effect of raw sugar composition on physical properties of various β-maltose crystal-containing powders>
The effect of the raw sugar composition on the physical properties of various β-maltose crystal-containing powders by the spray method was investigated. As the test powder, various raw material maltose-containing solutions having different sugar compositions were prepared and used as a powder containing β-maltose hydrous crystals by a spray method. Maltose-containing solutions are commercially available purified maltose (registered trademark “Sanmalto S”, sold by Hayashibara Shoji Co., Ltd.), or glucose (reagent grade sold by Wako Pure Chemical Industries, Ltd.), maltotriose, maltotetraose. And / or maltopentaose (all are reagents manufactured by Hayashibara Biochemical Laboratories Co., Ltd.) to prepare maltose-containing solutions of various compositions.
[0038]
Preparation of the β-maltose hydrous crystal-containing powder by a spraying method was performed as follows. That is, after concentrating the raw material maltose-containing solution to a water content of 25%, it was transferred to an auxiliary crystal machine, and 1% of β-maltose water-containing crystal was added as a seed crystal, and the temperature was gradually lowered to 30 ° C. while slowly stirring. Β-maltose hydrous crystals were partially crystallized over a period of 18 hours to obtain a mass kit. The crystallization rate of the mass kit was 36 to 43%. After the auxiliary crystal is finished, if the viscosity of the mass kit exceeds 50,000 cp, heat it before sending it with a high-pressure pump, and increase the viscosity to about 45,000 cp without substantially reducing the crystallization rate. While lowering, spraying was performed using a pressure nozzle. The temperature of the hot air for drying at the time of spraying is 75 ° C, the hot air blowing method is a vertical downward flow in the spray dryer, and the amount of blown air is such that the moisture of the dry powder when taken out from the spray dryer is about 8.5% Adjusted.
[0039]
The obtained powder was immediately mixed and contacted with 0.2% anhydrous α-maltose crystals as seed crystals, stored for 2 hours in a constant temperature and humidity machine at a temperature of 90 ° C. and a relative humidity (RH) of 20%, and then 30 It was kept for 5 hours in a constant temperature and humidity machine at 80 ° C. and a relative humidity (RH) and aged to obtain a β-maltose hydrous crystal-containing powder. This powder was subjected to various physical property tests described below.
[0040]
In the physical property test, purified maltose (registered trademark “Sanmalto S”, traded by Hayashibara Corporation), hydrated reagent β-maltose crystal (manufactured by Hayashibara Biochemical Laboratories Ltd., trade name “Maltose HHH”) and α were used as controls. -Anhydrous maltose crystal (registered trademark "Fine Tose" sold by Hayashibara Shoji Co., Ltd.) was used.
[0041]
The physical property test was conducted by the following method.
A. In the sugar composition analysis, liquid chromatography using a KS-801 column (manufactured by Showa Denko) or a CH04SS column (manufactured by MCI) was performed, and the sugar composition was determined from the area ratio of the chromatogram.
[0042]
B. In the hygroscopicity test, the sample placed in the aluminum cup is not covered, placed in a desiccator adjusted to 75.2% RH (equilibrated with a saturated sodium chloride aqueous solution), and left at 25 ° C. for 3 days. Measure and original sample In The ratio (%) of the weight increase with respect to the weight was determined to be hygroscopic.
[0043]
C. The sticking property was determined to be sticky if the sample in the aluminum cup taken out after being left for 3 days in the hygroscopic test was visually observed and solidified as a result of the sample absorbing moisture compared to before the test.
[0044]
D. The solubility test is as follows: (i) As a solubility test in water, 5 ml of deionized water at 25 ° C. is put in a plastic test tube, and 1 g of maltose crystal-containing powder having various sugar compositions is added to the solution at a time. The tube was sealed in a state where it was submerged in water, held in a thermostat at 50 ° C., and the dissolved state of the powder was visually observed every 20 minutes. In the evaluation, the time (minutes) required until the powder was completely dissolved and became transparent was determined. As a criterion for evaluation, it was judged that the shorter the time until the powder disappears, the better the solubility.
[0045]
(Ii) As a solubility test for a dextrin-containing solution, 5 ml of a dextrin having a viscosity of 17% (manufactured by Matsutani Chemical Industry Co., Ltd., “Paindex # 1”) in an aqueous solution is placed in a plastic test tube. Add 1 g of maltose crystal-containing powder with various sugar compositions in the same manner as in the water solubility test of (i) above, seal the powder completely in water, and hold it in a thermostat at 50 ° C. Then, the state of the powder was visually observed. The standard of evaluation was the same as in the case of the solubility test in water of (i) above.
[0046]
E. For analysis of maltose isomers, the sample was dissolved in anhydrous pyridine, TMS-treated, gas chromatography using 2% OV-17 chromosolve W (AW-DMCS) was performed, and α was determined from the area ratio of the chromatogram. , Β-anomeric ratio was determined.
[0047]
F. The measurement of the crystallinity of the powder was carried out using the X-ray diffractometer Geiger Flex RDA-IIB (using Cu and Kα rays) (manufactured by Rigaku Denki Co., Ltd.) and the method of Roland based on the powder X-ray diffraction pattern. (Actor Crystallographica : Acta Crystallographica, Vol. 14, page 1180, 1961). Among the measured powders, typical powder X-ray diffraction patterns are shown in FIGS.
[0048]
The sugar composition of the raw material maltose-containing solution and the test results on the hygroscopicity, stickiness, solubility, α-anomer content, and crystallinity of each powder obtained are summarized in Table 1 as the physical properties of various maltose crystal-containing powders. It was.
[0049]
[Table 1]
[0050]
As is apparent from Table 1, test no. Oligosaccharides containing maltotriose 86% or more and less than 93% and glucose 2% or more obtained by spraying method 3 to 6 as malt triose and
[0051]
On the other hand, test no. The maltose content of 1 is as high as 94.1%, the α-anomer content in maltose is as low as 7% or less as the maltose isomer, and β-maltose hydrous crystals are obtained by spraying with a crystallinity exceeding 72%. The powder was poor in solubility in an aqueous medium, although it had little hygroscopicity and no stickiness.
[0052]
In addition, test No. used as a control. “Sanmalto S” of 8 is a powder obtained by a spray method. However, the maltose purity was 95.0% and the crystallinity was 74.5%, both of which were poor in solubility in an aqueous medium, although there was almost no hygroscopicity and no stickiness. In addition, Test No. No. 9 “Maltose HHH” is a crystal powder obtained by honeying a mass kit. This powder is a very high-purity maltose, having a high maltose purity of 99.6% and a crystallinity of 82.6%, almost no hygroscopicity and no stickiness, but soluble in an aqueous medium. It was inferior in nature. Furthermore, test no. No. 10 “Fine Tose” is α-maltose anhydrous crystal powder, unlike other samples. This powder has a high α-anomer content in maltose, and the properties of the powder are significantly different from other powders mainly composed of β-maltose hydrous crystals, and it has high hygroscopicity regardless of the crystallinity. Further, the powder is unstable and has an inferior storage stability, and also has poor solubility in an aqueous medium.
[0053]
From the above results, in the production of the β-maltose crystal-containing powder by the spray method, a solution containing maltose 86% or more and less than 93% and glucose 2% or more in terms of anhydride is used as a raw material. It was found that a β-maltose crystal-containing powder having excellent solubility in an aqueous medium and easy to handle can be obtained by the production according to this production method.
[0054]
Therefore, containing β-maltose crystals containing maltose of 86% or more and less than 93% and glucose of 2% or more and having a crystallinity of 62% or more and less than 72% in terms of anhydride, obtained by employing the present invention. Powders have excellent solubility in aqueous media, are easy to handle, and can be manufactured in high yields. In addition, compared to conventional powders, the work time when dissolved in aqueous media is greatly reduced. It can be said that it is extremely valuable industrially.
[0055]
Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.
[0056]
Example A-1-a
<Preparation of maltose-containing solution>
Immediately after adding a commercially available bacterial liquefied α-amylase (Spytase HS manufactured by Nagase Sangyo Co., Ltd.) to a suspension of 1 part by weight of potato starch and 4 parts by weight of water, heating to 90 ° C. The enzyme reaction was stopped by heating to 130 ° C. to obtain a liquefied liquid of DE1.8. This starch liquefied solution is rapidly cooled to 55 ° C., and starch debranching enzyme (isoamylase prepared by culturing Pseudomonas fungus) is added at 100 units per 1 g of starch and β derived from soybean. − Amylase (trade name # 1500, manufactured by Nagase Sangyo Co., Ltd.) is 50 units per gram of starch, and maltogenase (manufactured by Novo Nordisk Co., Ltd.) is 10 units per gram of carbohydrate. In addition Saccharification was carried out for 40 hours while maintaining the pH at 5.0. This was purified by decolorization by activated carbon treatment and desalting by ion exchange resin treatment according to conventional methods, and concentrated under reduced pressure to obtain a maltose-containing solution. The sugar composition of the maltose-containing solution was 3.8% glucose, 92.5% maltose, 1.1% maltotriose, and 2.6% maltotetraose or higher.
[0057]
Example A-1-b
<Preparation of β-maltose hydrous crystal-containing powder>
After concentrating the maltose-containing solution obtained in Example A-1-a to a moisture content of 29%, it was transferred to an auxiliary crystal can, and 1% of β-maltose hydrous crystal was added as a seed crystal, and the temperature of the mass kit was slowly stirred. The temperature was gradually lowered to 29 ° C., and β-maltose hydrous crystals were partially crystallized over 12 hours. The crystallization rate of Muskit was 37%. After completion of the auxiliary crystal, the mass kit was fed with a high-pressure pump and sprayed into a spray dryer using a rotating disk. At this time, the temperature of the hot air for drying is 70 ° C., the blowing of the hot air is adjusted in the vertical descent in the spray dryer, and the amount of blown air is adjusted so that the moisture content of the dry powder when taken out from the spray dryer is 7.5%. did.
[0058]
This powder was immediately mixed and contacted with 0.2% anhydrous α-maltose crystals, held at a temperature of 85 ° C. and a relative humidity (RH) of 20% for 3 hours, and then at 30 ° C. and a relative humidity (RH) of 80% for 5 hours. Holding and ripening, a β-maltose hydrous crystal-containing powder having a crystallinity of 71.4% and a moisture content of 6.1% was obtained with a yield of 96% in terms of anhydride relative to the raw material potato starch. . This powder contains, in terms of anhydride, 92.5% maltose, 3.8% glucose, 1.1% maltotriose, and 2.6% oligosaccharide having a glucose polymerization degree of 4 or more, and maltose isomerism. It contained 7.8% α-anomer in maltose as a body and was excellent in solubility in an aqueous medium. Moreover, even when stored under the conditions of 25 ° C. and relative humidity (RH) 75.2%, it hardly showed hygroscopicity, had excellent storage stability, good fluidity, and was easy to handle. Further, as a result of measuring the particle size distribution of the present powder, it was found that 41% of particles having a particle size of 150 μm or more and 300 μm or less were included, including a powder in which fine particles aggregated.
[0059]
In addition, the powder is excellent in solubility in an aqueous medium, especially as a sweetener, taste improver, quality improver, stabilizer, anti-discoloring agent, extender, excipient, binder, etc. For example, it can be dissolved and contained not only in water but also in a paste or semi-solid material, and can be advantageously used in various compositions such as foods and drinks, foods, feeds, foods, cosmetics, and pharmaceuticals. Further, it can be used as it is or mixed with a bulking agent, excipient, binder, etc., and shaped into various shapes such as granules, spheres, short bars, plates, cubes, tablets, etc. Is voluntary.
[0060]
Example A-2-a
<Preparation of maltose-containing solution>
Commercially available bacterial liquefied α-amylase (Spytase HS manufactured by Nagase Sangyo Co., Ltd.) is added to a suspension of 1 part by weight of corn starch and 3 parts by weight of water, the temperature is raised to 90 ° C., and gelatinized by heating to 130 ° C. immediately. The enzyme reaction was stopped by heating to a DE2.5 liquefied solution. This starch liquefied liquid is rapidly cooled to 55 ° C., and starch debranching enzyme (isoamylase prepared by cultivating Pseudomonas bacteria) is added at 50 units per gram of starch and β derived from soybean. − Similarly, 20 units of amylase (trade name # 1500, manufactured by Nagase Sangyo Co., Ltd.) was added and the mixture was saccharified for 40 hours while maintaining the pH at 5.0 to obtain a high-purity maltose-containing saccharified solution having a maltose content of 84.6% per solid. The sugar composition of the maltose-containing saccharified solution was 3.5% glucose, 84.6% maltose, 8.2% maltotriose, and 3.7% or more maltotetraose.
[0061]
To this saccharified solution, takaamylase A was further added at 50 units per gram of sugar, and the pH was kept at 5.5, and the enzyme reaction was further continued for 20 hours. This was purified by decolorization by activated carbon treatment and desalting by ion exchange resin treatment in accordance with conventional methods, and concentrated under reduced pressure to obtain a maltose-containing solution. The sugar composition of the maltose-containing solution was 5.6% glucose, 91.2% maltose, 1.3% maltotriose, and 1.9% maltotetraose or higher.
[0062]
Example A-2-b
<Preparation of β-maltose hydrous crystal-containing powder>
After concentrating the maltose-containing solution obtained in Example A-2-a to a moisture content of 26%, the solution was transferred to an auxiliary crystal machine, and 1% of β-maltose hydrous crystals were added as seed crystals, and the temperature of the mass kit was adjusted while slowly stirring. The temperature was gradually lowered to 30 ° C., and β-maltose hydrous crystals were partially crystallized over 14 hours. The crystallization rate of the mass kit was 41%. After completion of the auxiliary crystal, the mass kit was fed with a high-pressure pump and sprayed into a spray dryer using a rotating disk. The temperature of the hot air for drying was 75 ° C., the blowing of the hot air was adjusted in the vertical descent in the spray dryer, and the amount of blown air was adjusted so that the water content of the dry powder when taken out from the spray dryer was 8.5%.
[0063]
This powder was immediately mixed and contacted with 0.2% α-maltose anhydrous crystals, kept at a temperature of 90 ° C. and a relative humidity (RH) of 25% for 2 hours, and then at 30 ° C. and a relative humidity (RH) of 80% for 5 hours. This was retained and aged to obtain a β-maltose hydrous crystal-containing powder having a crystallinity of 70.4% and a water content of 6.1% with respect to the raw material corn starch in a yield of 95% in terms of anhydride. This powder contains, in terms of anhydride, 91.2% maltose, 5.6% glucose, 1.3% maltotriose, and 1.9% oligosaccharides having a glucose polymerization degree of 4 or more, and maltose isomerism. It contained 9.2% α-anomer in maltose as a body and was excellent in solubility in an aqueous medium. Moreover, even when stored under the conditions of 25 ° C. and relative humidity (RH) 75.2%, it hardly showed hygroscopicity, had excellent storage stability, good fluidity, and was easy to handle. Further, as a result of measuring the particle size distribution of the present powder, 47% of particles having a particle size of 150 μm or more and 300 μm or less were included, including a powder in which fine particles were aggregated.
[0064]
In addition, the powder is excellent in solubility in an aqueous medium, especially as a sweetener, taste improver, quality improver, stabilizer, anti-discoloring agent, extender, excipient, binder, etc. For example, it can be dissolved and contained not only in water but also in a paste or semi-solid material, and can be advantageously used in various compositions such as foods and drinks, foods, feeds, foods, cosmetics, and pharmaceuticals. Further, it can be used as it is or mixed with a bulking agent, excipient, binder, etc., and shaped into various shapes such as granules, spheres, short bars, plates, cubes, tablets, etc. Is voluntary.
[0065]
Example A-3-a
<Preparation of maltose-containing solution>
Commercially available bacterial liquefied α-amylase (Spytase HS manufactured by Nagase Sangyo Co., Ltd.) was added to a suspension of 3 parts by weight of corn starch and 7 parts by weight of water, the temperature was raised to 90 ° C, and the mixture was heated to gelatin and immediately 130 ° C. To stop the enzyme reaction, and a liquefied liquid of DE 4.3 was obtained. This starch liquefied solution is rapidly cooled to 55 ° C., and starch debranching enzyme (isoamylase prepared by culturing Pseudomonas bacteria) is 50 units per gram of starch, soy-derived β − Amylase (trade name # 1500, manufactured by Nagase Sangyo Co., Ltd.) was similarly saccharified by adding 20 units and maintaining the pH at 5.0 for 40 hours to obtain a saccharified solution having a maltose content of 84.6% per solid. This was purified by decolorization by activated carbon treatment and desalting by ion exchange resin treatment according to conventional methods, and concentrated under reduced pressure to obtain a maltose-containing solution having a sugar concentration of 45%, which was used as a fraction raw material.
[0066]
The fractionation resin used for fractionation was an alkali metal strong acid cation exchange resin (trade name Amberlite XT-1007Na manufactured by Tokyo Organic Chemical Industry Co., Ltd.). + Mold, 6% cross-linkage), packed in a jacketed stainless steel column with an inner diameter of 5.4 cm with water suspension, and connected the two columns so that the saccharide solution flows in series. 10 m.
[0067]
While maintaining the temperature in the column at 55 ° C., the raw material sugar solution was added to the resin at 5 v / v%, and 55 ° C. warm water was fed at SV 0.3 to perform fractionation. The fraction was separated and removed, and a fraction containing a high content of maltose containing a high content of maltose and other oligos was collected. Subsequently, purifying by decolorization by activated carbon treatment and desalting by ion exchange resin treatment in accordance with a conventional method, the solution was concentrated under reduced pressure to obtain a maltose-containing solution. The sugar composition of this maltose-containing solution was 6.0% glucose, 90.1% maltose, 0.8% maltotriose, and 3.1% maltotetraose or higher.
[0068]
Example A-3-b
<Preparation of β-maltose hydrous crystal-containing powder>
After concentrating the maltose-containing solution obtained in Example A-3-a to a moisture content of 24%, the solution was transferred to an auxiliary crystallizer, and 1% of β-maltose hydrous crystals were added as seed crystals, and the temperature of the mass kit was slowly stirred. The temperature was gradually lowered to 29 ° C., and β-maltose hydrous crystals were partially crystallized over 15 hours. The crystallization rate was 40%. Since the mass kit after completion of the auxiliary crystallization has a high viscosity, it is heated at the time of feeding with a high-pressure pump, and the viscosity is reduced to about 40,000 cp without reducing the crystallization rate. Sprayed on. At this time, the temperature of the drying hot air is 75 ° C., the hot air is blown vertically downward in the spray dryer, and the amount of air blown is such that the moisture of the dry powder taken out from the spray dryer is 9.0%. Adjusted.
[0069]
This powder was immediately mixed and contacted with 0.2% anhydrous α-maltose crystals, held at a temperature of 85 ° C. and a relative humidity (RH) of 20% for 2 hours, and then at 35 ° C. and a relative humidity (RH) of 75% for 5 hours. Holding and aging, a β-maltose hydrous crystal-containing powder having a crystallinity of 69.0% and a water content of 6.4% was obtained with a yield of 89% in terms of anhydride relative to the raw material corn starch. This powder contains, in terms of anhydride, 90.1% maltose, 6.0% glucose, 0.8% maltotriose, and 3.1% oligosaccharide having a glucose polymerization degree of 4 or more, and maltose isomerism. It contained 9.9% α-anomer in maltose as a body and was excellent in solubility in an aqueous medium. Moreover, even when stored under conditions of 25 ° C. and relative humidity (RH) 75.2%, it exhibits almost no hygroscopicity, excellent storage stability, good flowability, and easy handling. Further, as a result of measuring the particle size distribution of the present powder, 51% of particles having a particle size of 150 μm or more and 300 μm or less were included, including a powder in which fine particles aggregated.
[0070]
In addition, the powder is excellent in solubility in an aqueous medium, especially as a sweetener, taste improver, quality improver, stabilizer, anti-discoloring agent, extender, excipient, binder, etc. For example, it can be dissolved and contained not only in water but also in a paste or semi-solid material, and can be advantageously used in various compositions such as foods and drinks, foods, feeds, foods, cosmetics, and pharmaceuticals. Further, it can be used as it is or mixed with a bulking agent, excipient, binder, etc., and shaped into various shapes such as granules, spheres, short bars, plates, cubes, tablets, etc. Is voluntary.
[0071]
Example A-4-a
<Preparation of maltose-containing solution>
Commercially available bacterial liquefied α-amylase (Spytase HS manufactured by Nagase Sangyo Co., Ltd.) was added to a suspension of 1 part by weight of corn starch and 2 parts by weight of water, the temperature was raised to 90 ° C, and gelatinized by heating to 130 ° C immediately. To stop the enzyme reaction, and a liquefied liquid of DE 4.3 was obtained. This starch liquefied solution is rapidly cooled to 55 ° C., and starch debranching enzyme (isoamylase prepared by culturing Pseudomonas bacteria) is 50 units per gram of starch, soy-derived β − Similarly, 10 units of amylase (trade name # 1500, manufactured by Nagase Sangyo Co., Ltd.) were added and saccharified for 40 hours while maintaining pH 5.0 to obtain a saccharified solution having a maltose content of 74.1% per solid matter. This was purified by decolorization by activated carbon treatment and desalting by ion exchange resin treatment according to conventional methods, and concentrated under reduced pressure to obtain a maltose-containing solution having a sugar concentration of 45%, which was used as a fraction raw material.
[0072]
The fractionation resin used for fractionation was an alkali metal strong acid cation exchange resin (trade name Amberlite XT-1007Na manufactured by Tokyo Organic Chemical Industry Co., Ltd.). + Mold, 6% cross-linkage), packed in a jacketed stainless steel column with an inner diameter of 5.4 cm with water suspension, and connected the two columns so that the saccharide solution flows in series. 10 m.
[0073]
While maintaining the temperature in the column at 55 ° C., the raw material sugar solution was added to the resin at 5 v / v%, and 55 ° C. warm water was fed at SV 0.3 to perform fractionation. The fraction was separated and removed, and a fraction containing a high content of maltose containing a high content of maltose and other oligos was collected. Subsequently, purifying by decolorization by activated carbon treatment and desalting by ion exchange resin treatment in accordance with a conventional method, the solution was concentrated under reduced pressure to obtain a maltose-containing solution. The sugar composition of the maltose-containing solution was 9.8% glucose, 87.4% maltose, 1.0% maltotriose, and 1.8% maltotetraose or higher.
[0074]
Example A-4-b
<Preparation of β-maltose hydrous crystal-containing powder>
After concentrating the maltose-containing solution obtained in Example A-4-a to 20% moisture, it was transferred to an auxiliary crystallizer, and 1% β-maltose hydrous crystals were added as seed crystals, and the temperature of the mass kit was adjusted while slowly stirring. The temperature was gradually lowered to 32 ° C., and β-maltose hydrous crystals were partially crystallized over 16 hours. The crystallization rate was 39%. Since the mass kit after completion of the auxiliary crystal has high viscosity, it is heated at the time of feeding with a high-pressure pump, the viscosity is reduced to about 45,000 cp or less without reducing the crystallization rate, and spray drying using a rotating disk. Sprayed into the machine. At this time, the temperature of the hot air for drying is 90 ° C., the blowing of the hot air is a vertical downward co-current flow in the spray dryer, and the amount of blown air is such that the moisture of the dry powder when taken out from the spray dryer is 9.5%. Adjusted.
[0075]
This powder was immediately mixed and contacted with 0.2% α-maltose anhydrous crystals, held at a temperature of 90 ° C. and a relative humidity (RH) of 20% for 3 hours, and then at 30 ° C. and a relative humidity (RH) of 80% for 5 hours. This was retained and aged to obtain a β-maltose hydrous crystal-containing powder having a crystallinity of 64.6% and a water content of 6.8%, based on the raw material corn starch, in an yield of 80% in terms of anhydride. This powder contains, in terms of anhydride, 87.4% maltose, 9.8% glucose, 1.0% maltotriose, and 1.8% oligosaccharides having a glucose polymerization degree of 4 or more, and maltose isomerism. It contained 12.7% α-anomer in maltose as a body and was excellent in solubility in an aqueous medium. Moreover, even when stored at 25 ° C. and a relative humidity (RH) of 75.2%, it exhibits almost no hygroscopicity, Save The powder was excellent in stability, good fluidity and easy to handle. Further, as a result of measuring the particle size distribution of the present powder, 53% of particles having a particle size of 150 μm or more and 300 μm or less were included, including a powder in which fine particles aggregated.
[0076]
In addition, the powder is excellent in solubility in an aqueous medium, especially as a sweetener, taste improver, quality improver, stabilizer, anti-discoloring agent, extender, excipient, binder, etc. For example, it can be dissolved and contained not only in water but also in a paste or semi-solid material, and can be advantageously used in various compositions such as foods and drinks, foods, feeds, foods, cosmetics, and pharmaceuticals. Further, it can be used as it is or mixed with a bulking agent, excipient, binder, etc., and shaped into various shapes such as granules, spheres, short bars, plates, cubes, tablets, etc. Is voluntary.
[0077]
Example B-1
<Sweetener>
0.5 part by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-1-b, 0.5 part by weight of anhydrous sorbitol crystals, α-glycosyl stevioside (trade name “αG Sweet” sold by Toyo Seika Co., Ltd.) ]) 0.01 parts by weight and 0.01 parts by weight of L-aspartyl-L-phenylalanine methyl ester (registered trademark “Aspartame” sold by Ajinomoto Co., Inc.) are uniformly mixed and applied to a granule molding machine to form a granular sweetener. Got. This product has excellent sweetness quality, has about twice the sweetness of sucrose, and is substantially low in calories. This sweetener has no degradation of high-intensity sweetener blended in it, has excellent stability, and as a low-calorie sweetener, low-calorie food and drink for obese people, diabetics, etc. who restrict caloric intake Suitable for sweetening products. In addition, the present sweetener is suitable for sweetening foods and the like that suppress dental caries because it produces less acid by caries-inducing bacteria and produces less insoluble glucan.
[0078]
Example B-2
<Hard candy>
50 parts by weight of sucrose and 50 parts by weight of the β-maltose hydrous crystal-containing powder obtained by the method of Example A-2-b are dissolved in 100 parts by weight of water, heated and mixed, and then under reduced pressure until the water content is less than 2% The mixture was heated and concentrated, and 0.6 parts by weight of citric acid and an appropriate amount of lemon flavor and color were mixed and molded according to a conventional method to obtain a product. This product is a stable, high-quality hard candy that has good crispness, color, taste, and flavor, does not cause sucrose crystallization, has low hygroscopicity, and does not cause dripping.
[0079]
Example B-3
<Chewing gum>
3 parts by weight of gum base was heated and melted to a degree of softening, and then 2 parts by weight of anhydrous crystalline maltitol (trademark “Mabbit” sold by Hayashibara Corporation), 2 parts by weight of xylitol, the method of Example A-3-b 2 parts by weight of the β-maltose hydrous crystal-containing powder obtained in 1 above and 1 part by weight of hydrous crystal trehalose (trademark “Trehha”, Hayashibara Shoji Co., Ltd.) are added, and an appropriate amount of fragrance and coloring are mixed. According to the law, the product was obtained by kneading with a roll, molding and packaging. This product is suitable as a chewing gum having a good texture, taste and flavor, low caries and low calories.
[0080]
Example B-4
<Sweetened condensed milk>
In 100 parts by weight of raw milk, 2 parts by weight of the β-maltose hydrous crystal-containing powder obtained by the method of Example A-4-b and 2 parts by weight of sucrose are dissolved, heat sterilized with a plate heater, and then concentrated to a concentration of 70%. And canned under aseptic conditions to obtain a product. This product has mild sweetness and good flavor, and can be advantageously used for seasoning fruits, coffee, cocoa, tea, and the like.
[0081]
Example B-5
<Lactic acid bacteria beverage>
175 parts by weight of skim milk powder, 60 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-2-b, and powder containing high lactosucrose (trademark “Hayashi Oligo”) Dissolve parts by weight in 1,150 parts by weight of water, sterilize at 65 ° C. for 30 minutes, cool to 40 ° C., inoculate 30 parts by weight of a starter of lactic acid bacteria, and then incubate at 37 ° C. for 8 hours. The lactic acid bacteria beverage was obtained by culturing. This product has a good flavor, contains oligosaccharides, and not only keeps lactic acid bacteria stable, but is also suitable as a lactic acid bacteria drink having bifidobacteria growth promoting action and intestinal regulating action.
[0082]
Example B-6
<Powder juice>
With respect to 33 parts by weight of orange fruit juice powder produced by spray drying, 50 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-4-b, anhydrous crystal maltitol (sales of Hayashibara Corporation) Trademark "Mabit") 10 parts by weight, anhydrous citric acid 0.65 parts by weight, malic acid 0.1 parts by weight, ascorbic acid 2-glucoside crystal powder (sales by Hayashibara Corporation), sodium citrate 0.1 part by weight, Pullulan (Hayashibara Shoji PF-20) 0.5 part by weight and appropriate amount of powdered fragrance are mixed and stirred well, pulverized into a fine powder, and charged into a fluid bed granulator The exhaust air temperature is 40 ° C. A An appropriate amount of a 70% solution obtained by dissolving the β-maltose hydrous crystal-containing powder obtained by the method of 4-b in water was sprayed as a binder, granulated for 30 minutes, weighed and packaged to obtain a product. This product is a powdered juice with a fruit juice content of about 30%. Moreover, this product has no off-flavor and off-flavor, and has a high commercial value as a high-quality juice.
[0083]
Example B-7
<Coffee drink>
100 parts by weight of roasted coffee beans were pulverized and extracted with 1,000 parts by weight of hot water to obtain 860 parts by weight of an extract. To 450 parts by weight of this solution, 90 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-1-b and 400 parts by weight of water containing an appropriate amount of baking soda were added and mixed uniformly. A coffee drink was prepared, and then filled into a can according to a conventional method, and heat sterilized at 120 ° C. for 30 minutes to produce a canned coffee drink. This product is a high quality coffee drink with good aroma and taste. Further, even after the product was put in a vending machine and held at 60 ° C. for 1 month, the good flavor was well maintained. In addition, this product is a high-quality coffee drink with good fragrance and taste even after being cooled and stored for summer.
[0084]
[Example B-8]
<Custard cream>
100 parts by weight of corn starch, 50 parts by weight of β-maltose hydrated crystal-containing powder obtained by the method of Example A-2-b, 60 parts by weight of hydrated crystal trehalose (trademark “Treha”, Hayashibara Corporation), sugar 40 Thoroughly mix 1 part by weight and 1 part by weight of salt, add 280 parts by weight of chicken egg and stir. To this, gradually add 1,000 parts by weight of boiled milk. When gelatinized and the whole became translucent, the fire was stopped, cooled, added with an appropriate amount of vanilla flavor, weighed, filled and packaged to obtain a product. This product is a high-quality custard cream with a smooth luster, good flavor, and reduced starch aging.
[0085]
Example B-9
<Uiro no Moto>
Contains 90 parts by weight of rice flour, 20 parts by weight of corn starch, 70 parts by weight of anhydrous crystal maltitol (registered trademark “Mabit” sold by Hayashibara Corporation), and β-maltose hydrous crystals obtained by the method of Example A-1-b 50 parts by weight of powder and 4 parts by weight of pullulan (Hayashibara Shoji Sales PF-20) were mixed uniformly to produce Uiro. Ui-no-Moto, an appropriate amount of Matcha and water were kneaded, and the mixture was placed in a container and steamed for 60 minutes to produce Matcha Uiro. This product has good shine, mouthfeel, and good flavor. In addition, aging of starch is suppressed, the shelf life is good, and it is also suitable as a low calorie umbilicus.
[0086]
Example B-10
<Fertilization>
Dissolve 4 parts by weight of starch in 6 parts by weight of water, pour into a wooden frame with a wet cloth and steam it at 100 ° C. for 20 minutes, and then obtain it by the method of Example A-1-b. Further, 2 parts by weight of β-maltose hydrous crystal-containing powder and 2 parts by weight of sugar were added and kneaded sufficiently to form a fertilizer. This product has a good flavor, and the aging of the gelatinized brown rice starch is suppressed, and the shelf life can be extended significantly.
[0087]
Example B-11
<An>
In accordance with a conventional method, water was added to 10 parts by weight of raw azuki and boiled, astringent and extracted, and water-soluble impurities were removed to obtain about 21 parts by weight of red bean paste. Add 14 parts by weight of sugar, 3 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-3-b and 7 parts by weight of water and boil it. Add a small amount of salad oil to it. About 35 parts by weight of the product was obtained. This product is stable without color burns and water separation, has a good touch and good taste, and is suitable as a confectionery material such as anpan, manju, dumplings, and ice confectionery.
[0088]
Example B-12
<Bread>
100 parts by weight of wheat flour, 2 parts by weight of yeast, 5 parts by weight of sugar, 5 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-1-b, and 0.1 part by weight of an inorganic food were prepared according to a conventional method. Kneaded with water, the middle seed was fermented at 26 ° C. for 2 hours, and then aged and baked for 30 minutes. This product is a high-quality bread with good hue and quality, moderate elasticity and mild sweetness.
[0089]
Example B-13
<Icing>
1.2 parts by weight of an emulsifier (sugar ester) was heated and mixed with 10 parts by weight of the β-maltose hydrous crystal-containing powder obtained by the method of Example A-2-b, and then hydrous crystal trehalose (Hayashibara Corporation sales) 107 parts by weight of a registered trademark “Trehha”) were mixed, and 7.5 parts by weight of fats and oils were mixed while maintaining the temperature at 45 ° C. to produce an icing. This product contains trehalose microcrystals, has good moldability, is not sticky, and has little change over time.
[0090]
Example B-14
<Bonbon>
3 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-3-b, 300 parts by weight of hydrous crystal trehalose (registered trademark “Treha”, Hayashibara Shoji Co., Ltd.) and 115 parts by weight of water were mixed. The mixture was heated and boiled to Bx70, the product temperature was cooled to 80 ° C., 40 parts by weight of brandy were mixed, and then molded according to a conventional method to obtain a bonbon. This product contains trehalose microcrystals, rich in brandy flavor, Days It is a high-quality bonbon with little change.
[0091]
Example B-15
<Ham>
The pork thigh is uniformly rubbed with 1,000 parts by weight of meat and 15 parts by weight of sodium chloride and 3 parts by weight of potassium nitrate, and deposited in a cold room for a whole day and night. In a cold room, add 500 parts by weight of water, 100 parts by weight of sodium chloride, 3 parts by weight of potassium nitrate, 40 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-4-b, and spices in a cold room. The product was soaked for days, then washed with cold water, wound with string, smoked, cooked, cooled, and packaged according to a conventional method. This product is a high-quality ham with good color and good flavor.
[0092]
Example B-16
<Simmered>
Sanded, acid-treated kelp 250 parts by weight, soy sauce 212 parts by weight, amino acid solution 318 parts by weight and 35 parts by weight β-maltose hydrous crystal-containing powder obtained by the method of Example A-3-b and sugar While adding 20 parts by weight and boiling, 12 parts by weight of sodium glutamate and 8 parts by weight of caramel were added and cooked to obtain a boiled kelp. This product is a low carious boiled eel. Moreover, not only taste and fragrance, but also appetite both in color and gloss.
[0093]
[Example B-17]
<Bath agent>
It mixed in the ratio of 10 weight part of (beta) -maltose hydrous crystal containing powder obtained by the method of Example A-1-b with respect to 1 weight part of yuzu peel juice, and the yuzu peel extract containing powder was obtained. To 5 parts by weight of the powder, 90 parts by weight of baked salt, 2 parts by weight of hydrous crystal trehalose (trademark “Trehha” sold by Hayashibara Corporation), 1 part by weight of silicic anhydride and α-glucosyl hesperidin (sales by Hayashibara Corporation) , Trade name αG hesperidin) 0.5 parts by weight and 2 parts by weight of ascorbic acid 2-glucoside crystal powder (produced by Hayashibara Shoji Co., Ltd.) were mixed to prepare a bath preparation. This product is rich in scent of yuzu and can be used by diluting it 100-10,000 times in hot water for bathing. After bathing, it is a high quality bathing agent that keeps your skin moist and smooth and does not cool down. is there.
[0094]
[Example B-18]
<Cosmetic cream>
2 parts by weight of polyoxyethylene glycol monostearate, 5 parts by weight of self-emulsifying glyceryl monostearate, 5 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-1-b, α-glucosylrutin ( 1 part by weight of Hayashibara Co., Ltd., registered trademark “αG rutin”, 1 part by weight of ascorbic acid 2-glucoside crystal powder (sales by Hayashibara Corporation), 1 part by weight of liquid paraffin, 10 parts by weight of glycerin trioctanoate and preservatives An appropriate amount is dissolved by heating in accordance with a conventional method. To this, 2 parts by weight of L-lactic acid, 5 parts by weight of 1,3-butylene glycol and 66 parts by weight of purified water are added, emulsified with a homogenizer, and further added with an appropriate amount of a perfume and stirred. And a cosmetic cream was produced. This product has antioxidant properties, high stability, and can be advantageously used as a high-quality sunscreen, skin beautifying agent, whitening agent, and the like.
[0095]
Example B-19
<Toothpaste>
Dicalcium phosphate 45 parts by weight, sodium lauryl sulfate 1.5 parts by weight, glycerin 25 parts by weight, Poly 0.5 parts by weight of oxyethylene sorbitan laurate, 10 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-2-b, 0.02 parts by weight of saccharin and 0.05 parts by weight of preservative A toothpaste was obtained by mixing with 13 parts by weight. This product improves taste and does not deteriorate the detergency of the surfactant and has a good feeling after use.
[0096]
Example B-20
<Food edible solid formulation>
100 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-3-b, 200 parts by weight of trehalose hydrous crystal, 200 parts by weight of high maltotetraose-containing powder, 270 parts by weight of powdered egg yolk, 209 parts by weight of skim milk powder Parts 4.4 parts by weight sodium chloride 1.8 parts by
[0097]
Example B-21
<Tablets>
After fully mixing 14 parts by weight of the β-maltose hydrous crystal-containing powder obtained by the method of Example A-4-b and 4 parts by weight of corn starch with 50 parts by weight of aspirin, the mixture was compressed by a tableting machine according to a conventional method. Tablets having a thickness of 5.25 mm and one tablet of 680 mg were produced. This product utilizes the formability of β-maltose hydrous crystal-containing powder, is not hygroscopic, has sufficient physical strength, and is very good in disintegration in water.
[0098]
[Example B-22]
<Sugar-coated tablets>
A core tablet of 150 mg in weight is used as a core, and 40 parts by weight of β-maltose hydrous crystal-containing powder obtained by the method of Example A-4-b, 2 parts by weight of pullulan (Hayashibara Shoji PF-20) , 30 parts by weight of water, 25 parts by weight of talc and 3 parts by weight of titanium oxide and sugar coated until the tablet weight reaches about 230 mg, and then 65 parts by weight of the same β-maltose hydrous crystal-containing powder, pullulan (Co., Ltd. Hayashibara Shoji Co., Ltd. PF-20) Sugar coating using 1 part by weight and 34 parts by weight of water, and then glazing with wax solution to obtain a sugar coated tablet with an excellent glossy appearance. It was. This product has excellent impact resistance and maintains high quality for a long time.
[0099]
【The invention's effect】
As is apparent from the above description, it is pulverized by the spray method of the present invention and contains, in terms of anhydride, maltose of 86% to less than 93% and glucose of 2% or more, and the crystallinity is from 62% to less than 72%. The β-maltose hydrous crystal-containing powder is a maltose isomer containing an α-anomer in maltose of 7% to less than 14%, excellent solubility in aqueous media, excellent storage stability, and fluidity. Good and easy to handle powder. These β-maltose hydrous crystal-containing powders contain a relatively large amount of carbohydrates other than maltose, such as glucose, maltotriose and oligosaccharides having a glucose polymerization degree of 4 or more, such as 7% to less than 14%. Nevertheless, it is easy to manufacture by spraying, it can be manufactured continuously and in a short time, and the powder yield is high, so it is easy to reduce costs.
[0100]
Therefore, the establishment of the present invention allows easy production of β-maltose hydrous crystal-containing powder having excellent solubility in an aqueous medium at low cost, so that not only starch sugar manufacturers but also those who use it. This is advantageous because improvement in workability can be expected, and the industrial significance given to the industry including the corresponding industry is extremely large.
[Brief description of the drawings]
FIG. 1 is a powder X-ray diffraction pattern of a β-maltose hydrous crystal-containing powder having a maltose content of 86.2% in terms of anhydride and a crystallinity of 62.1%.
FIG. 2 is a powder X-ray diffraction pattern of a β-maltose hydrous crystal-containing powder having a maltose content of 91.3% in terms of anhydride and a crystallinity of 70.8%.
FIG. 3 is a powder X-ray diffraction pattern of purified maltose registered trademark “Sanmalto S” showing a maltose content of 95.0% in terms of anhydride and a crystallinity of 74.5%.
FIG. 4 is a powder X-ray diffraction pattern of a reagent β-maltose hydrous crystal having a maltose content of 99.6% in terms of anhydride and a crystallinity of 82.6%, under the trade name “Maltose HHH”.
FIG. 5 is a powder X-ray diffraction pattern of anhydrous α-maltose crystal having a maltose content of 98.5% in terms of anhydride and a crystallinity of 76.3%.
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