JP4849384B2 - Thermoplastic trehalose molding, its production method and use - Google Patents
Thermoplastic trehalose molding, 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、熱可塑性トレハロース成形物とその製造方法並びに用途に関し、詳細には、熱可塑性トレハロース成形物とこれをトレハロース溶液を用いて成形することを特徴とする当該熱可塑性トレハロース成形物の製造方法並びに当該成形物を加熱して流動可能とし、成形することを特徴とするトレハロース含有成形物の製造方法、加えてトレハロース溶液の付着力低減方法とその用途に関する。
【０００２】
【従来の技術】
トレハロースは、「化学工業」１９９９年６月号５７乃至６５頁の記載にも見られるように、近年、澱粉を原料に大量に生産され、食品工業を中心に広く利用されるようになってきた。しかしながら、トレハロースを成形して利用する方法は限られている。例えば、結晶又は粉末状のトレハロースを賦形剤又は結合剤などと混合し、錠剤に成形して利用するか、又は結晶又は粉末状のトレハロースをこれを越える量の他の糖質と共に水に加熱溶解し、これを煮詰めて型に流し込み、冷却して、キャンディーに成形して利用する程度である。しかも、これらの方法は、比較的特殊な装置、高度な技術を必要としているにもかかわらず、得られる成形物の形状が単調に過ぎる。随意な形状のトレハロース含有成形物、例えば綿状成形物の製造は困難で、市販の結晶又は粉末状トレハロースは、綿菓子製造機にかからず、氷砂糖を用いた場合のようには上手く綿状成形物が製造できないのが実状である。トレハロースを用いて、随意な形状の成形物を容易に製造する方法が望まれる。
【０００３】
【発明が解決しようとする課題】
本発明は、トレハロースを用いて、随意な形状の成形物を容易に製造することを課題とする。
【０００４】
【課題を解決するための手段】
本発明者は、上記課題を解決するために、トレハロース成形物の製造方法につき、鋭意研究してきた。その結果、トレハロース高含有のガラス質成形物は、他の糖質の場合よりも保存安定性が良好であること、熱可塑性を有していること、耐熱性が良好であること、加熱して流動可能にしたものを随意な形状に成形することの容易であること、更には、これら性質を利用して繰り返し成形することも容易であることを見出し、本発明を完成した。即ち、本発明は、トレハロース高含有のガラス質成形物が優れた熱可塑性を有し、安定な成形物であることを見いだしたことに基づき、熱可塑性トレハロース成形物を提供し、又、トレハロース溶液の付着力低減能を有する物質を含有し、水分を約８．３ｗ／ｗ％（以下、本明細書では、特に断らない限り、ｗ／ｗ％を％と略記する。）以下含有しているトレハロース溶液、又は、付着力低減能を有する物質を含有せずに、水分を約２．４％以下含有しているトレハロース溶液を用いて成形することを特徴とする当該熱可塑性トレハロース成形物の製造方法を提供し、又、当該熱可塑性トレハロース成形物を加熱して流動可能とし、そのまま随意の形状に成形するか、又はこれを他の物質と共に用いて随意の形状に成形することを特徴とするトレハロース含有成形物の製造方法を提供し、更に、トレハロース水溶液を加熱濃縮するに際し、トレハロース溶液の付着力低減能を有する物質を共存させ水分を約８．３％以下にせしめるか、又は共存せしめないままで水分を約２．４％以下にせしめることを特徴とするトレハロース溶液の付着力低減方法とこの方法を利用し得られる当該熱可塑性トレハロース成形物を確立して前記課題を解決する。
【０００５】
【発明の実施の形態】
本発明で使用するトレハロースは、別名α、α―トレハロースであり、その由来は問わない。例えば、特開平７−２４６０９７号公報に記載される酵母からのトレハロース、特開昭５８−２１６６９５号公報に記載されるマルトースからのホスホリラーゼ法によるトレハロース、特開平７−１７０９７７号公報、特開平７−２１３２８３号公報等に記載される澱粉からの酵素糖化法によるトレハロース等各種トレハロースが適宜採用できる。市販の高純度トレハロース含水結晶、高純度トレハロース無水結晶等を使用することも適宜採用できる。例えば、株式会社林原商事が販売している高純度トレハロース含水結晶製品（登録商標『トレハ』）を使用することも有利に実施できる。
【０００６】
また、本発明の熱可塑性トレハロース成形物は、室内の温度、湿度環境条件下で保存安定性が良好で、経日変化を起こしにくく、しかも、これを加熱して溶融させ流動可能とし、随意の形状に容易に成形でき、成形、溶融を二度以上繰り返してもその性質に変化がなく、成形物の再生も容易に行えるものである。
【０００７】
本発明の熱可塑性トレハロース成形物は、トレハロース溶液の付着力低減能を有する物質を含有し水分を約８．３％以下、望ましくは約４．４％以下含有しているか、又は、当該付着力低減能を有する物質を含有せずに水分を約２．４％以下、望ましくは２．０％以下を含有する成形物である。これらの成形物を加熱し、可塑化してくる温度を調べたところ、品温約７０乃至９０℃にすると柔らかくなり、品温約９０℃以上、高いものでも約１００乃至１２０℃にすると流動可能となることが判明した。その製造方法としては、適宜の方法が選択できる。例えば、トレハロースの含水結晶又は無水結晶を、そのまま又は適量の加湿をして、加熱、溶融、望ましくは品温としてできるだけ高温、好ましくは、１６０℃を越える温度、更に望ましくは約１６５乃至２３０℃、更に望ましくは、約１７０乃至２２０℃で加熱溶融させ、これをガラス質状態に成形する方法で成形すればよい。また、例えば、前記の各種酵素反応により調製したトレハロース水溶液や、これを水素添加して調製したトレハロース水溶液、更にはトレハロース含水結晶を水に溶解したトレハロース水溶液を、望ましくは水分３０％以上、更に望ましくは水分３０％以上５０％未満、換算すれば、トレハロースを濃度７０％未満、更に望ましくは約５０％以上７０％未満含有するトレハロース水溶液を、常圧又は減圧下で加熱濃縮して高濃度溶液とし、これをガラス質状態に成形する方法で製造すればよい。
【０００８】
このトレハロース水溶液を加熱濃縮する場合には、その水分と溶液温度とは、密接に関係しており、例えば、常圧の場合、水分１５．３％で温度１１５℃であり、以下、同様に９．９％で１２５℃、５．２％で１４５℃、２．４％で１６５℃、１．１％で１８５℃の関係にある。この関係を求める過程で、加熱濃縮時の溶液の水分（溶液の温度）の違いによって溶液の付着力が大きく変動するという意外な現象を見出した。即ち、加熱濃縮して、溶液の水分が約１０％を下回ると付着力が高まり、とりわけ、水分約８．３％以下では付着力が著しく高まり、更に濃縮して水分約４．４乃至３．０％で付着力はピークに達し流動性が弱まり、更に加熱濃縮を続け、水分３％未満になると逆に付着力が低下し、更に水分約２．４％以下、望ましくは約２．０％以下になるとその付着力、流動性も成形時の作業性に支障がない程に改善されることが判明した。
【０００９】
この異常に高まった付着力を低減させ作業性を改善することを目的に鋭意検討したところ、付着力低減能を有する物質の共存が好適であり、これにより、高純度トレハロース溶液の付着力が大幅に低減され、加熱濃縮時の泡立ちが低くなり、作業性が向上し、成形物の製造も容易となることが判明した。
【００１０】
付着力低減能を有する物質としては、前記トレハロース溶液の付着力が低減できる物質であればよく、例えば、脂質、炭化水素などの疎水性物質や、糖質、ポリアルコールなどの親水性物質、更には、疎水性及び親水性の両性質を有している乳化剤などから選ばれる有機物質が好適であり、その使用方法は、無水物換算で、トレハロースに対して４０％未満、望ましくは３０％未満の量を共存させるのが好適である。
【００１１】
脂質としては、油脂、脂肪酸など、炭化水素としては、約１００乃至２３０℃で液状を示す、例えば、アルカン、アルケン、複素環化合物など、糖質としては、単糖類、トレハロース以外のオリゴ糖、単糖アルコール、二糖アルコールなど、ポリアルコールとしては、グリセリン、ジエチレングリコール、プロピレングリコールなど、乳化剤としては、蔗糖脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、レシチンなどから１種又は２種以上のものが適宜選ばれる。
【００１２】
以上述べてきたように、トレハロース溶液は、望ましくは、前記の付着力低減能を有する物質を共存させる付着力低減方法を採用して、所定の水分、望ましくは水分約８．３％以下に濃縮し、これをガラス質状態に成形するか、又は、当該付着力低減能を有する物質を共存させないで、望ましくは水分約２．４％以下に濃縮し、これをガラス質状態に成形して当該熱可塑性トレハロース成形物を製造すればよい。成形方法としては、公知の各種の方法、例えば、スタンピング成形、カッティング成形、大気中成形、水中又は油中成形、押出成形、加圧成形、とりわけ二軸式押出成形などが有利に実施できる。
【００１３】
このようにして得られる熱可塑性トレハロース成形物は、その良好な保存安定性、熱可塑性を保つ上で、できるだけトレハロース含量の高いものが望ましく、通常、無水物換算でトレハロースを６０％を越える量含有するのが好適であり、望ましくは約７０％以上、更に望ましくは約８０％以上、更に望ましくは９０％以上含有しているものが好適である。
【００１４】
熱可塑性トレハロース成形物の形状としては、通常、これを原料とし、加熱して流動可能とし随意の形状に成形する際に、公知の各種成形機又は成形装置に容易に適用できるものが望ましく、これら成形機又は成形装置を利用して、容易に加熱し、必要に応じて加圧又は減圧して、容易に溶融させ流動可能とし、随意の形状に成形できるものが好適である。
【００１５】
この具体例としては、通常、短径として約０．１乃至２０ｍｍ、望ましくは約２乃至１５ｍｍから選ばれる長さを有し、長径として短径と同等以上の長さを有するものが好適である。形状としては、粒、球、半球、楕円球、短棒、半円錐、短角錐、立方体、直方体、短管、繊維などが有利に利用できる。一般的には、ペレットと称される形状が好適である。
【００１６】
このようにして得られた熱可塑性トレハロース成形物は、通常、トレハロース溶液の付着力低減能を有する物質を含有し水分を約８．３％以下、望ましくは約４．４％以下含有しているか、又は当該付着力低減能を有する物質を含有せずに、水分を約２．４％以下、望ましくは約２．０％以下含有しており、併せてトレハロースを無水物換算で６０％を越える量、望ましくは約７０％以上を含有するトレハロース成形物であって、しかも、トレハロースが非晶質で透明乃至半透明で、耐湿性、耐熱性、耐酸性、耐アルカリ性、保存安定性に優れ、取扱い容易である。当該熱可塑性トレハロース成形物の用途としては、例えば、これを少量の熱水に溶解して、トレハロース高含有ペースト状物を調製することや、更にこのペースト状物を他の機能性物質や有効成分と混合して用いることや、更にはこの混合物にトレハロースの結晶核などを共存させ、トレハロースを起晶させて粉末化を容易にする粉末化基剤などとして用いたりすることもできる。
【００１７】
しかし、最も重要な用途は、熱可塑性を利用する用途である。即ち、熱可塑性トレハロース成形物は、これを再び加熱して溶融させ流動可能とし、これをそのまま随意の形状に成形してもよいし、又、これを他の物質と共に用いて、例えば、これを他の物質に被覆、混合、固着、挿入、封入させるなどして、随意の形状に成形してトレハロース含有成形物を得ることも有利に実施できる。
【００１８】
加熱する条件としては、付着力低減能を有する物質の種類や共存の程度によって異なるものの、熱可塑性トレハロース成形物が溶融して柔らかくなり、望ましくは流れる状態、換言すれば、流動可能となり、随意の形状に成形できればよく、柔らかくなる温度としては、通常、品温約７０乃至９０℃、流動可能温度としては、品温約９０℃以上、望ましくは約１００乃至１２０℃又はこれ以上に加熱すればよい。具体的には、流動可能温度は、通常、当該熱可塑性トレハロース成形物の水分が比較的高い約８．３％以下で２．４％を越える場合、比較的低く、通常、約９０℃以上、望ましくは約１００乃至１６０℃から選ばれ、その水分が比較的低い約２．４％以下の場合、比較的高く、通常、約１００℃以上、望ましくは約１１０乃至２３０℃から選ばれる温度に加熱すればよい。
【００１９】
他の物質と共に用いて成形する際には、例えば、当該熱可塑性トレハロース成形物を、予め他の物質と混合し、次いで、加熱して、流動可能として随意の形状に成形することも、又、当該熱可塑性トレハロース成形物だけを予め加熱して流動可能とし、次いで他の物質と混合して成形することも適宜選択できる。必要ならば、加湿するか、又は少量の水を加えて、溶融温度を下げたり、混和を促進したりすることもできる。
【００２０】
他の物質としては、共に用いて随意の安定な形状に成形できるものであればいずれも有利に用いることができる。即ち、化学工業分野をはじめとする本発明の成形物が利用される個々の分野、例えば、飲食品分野、化粧品分野、医薬品分野、農水畜産分野、プラスチック工業、家庭用品などの分野において通常用いられる添加物を含む材料ないしは素材であって、共に用いて安定な形状に成形できるものであればいずれでもよい。詳細には、上記の分野から選ばれる１又は２以上の分野で通常用いられる、例えば、甘味料、フィリング剤、着色剤、発色剤、発酵調整剤、着香料、香料、芳香剤、強化剤、膨張剤、保存料、殺菌料、酸化防止剤、抗酸化剤、漂白剤、糊料、安定剤、乳化剤、軟化剤、品質改良剤、調味料、香辛料、光沢剤、苦味料、酸味料、食品製造用剤、酵素剤、ガムベース、界面活性剤、可塑剤、滑沢剤、可溶化剤、還元剤、緩衝剤、基材、吸着剤、矯味剤、結合剤、懸濁剤、コーティング剤、潤滑剤、潤滑調整剤、充填剤、消泡剤、清涼化剤、接着剤、増強剤、咀嚼剤、糖衣剤、等張化剤、粘着剤、粘着増強剤、粘稠剤、粘稠化剤、発炎抑制剤、発熱剤、発泡剤、皮膚保護剤、賦形剤、分散剤、ｐＨ調節剤、崩壊剤、崩壊補助剤、防錆剤、防湿剤、防腐剤、防黴剤、保存剤、無痛化剤、ビタミン剤、抗生物質、化学療法剤、アレルギー用剤、抗ヒスタミン剤、鎮痛剤、鎮痒剤、収斂剤、消炎剤、ステロイド剤、ホルモン剤、強心剤、歯科・口腔用剤、止血剤、紫外線吸収剤、除草剤、熱可塑性樹脂、合成樹脂、晶出防止剤、劣化防止剤、老化防止剤、焼け防止剤、樹脂硬化剤、凝固剤、起泡剤、気泡安定剤、帯電防止剤、加硫剤などから目的に応じて適宜選択することができる。例えば、飲食品分野でより具体的に述べれば、例えば、澱粉、アミロース、アミロペクチン、α化澱粉、デキストリン、難消化性デキストリン、澱粉誘導体、プルラン、ペクチン、アルギン酸、多糖類、食物繊維、単糖類、オリゴ糖、機能性オリゴ糖、糖アルコールなどの糖質、カゼイン、ゼラチン、コラーゲン、アルブミン、ミオシンなどの蛋白質、ポリペプチド、オリゴペプチド、アミノ酸、油脂、脂肪酸、ミネラルなどが挙げられる。更には、農水畜産物、例えば、米、大麦、小麦、とうもろこし、きび、あわ、大豆、銀杏、アーモンドなどの種実なども挙げられる。
【００２１】
このようにして他の物質と共に用いて成形し得られるトレハロース含有成形物に含まれるトレハロースは、通常、前記ビタミン、脂質、蛋白質、薬効物質、生理活性物質などの比較的不安定な機能性物質や有効成分の安定性を向上することから、そのトレハロース含量が高い程望ましく、一般的には、表面を被覆する成形物の場合にその含量が比較的少なく、均一に混合し全体を固着成形させるような場合にはその含量が比較的多い。随意の形状に成形する必要があることから、通常、熱可塑性トレハロース成形物を他の物質に対して、無水物換算で、約１．０％以上、望ましくは、約２．０％以上、より望ましくは約５．０％以上、更に望ましくは約１０％以上が好適である。成形物の形状としては、粒、棒、板、シート、フィルム、管、積層、スポンジなどの点、線、面、立体の各種形状の成形物が適宜選ばれる。
【００２２】
これら成形物を成形する方法は、目的とする形状によって、適宜の方法が採用できる。公知の成形方法、例えば、スタンピング成形、カッティング成形、射出成形、押出成形、吹込成形、板成形、注型成形、圧縮成形、加圧成形、カレンダ成形、積層成形、被膜成形、回転成形、吹付成形、固着成形、膨化成形、発泡成形などが有利に実施できる。
【００２３】
このようにして、他の形状に変換して得られるトレハロース含有成形物は、共に用いる他の物質やこれに含まれる機能性物質や有効成分などによって、例えば、飲食品、化粧品、医薬品、農水畜産用品、徐崩性プラスチック、生分解性成形物、家庭用品などとして利用される成形物に好適である。
【００２４】
以下、本発明を実験で説明する。
【００２５】
【実験１】
〈糖質溶液の煮詰温度（水分）による溶液の付着性とその成形物の保存安定性に与える影響〉
糖質として、非還元性の糖質、即ちマルチトール無水結晶又はトレハロース２含水結晶を用意し、手鍋にこれら糖質のいずれかをとり、これに水を加えて加熱し、それぞれ濃度５０％の溶液を調製し、これら糖質溶液の加熱を続け沸騰させ、糖質溶液を煮詰めた。糖質溶液が、１２０℃、１３０℃、１４０℃、１５０℃、１６０℃、１７０℃、１８０℃、１９０℃の各温度に達した時、糖質溶液にほぼ垂直に、直径４ｍｍのガラス棒を液面から３ｃｍの深さまで差込み、そのまま約３秒間保持した後、緩やかに引き上げた。ガラス棒に付着した糖質溶液の重量は、糖質溶液が付着したガラス棒の重量から、ガラス棒のみの重量を差し引くことによって、算出した。また、それぞれの煮詰め液を小型成形器（デポジッター）にサンプリングし、室温まで冷却させ、形状が、長さ２０ｍｍ、幅１５ｍｍ、厚さ５ｍｍの成形物の試料を得た。この製造当日の試料を用いて、水分を測定した。水分含量は、常法により、珪藻土法（温度８０℃、５０ｍｍＨｇ以下の減圧下で一晩乾燥）で測定した。
【００２６】
また、同じ試料をシャーレに入れて、相対湿度約７０％で、温度約２５℃の室内に１０日間放置後の固着性の有無を観察した。
【００２７】
固着性は、試料が吸湿し、シャーレに固着する程度を調べ、有、無の２段階に分けて示し、保存安定性の目安とした。結果は、表１に示した。
【００２８】
【表１】
表１から明らかなように、トレハロースの場合、意外にも温度１２０℃（溶液の水分約１２％）から１６０℃（溶液の水分約３．０％）まで、ガラス棒に付着するトレハロース溶液の重量は著しく増加し、この温度を越えると、水分が減少する、換言すれば濃度が高まるにもかかわらず、温度１９０℃まで付着量が減少してくることがわかった。即ち、トレハロース溶液の付着力は、温度１３０℃（溶液の水分約８．３％）以上で著しく高まり、温度約１５０℃乃至１６０℃（溶液の水分約４．４乃至３．０％）でピークに達し、１６０℃を越える（溶液の水分約３．０％未満になる）とその付着力が漸次低下することが判明した。
【００３０】
なお、対照のマルチトールの場合、付着量の僅かな増加と減少（温度１２０℃から１５０℃までの増加と、その後の温度１９０℃までの減少）が観察されたが、その増減の程度は、トレハロースの場合と比べ、微少であることが判明した。以上のことから、トレハロース溶液を煮詰める際、温度１６０℃までは急激に付着力が上昇し、成形時の作業性に悪影響を及ぼすので、これを改善する必要のあることが判明した。一方、このトレハロース溶液を温度１６５℃以上（溶液の水分約２．４％以下）の高温に煮詰めると付着力が低下し、流動性が著しく改善され、トレハロース溶液を取扱う際の作業性が極めて容易になることも判明した。トレハロースの場合はマルチトールとは違って、成形物は、相対湿度７０％の室温下に保存しても経時変化が少なく、耐湿性に優れ、保存安定性良好であることが判明した。
【００３１】
【実験２】
〈付着力の低減方法〉
トレハロース２含水結晶５５０重量部をステンレス製の手鍋に入れ、そこへ付着力低減能を有する物質として、サフラワー油５０重量部、サラダ油５０重量部、マルチトール無水結晶１５０重量部、又は、ラクチトール１含水結晶１５８重量部から選ばれるいずれか１種を加え、更に水４５０重量部を加えた後、加熱しながら糖質を完全に溶解させた。更に、加熱を続け沸騰させ、糖質溶液を煮詰めた。糖質溶液が、１２０℃、１３０℃、１４０℃、１５０℃、１６０℃、１７０℃、１８０℃の各温度に達した時、実験１と同様の方法で、ガラス棒に付着する糖質溶液の重量を測定した。また、それぞれの煮詰め液を用いて、実験１と同様の方法に従い、成形物を製造し、その製造当日の材料を用いて水分を測定した。結果は、表２に示した。なお、糖質溶液中のトレハロース含量は、無水物換算で算出し、表２に併せて示した。
【００３２】
【表２】
表２から明らかなように、トレハロース単独の場合の温度１２０℃から１６０℃までの付着力の増加、中でも温度１３０℃（溶液の水分約８．３％）から１６０℃（溶液の水分約３．０％）までの急激な付着力の増加は、サフラワー油、サラダ油、マルチトール、ラクチトール共存下のいずれの場合も、著しく抑制され、その付着力が激減することが判明した。とりわけ、温度約１５０℃（溶液の水分約４．４％）乃至１６０℃（水分約３．０％）における付着力のピークは、いずれの場合も顕著に低減し、その付着力が激減することが判明した。
【００３４】
更に、温度１６０℃を越す高温での付着力も、これら付着力低減能を有する物質の共存下では、トレハロース単独の場合と比べ、その付着力はいずれも低いことが判明した。
【００３５】
以上のことから、トレハロース溶液を煮詰め中に認められた温度１３０℃（溶液の水分約８．３％）から１６０℃（溶液の水分約３．０％）までの急激な付着力の上昇は、サフラワー油、サラダ油などの油脂、マルチトール、ラクチトールなどの糖質など付着力低減能を有する物質を煮詰の際に共存させることにより、著しく抑制され、とりわけ、温度約１５０℃（溶液の水分約４．４％）乃至１６０℃（溶液の水分約３．０％）での付着力のピークは、顕著に低減し、更に、温度１６０℃を越す高温煮詰においても、これら物質がトレハロース溶液の付着力を一層低下させ、流動性を著しく改善することがわかり、熱可塑性トレハロース成形物の成形時の作業性を顕著に改善できることが判明した。
【００３６】
以下、本発明の熱可塑性トレハロース成形物を実施例Ａで、その用途例としてトレハロース含有成形物を実施例Ｂで説明する。
【００３７】
【実施例Ａ−１ 短棒状成形物】
高純度トレハロース含水結晶製品（株式会社林原商事販売、登録商標『トレハ』）１１０重量部を溶解タンクにとり、水９０重量部を加えて加熱溶解し、これを加熱濃縮し、溶液温度約１９０℃（水分約０．９％）まで煮詰めて溶液の付着力を低減させた後、これを押出成形機にかけて、成形し、室温まで放冷して直径約２ｍｍ、長さ約４ｍｍの短棒状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃に再加熱して流動可能とし、随意な他の形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用い、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、このペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００３８】
【実施例Ａ−２ 楕円球状成形物】
高純度トレハロース含水結晶製品を実施例Ａ−１と同様に加熱溶解し、これを加熱濃縮し、付着力が高まり始める液温が１１０℃を越える付近で、無水物換算で、トレハロースに対し約５％のオリーブ油を加え、溶液の付着力を低減させて加熱濃縮を続け、溶液温度約１７０℃（水分約２．０％）まで煮詰め、これをスタンピング成形機にかけて、長さ約１５ｍｍ、楕円球状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃に再加熱して流動可能とし、随意な他の形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用いて、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、ペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００３９】
【実施例Ａ−３ 短四角柱状成形物】
高純度トレハロース含水結晶製品を実施例Ａ−１と同様に加熱溶解し、これを加熱濃縮し、付着力が高まり始める液温が１１０℃を越える付近で、無水物換算でトレハロースに対して約３％のプロピレングリコールを加え、溶液の付着力を低減させて加熱濃縮を続け、溶液温度約１６５℃（水分約２．４％）まで煮詰め、これをカッティング成形機にかけて、一辺が約５ｍｍ、長さ約１０ｍｍの短四角柱状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃以上に再加熱して流動可能とし、随意な他の形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用いて、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、このペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００４０】
【実施例Ａ−４ 半球状成形物】
特開平８−７３４８２号公報に開示される方法に従って、リゾビウム・スピーシーズ Ｍ−１１（ＦＥＲＭ ＢＰ−４１３０）の変異株をファーメンターで栄養培地に約７０時間培養した。培養後、ＳＦ膜を用いて除菌濾過し、約１００ｌの培養濾液を回収し、更に、その濾液をＵＦ膜濃縮し、非還元性糖質生成酵素（約４１０単位／ｍｌ）とトレハロース遊離酵素（約４９０単位／ｍｌ）とを含む濃縮酵素液約５ｌを回収した。とうもろこし澱粉を濃度約３３％の澱粉乳とし、これにα−アミラーゼを作用させてＤＥ約４の液化溶液を得、次いで、前記方法で調製した非還元性糖質生成酵素とトレハロース遊離酵素とを含む濃縮酵素液を澱粉グラム当たり０．０２ｍｌ、イソアミラーゼを澱粉グラム当たり５００単位及びシクロマルトデキストリン・グルカノトランスフェラーゼを澱粉グラム当たり５単位加え、ｐＨ６．２、温度４０℃で４８時間反応させた。本反応液を加熱失活し、次いで、グルコアミラーゼを基質グラム当たり１０単位加え、ｐＨ５．０、温度５０℃で１０時間反応させた。本反応液には、固形物当たりトレハロースを８５．６％含有していた。本反応液を加熱失活し、常法に従って、脱色、脱塩して精製し、濃縮して濃度４５％のシラップを得た。本トレハロース高含有低還元性糖質シラップを、常法に従って、水素添加し、脱色、脱塩して精製し、濃縮して、無水物換算でトレハロースを約８５％、残りは主としてソルビトールを含有するシラップを得た。これを加熱濃縮し、溶液温度約１８０℃（水分約１．３％）まで煮詰めて溶液の付着力を低減させ、これを細管を通してサラダ油中に滴下して冷却固化させ、底面直径約８ｍｍの半球状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃に再加熱して流動可能とし、随意な形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用いて、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、ペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００４１】
【実施例Ａ−５ 繊維状成形物】
トレハロース含水結晶を電気炉で約２００乃至２１０℃（水分約０．５％以下）に加熱し、溶融させ、得られる溶液を、この電気炉の下部に設けた取り出し口から流出させつつ、これに空気を吹き付けて太さ約０．１乃至０．２ｍｍの繊維状物とし、これを更に破砕して長さ約２０ｍｍ以下の短繊維状物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃に再加熱して流動可能とし、随意な形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用いて、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、ペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００４２】
【実施例Ａ−６ 短棒状成形物】
実施例Ａ−３の方法で得た熱可塑性トレハロース成形物を、更に約１２０℃に加熱し押出成形機にかけて、直径約２ｍｍ、長さ約４ｍｍの短棒状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃に再加熱して流動可能とし、随意な形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用いて、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、このペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００４３】
【実施例Ａ−７ 楕円球状成形物】
高純度トレハロース含水結晶製品１００重量部及び高純度マルチトール無水結晶製品（株式会社林原商事販売、登録商標「マビット」１０重量部を溶解タンクにとり、水９０重量部を加えて加熱溶解し、これに乳化剤（蔗糖ステアリン酸エステル）０．２重量部を加えて加熱濃縮し、溶液温度１５０℃（水分約４．３％）まで煮詰め、これをスタンピング成形機にかけて、長さ約１５ｍｍ、楕円球状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約９０乃至１６０℃に再加熱して流動可能とし、随意な他の形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用いて、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、このペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００４４】
【実施例Ａ−８ 短棒状成形物】
高純度トレハロース含水結晶製品９５重量部及びパラチニット１８重量部を溶解タンクにとり、水６３重量部を加えて加熱溶解し、これを濃縮器に入れ、まず常圧下で１２５℃まで煮詰め、次いで減圧下でこの温度を維持しつつ加熱濃縮し、水分約１．０％まで煮詰め、これを、実施例Ａ−１と同様に押出成形機にかけて成形し、室温まで放冷して、直径約２ｍｍ、長さ約４ｍｍの短棒状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃に再加熱して流動可能とし、随意な他の形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用い、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、このペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００４５】
【実施例Ａ−９ 短棒状成形物】
高純度トレハロース含水結晶製品８０重量部及び高純度マルチトール無水結晶製品２０重量部を混合し粉末化した後、これをこの粉末重量の約２０倍量のサラダ油（約１８０℃）に入れ、加熱し、溶融し、水分約１．３％とし、これを取り出して、カッティング成形機にかけ、直径約５ｍｍ、長さ約８ｍｍの短棒状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃に再加熱して流動可能とし、随意な他の形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用い、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、このペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００４６】
【実施例Ａ−１０ 円盤状成形物】
高純度トレハロース含水結晶８５重量部及び還元水飴（株式会社林原商事販売、商品名『ＨＳ−３００』）１５重量部を均一に混合し、これを直径約８ｍｍ、深さ約５ｍｍのくぼみを複数有しているテフロン製型枠に詰め、これを電子レンジにかけて加熱し、溶融し、水分約２．０％まで煮詰め、次いで、放冷して、直径約８ｍｍ、厚さ約３ｍｍの円盤状の熱可塑性トレハロース成形物を得た。本品は、無色で透明乃至半透明な実質的に非晶質な成形物で、室内環境での保存安定性が良好で、熱可塑性を有していることから、これを品温約１００乃至２３０℃に再加熱して流動可能とし、随意な他の形状の成形物に変化させることも、又、これを各種機能を有する他の物質と共に用い、随意な形状の成形物に仕上げることも有利に実施できる。また本品は、比較的少量の熱水に溶解させてトレハロース含有ペーストを調製したり、更に、このペーストを非晶質のままで利用することも、又は結晶化させて用いる粉末化基剤として利用することも有利に実施できる。
【００４７】
【実施例Ｂ−１ 綿状成形物】
実施例Ａ−７の方法で得た熱可塑性トレハロース成形物１重量部に、レモン濃縮果汁０．０５重量部を均一に噴霧して付着させ、乾燥した後、これを綿菓子製造機にかけて約１００℃以上に加熱溶融し綿菓子を製造した。本品は、従来の砂糖を用いた綿菓子が経時的にその体積を縮小し易く、また酸味も付けられない欠点を有しているのとは違って、経時変化の無い酸味の効いたレモン風味のトレハロース含有綿菓子である。
【００４８】
【実施例Ｂ−２ 被覆成形物】
小麦粉１００重量部、イースト２重量部、砂糖５重量部、マルトース１重量部及び無機フード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分間熟成し、得られたパン生地を手で丸めた。この表面に実施例Ａ−４の方法で得た熱可塑性トレハロース成形物をパン生地に対し、無水物換算で、約２％を部分的に押し込んだ後、常法に従って約１８０℃で焼き上げた。本品は、表面に溶融変形した趣きのあるトレハロース含有被覆成形物を配置したユニークなパンであり、又色相、すだちともに良好で適度な弾力、温和な甘味を有する高品質のパンである。
【００４９】
【実施例Ｂ−３ 被覆成形物】
バター６０重量部、砂糖２０重量部、マルトース２０重量部及びトレハロース２含水結晶の粉末１０重量部をよく練り合わせ、これに鶏卵４０重量部を加えてクリーム状にする。更に、薄力粉１４０重量部、コーンスターチ１０重量部及びプルラン３重量部を加えて混合し、得られたクッキー生地を天板上に菊口金で絞り出して花模様に成形し、この上に、実施例Ａ−５の方法で得た熱可塑性トレハロース成形物をクッキー生地に対し、無水物換算で約１％付着させて、オーブンにより約１７０℃で１５分間焼き上げた。この製品は、溶融変形した趣きのあるトレハロース含有被覆成形物とクッキー生地の肌別れもなく、充分接着しており、又、風味、口当たりも良好であった。
【００５０】
【実施例Ｂ−４ 顆粒状成形物】
実施例Ａ−２の方法で得た熱可塑性トレハロース成形物１５重量部及びプレーンヨーグルト２重量部と無水トレハロース粉末１０重量部との混合粉末を、約１００℃に加熱し二軸式押出成形機にかけてトレハロース含有顆粒状成形物を製造した。本品は、ヨーグルト風味の甘味成形物で、プレミックス、冷菓、ケーキなどの製菓材料、経管流動食などの治療用栄養剤として、更には、例えば、マーガリンホイップクリーム、スプレッド、チーズケーキ、ゼリーなどに含有せしめヨーグルト風味の製品にするなど有利に利用できる。
【００５１】
【実施例Ｂ−５ 台形状成形物】
実施例Ａ−３の方法で得た熱可塑性トレハロース成形物３０重量部、α−グルコシル−Ｌ−アスコルビン酸１重量部、α−グルコシルヘスペリジン１重量部、硫酸ナトリウム１重量部及び適量の着色料、香料を溶解したアルコール水１重量部を、約１００℃に加熱し加圧成形機にかけてトレハロース含有台形状成形物を製造した。本品は、１個約１０ｇで、美肌剤、色白剤として浴用に好適であり、浴槽に沈めて利用すればよい。本品は、入浴用の場合と同様に、洗顔用水、化粧水などに溶解して利用することも有利に実施できる。
【００５２】
【実施例Ｂ−６ 楕円球状成形物】
実施例Ａ−２の方法で得た熱可塑性トレハロース成形物５００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１．８５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重量部の混合物を、約１００℃に加熱し加圧成形機にかけてトレハロース含有楕円球状成形物を製造した。本品は、栄養剤成形物として好適であり、１球約５ｇで、口で溶かして利用され、病人の治療用栄養剤として、又、健常人の健康の維持、増進などに有利に利用される。
【００５３】
【実施例Ｂ−７ 顆粒状成形物】
実施例Ａ−１の方法で得た熱可塑性トレハロース成形物１０重量部及び炭酸ナトリウム粉末１重量部の混合物を、約１００℃に加熱し二軸式押出成形機にかけてトレハロース含有顆粒状成形物を製造した。本品は、炭酸ナトリウム粉末の飛散の恐れのない取扱い容易なｐＨ調節剤として、各種用途に幅広く利用できる。
【００５４】
【実施例Ｂ−８ 短管状成形物】
実施例Ａ−２の方法で得た熱可塑性トレハロース成形物１００重量部、魚粉２００重量部、α化澱粉２０重量部、プルラン３重量部及び水１０重量部の混合物を、約１１０℃に加熱し押出成形機にかけて短管状成形物とし、これを約１０％セラックアルコール溶液に浸漬し、直ちに引き上げて熱風で乾燥して、トレハロース含有短管状成形物を製造した。本品は、水を汚染することの少ない飼料で、淡水、海水を問わず、養殖用、観賞用、魚介類、甲殻類などの飼料として好適である。
【００５５】
【実施例Ｂ−９ 植木鉢】
実施例Ａ−６の方法で得た熱可塑性トレハロース成形物１００重量部とグリセリン１５重量部及び古紙パルプ５０重量部の混合物を、約１５０℃に加熱し射出成形機にかけて植木鉢を成形し、溶融ワックスに浸漬し、放冷してトレハロース含有植木鉢を製造した。本品は、徐崩性、生分解性であるため、移植用植木鉢として好適であり、鉢をはずすことなく移植することができるので、植え痛みがない。
【００５６】
【実施例Ｂ−１０ 短棒状成形物】
実施例Ａ−１の方法で得た熱可塑性トレハロース成形物６０重量部、サンゴ粉末３０重量部、α−グルコシルルチン０．１重量部、及びコーンスティープリカー２重量部の混合物を、約１１０℃に加熱し押出成形機にかけて短棒状のトレハロース含有植物活性化剤成形物を得た。本品は、容器が不要で、取り扱いが容易であり、使用時に適度な速度で溶解、崩壊するので持続性植物活性化剤として好適である。
【００５７】
【実施例Ｂ−１１ ゴルフティー】
実施例Ａ−４の方法で得た熱可塑性トレハロース成形物１０重量部、酸性白土４重量部及びプルラン０．５重量部の混合物を、約１６０℃に加熱し射出成形機にかけてゴルフティーを成形し、約１０％セラックアルコール溶液に浸し、乾燥して製品を得た。本品は、ショットにより、小塊に破壊され、雨水で徐々に崩壊し、生分解される。従って、ゴルフ場の美観を損なわず、環境も破壊しない。また、適度なトレハロースの散布は、ゴルフ場の芝の生育を活性化する。
【００５８】
【実施例Ｂ−１２ フィルム状成形物】
低密度ポリエチレン９２重量部、実施例Ａ−３の方法で得た熱可塑性トレハロース成形物８重量部、ステアリン酸カルシウム０．０５重量部、酵素処理ルチン０．５重量部及び茶抽出物０．５重量部の混合物を、約１２０℃に加熱し加圧成形機にかけて短棒状成形物とし、次いで、これを常法に従って、約１３０℃に加熱し押出成形機（インフレーション法）にかけてフィルム状成形物を製造した。本品は、花、野菜、果物、肉、魚など生鮮食品の鮮度保持用フィルムとして有利に利用できる。
【００５９】
【実施例Ｂ−１３ 直方体成形物】
実施例Ａ−７の方法で得た熱可塑性トレハロース成形物１５０重量部を約１００℃に加熱し、これにゼラチン１３重量部を水１８重量部に加熱溶解したものを混合し、更に旨味料、着色料、香料及びトレハロース含水結晶の適量を混合して押出し成形機にかけ、冷却してシート状成形物を得た。これを切断して直方体成形物とした。本品は、トレハロース含水結晶のツブツブ感と適度な弾力性を有し、風味良好なグミキャンディーとして好適である。
【００６０】
【実施例Ｂ−１４ 膨化成形物】
大型の紙コップの約１／２０容に、ポップコーン１重量部及び実施例Ａ−７の方法で、溶液温度１５０℃（水分約４．３％）まで煮詰めて調製したトレハロース含有煮詰液２．０重量部の割合で入れて放冷し、紙コップの底部にポップコーンを封入した熱可塑性トレハロース成形物を形成させた。本成形物は、電子レンジ対応ポップコーン製品として好適であり、吸湿性も無く安定で、高品価値の高いものである。これを電子レンジにかけて、当該成形物を約１８０℃に加熱し膨化させて、ポップコーンを被覆及び固着したトレハロース含有成形物を得た。本品は、風味良好で、おやつ、スナック食品などとして好適である。
【００６１】
また、本品は、食品だけでなく、屋内においては吸湿性が低く、安定性も良好で、断熱性、緩衝性、吸音性に優れていることから、断熱材料、緩衝材料、吸音材料などとしても有利に利用される。更に、本品は、廃棄時に燃焼させても、合成プラスチックとは違って、高温にならず、燃焼炉を痛めることもなく、しかも、生分解性であって、環境に優しい成形物である。
【００６２】
【発明の効果】
上記したように、本発明の熱可塑性トレハロース成形物は、良好な熱可塑性を有し、耐湿性、耐熱性、耐酸性、耐アルカリ性、保存安定性に優れ取扱い容易であることから、この熱可塑性を利用して繰り返し成形できる特徴を有している。
【００６３】
この熱可塑性トレハロース成形物の製造に際し、トレハロース溶液の付着力を低減させて、成形時の作業性を改善することも有利に実施できる。
【００６４】
本発明の熱可塑性トレハロース成形物を加熱して流動可能とし、随意な形状の成形物を容易に製造することができる。この成形に際して、各種の機能性物質や有効成分、例えば飲食品材料、化粧品材料、医薬品材料、農水畜産材料、プラスチック成形材料などを混合して成形することも好都合である。
【００６５】
このようにして得られる成形物は、随意な形状に容易に成形できるだけでなく、トレハロースが比較的不安定な機能性物質や有効成分を安定化することから付加価値が向上し、加えて、トレハロースを含んでいることから、徐崩性、生分解性の成形物となり、地球環境に優しい成形物と言える。
【００６６】
従って、本発明が与える影響は、広範囲に及び、食品業界、化粧品業界、医薬品業界、農水畜産業界、プラスチック業界、家庭用品業界などの産業界に与える工業的意義は極めて大きい。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a thermoplastic trehalose molded article, a method for producing the same, and a use thereof, and more specifically, a thermoplastic trehalose molded article and a method for producing the thermoplastic trehalose molded article characterized by molding the thermoplastic trehalose molded article using a trehalose solution. In addition, the present invention relates to a method for producing a trehalose-containing molded product characterized in that the molded product is heated to be flowable and molded, in addition, a method for reducing the adhesion of a trehalose solution and its use.
[0002]
[Prior art]
Trehalose is produced in large quantities using starch as a raw material in recent years, and has been widely used mainly in the food industry, as can be seen from the description of pages 57 to 65 of the June 1999 issue of “Chemical Industry”. . However, methods for forming and using trehalose are limited. For example, crystalline or powdered trehalose is mixed with excipients or binders and molded into tablets for use, or crystalline or powdered trehalose is heated to water with other sugars in excess. It is dissolved, boiled and poured into a mold, cooled, molded into a candy and used. Moreover, although these methods require relatively special equipment and advanced technology, the shape of the obtained molded product is too monotonous. Arbitrary shaped trehalose-containing moldings, such as cotton-like moldings, are difficult to produce, and commercially available crystals or powdered trehalose does not run on a cotton candy maker, and is well-like cotton using icing sugar. The actual condition is that the molded product cannot be manufactured. A method for easily producing a molded article having an arbitrary shape using trehalose is desired.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to easily produce a molded article having an arbitrary shape using trehalose.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventor has intensively studied on a method for producing a trehalose molded product. As a result, the glassy molded product with a high content of trehalose has better storage stability than other saccharides, has thermoplasticity, has good heat resistance, and is heated. The present invention has been completed by finding that it is easy to form a flowable material into an arbitrary shape, and that it is also easy to repeatedly form using these properties. That is, the present invention provides a thermoplastic trehalose molded product based on the finding that a glassy molded product having a high trehalose content has excellent thermoplasticity and is a stable molded product, and also provides a trehalose solution. A substance having the ability to reduce the adhesion strength of the water and about 8.3 w / w% (hereinafter, unless otherwise specified, w / w% is abbreviated as%). Production of a thermoplastic trehalose molded product characterized by molding using a trehalose solution or a trehalose solution containing no more than about 2.4% of water without containing a substance capable of reducing adhesive strength A method is provided, and the thermoplastic trehalose molding is heated to be flowable, and is molded into an arbitrary shape as it is, or is formed into an arbitrary shape using this together with other substances. Provided is a method for producing a rehalose-containing molded article. Further, when a trehalose aqueous solution is concentrated by heating, a substance having an ability to reduce the adhesive strength of the trehalose solution is allowed to coexist and the water content is reduced to about 8.3% or less. The present invention solves the above problems by establishing a method for reducing the adhesive strength of a trehalose solution characterized in that the water content is reduced to about 2.4% or less, and the thermoplastic trehalose molded product obtained by using this method.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The trehalose used in the present invention is also called α, α-trehalose, and its origin is not limited. For example, trehalose from yeast described in JP-A-7-246097, trehalose from maltose described in JP-A-58-216695, trehalose by the phosphorylase method, JP-A-7-170977, JP-A-7- Various trehaloses such as trehalose obtained by enzymatic saccharification from starch described in Japanese Patent No. 211283 can be appropriately employed. Use of commercially available high-purity trehalose hydrated crystals, anhydrous high-purity trehalose anhydrous crystals, and the like can also be appropriately employed. For example, the use of a high-purity trehalose hydrous crystal product (registered trademark “Treha”) sold by Hayashibara Corporation can be advantageously implemented.
[0006]
In addition, the thermoplastic trehalose molded product of the present invention has good storage stability under indoor temperature and humidity environmental conditions, hardly changes over time, and can be heated to melt and flow, and optionally. It can be easily molded into a shape, and even if molding and melting are repeated twice or more, its properties do not change and the molded product can be easily regenerated.
[0007]
The thermoplastic trehalose molded article of the present invention contains a substance having the ability to reduce the adhesive strength of a trehalose solution and contains about 8.3% or less of moisture, desirably about 4.4% or less, or the adhesive strength. The molded product contains about 2.4% or less, preferably 2.0% or less of water without containing a substance having a reducing ability. When these moldings are heated and examined for plasticizing temperature, they become soft when the product temperature is about 70 to 90 ° C., and even when the product temperature is about 90 ° C. or higher and about 100 to 120 ° C., they can flow. Turned out to be. An appropriate method can be selected as the manufacturing method. For example, the water-containing or anhydrous crystals of trehalose are heated or melted as it is or with an appropriate amount of humidification, desirably as high as possible product temperature, preferably above 160 ° C., more desirably about 165 to 230 ° C., More preferably, it may be formed by a method in which it is melted by heating at about 170 to 220 ° C. and formed into a glassy state. Further, for example, a trehalose aqueous solution prepared by the various enzyme reactions described above, a trehalose aqueous solution prepared by hydrogenating this, or a trehalose aqueous solution in which trehalose-containing crystals are dissolved in water, preferably 30% or more in water, more preferably Is converted to a high-concentration solution by heating and concentrating an aqueous trehalose solution containing trehalose at a concentration of less than 70%, more preferably less than 70%, more preferably less than about 50% to less than 70%. What is necessary is just to manufacture by the method of shape | molding this to a vitreous state.
[0008]
When this trehalose aqueous solution is concentrated by heating, the water content and the solution temperature are closely related. For example, at normal pressure, the water content is 15.3% and the temperature is 115 ° C. It has a relationship of 125 ° C. at 9.9%, 145 ° C. at 5.2%, 165 ° C. at 2.4%, and 185 ° C. at 1.1%. In the process of obtaining this relationship, an unexpected phenomenon was found in which the adhesive force of the solution greatly fluctuated due to the difference in the moisture (solution temperature) of the solution during heating and concentration. That is, when the solution is concentrated by heating and the water content of the solution is less than about 10%, the adhesive strength is increased. Particularly, when the water content is about 8.3% or less, the adhesive strength is remarkably increased. At 0%, the adhesive force reaches a peak and the fluidity is weakened. Concentration with heating is further continued, and when the water content is less than 3%, the adhesive force is decreased, and the water content is about 2.4% or less, preferably about 2.0%. It has been found that the adhesion strength and fluidity are improved to the extent that the workability during molding is not hindered at the following levels.
[0009]
As a result of intensive studies aimed at reducing the abnormally increased adhesion and improving workability, coexistence of substances having the ability to reduce adhesion is suitable, which greatly increases the adhesion of high-purity trehalose solutions. It has been found that the foaming during heating and concentration is reduced, the workability is improved, and the production of the molded product is facilitated.
[0010]
The substance having the ability to reduce adhesion may be any substance that can reduce the adhesion of the trehalose solution. For example, hydrophobic substances such as lipids and hydrocarbons, hydrophilic substances such as carbohydrates and polyalcohols, and Is preferably an organic material selected from emulsifiers having both hydrophobic and hydrophilic properties, and its usage is less than 40%, preferably less than 30%, relative to trehalose in terms of anhydride. It is preferable to coexist the amount of.
[0011]
Examples of lipids include fats and oils, fatty acids, and hydrocarbons that are liquid at about 100 to 230 ° C., such as alkanes, alkenes, and heterocyclic compounds. Examples of carbohydrates include monosaccharides, oligosaccharides other than trehalose, simple substances. Examples of polyalcohols such as sugar alcohols and disaccharide alcohols include glycerin, diethylene glycol, and propylene glycol, and emulsifiers include sucrose fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, and lecithin. It is chosen appropriately.
[0012]
As described above, the trehalose solution is preferably concentrated to a predetermined moisture, preferably about 8.3% or less, by adopting the adhesion reducing method in which the substance having the ability to reduce the adhesion coexists. Then, it is molded into a glassy state, or it is preferably concentrated to a water content of about 2.4% or less without coexisting a substance having the ability to reduce adhesion, and this is molded into a glassy state. What is necessary is just to manufacture a thermoplastic trehalose molding. As the molding method, various known methods such as stamping molding, cutting molding, molding in air, molding in water or oil, extrusion molding, pressure molding, especially biaxial extrusion molding can be advantageously performed.
[0013]
The thermoplastic trehalose molded product thus obtained preferably has a trehalose content as high as possible in order to maintain its good storage stability and thermoplasticity, and usually contains an amount of trehalose exceeding 60% in terms of anhydride. It is preferable to contain about 70% or more, more preferably about 80% or more, and more preferably 90% or more.
[0014]
As the shape of the thermoplastic trehalose molded product, it is usually desirable to use this as a raw material, which can be heated to flow and can be easily applied to various known molding machines or molding devices when molded into an arbitrary shape. It is preferable to use a molding machine or a molding apparatus, which can be easily heated, pressurized or depressurized as necessary, easily melted and flowable, and molded into an arbitrary shape.
[0015]
As this specific example, a material having a length usually selected from about 0.1 to 20 mm, preferably from about 2 to 15 mm as a short diameter, and having a length equal to or greater than the short diameter as a long diameter is suitable. . As the shape, grains, spheres, hemispheres, ellipsoids, short bars, half cones, short pyramids, cubes, rectangular parallelepipeds, short tubes, fibers, and the like can be advantageously used. In general, a shape called a pellet is suitable.
[0016]
The thermoplastic trehalose molded product thus obtained usually contains a substance having the ability to reduce the adhesive strength of the trehalose solution and contains about 8.3% or less of moisture, desirably about 4.4% or less. Or about 2.4% or less, preferably about 2.0% or less of water without containing the substance having the ability to reduce the adhesive strength, and more than 60% of trehalose in terms of anhydride. A trehalose molded product containing an amount, preferably about 70% or more, and trehalose is amorphous and transparent to translucent, and has excellent moisture resistance, heat resistance, acid resistance, alkali resistance, and storage stability. Easy to handle. The thermoplastic trehalose molded product can be used, for example, by dissolving it in a small amount of hot water to prepare a paste-like product containing a high amount of trehalose, and further using this paste-like product with other functional substances and active ingredients. It is also possible to use it as a pulverized base that facilitates pulverization by allowing trehalose to crystallize by allowing a crystal nucleus of trehalose to coexist in the mixture.
[0017]
However, the most important uses are those that utilize thermoplasticity. That is, the thermoplastic trehalose molded product is heated again to be melted and flowable, and may be molded into an arbitrary shape as it is, or may be used together with other substances, for example, It is also advantageous to obtain a trehalose-containing molded product by coating, mixing, adhering, inserting, encapsulating, etc. with other substances and forming into an arbitrary shape.
[0018]
Although the heating conditions vary depending on the type of substance having the ability to reduce adhesion and the degree of coexistence, the thermoplastic trehalose molded product melts and softens, and preferably flows, in other words, becomes flowable. As long as it can be molded into a shape, the softening temperature is usually about 70 to 90 ° C., and the flowable temperature is about 90 ° C. or higher, preferably about 100 to 120 ° C. or higher. . Specifically, the flowable temperature is usually relatively low when the water content of the thermoplastic trehalose molding is relatively high at about 8.3% or less and exceeds 2.4%, usually about 90 ° C. or more, Desirably, the temperature is selected from about 100 to 160 ° C. When the moisture content is relatively low, about 2.4% or less, the temperature is relatively high, usually heated to a temperature selected from about 100 ° C or higher, preferably about 110 to 230 ° C. do it.
[0019]
When molding with other materials, for example, the thermoplastic trehalose molding can be premixed with other materials and then heated to form a flowable and optional shape. Only the thermoplastic trehalose molded product can be preheated to be flowable, and then mixed with other substances for molding. If necessary, it can be humidified or a small amount of water can be added to lower the melting temperature or promote mixing.
[0020]
Any other substance can be advantageously used as long as it can be used together to form an arbitrary stable shape. That is, it is usually used in individual fields where the molded product of the present invention is used, including the chemical industry field, such as the food and drink field, the cosmetic field, the pharmaceutical field, the agricultural and fishery field, the plastics industry, and the household goods field. Any material may be used as long as it is a material or a material containing an additive and can be used together to form a stable shape. Specifically, it is usually used in one or more fields selected from the above fields, for example, sweeteners, filling agents, colorants, color formers, fermentation regulators, flavors, fragrances, fragrances, fortifiers, Swelling agent, preservative, disinfectant, antioxidant, antioxidant, bleach, paste, stabilizer, emulsifier, softener, quality improver, seasoning, spice, brightener, bitter, acidulant, food Manufacturing Agent, Enzyme Agent, Gum Base, Surfactant, Plasticizer, Lubricant, Solubilizer, Reducing Agent, Buffering Agent, Substrate, Adsorbent, Flavoring Agent, Binder, Suspending Agent, Coating Agent, Lubrication Agent, lubrication regulator, filler, antifoaming agent, cooling agent, adhesive, enhancer, chewing agent, sugar coating, isotonic agent, adhesive, adhesion enhancer, thickener, thickener, Flame retardant, exothermic agent, foaming agent, skin protectant, excipient, dispersant, pH adjuster, disintegrant, disintegration aid, rust preventive, moistureproof, anti-proof Agents, antifungal agents, preservatives, soothing agents, vitamins, antibiotics, chemotherapeutic agents, allergic agents, antihistamines, analgesics, antipruritic agents, astringents, anti-inflammatory agents, steroids, hormones, cardiotonics, dentistry・ Oral preparations, hemostatic agents, UV absorbers, herbicides, thermoplastic resins, synthetic resins, anti-crystallization agents, anti-degradation agents, anti-aging agents, anti-burning agents, resin curing agents, coagulants, foaming agents, A bubble stabilizer, an antistatic agent, a vulcanizing agent, and the like can be appropriately selected according to the purpose. For example, more specifically in the food and drink field, for example, starch, amylose, amylopectin, pregelatinized starch, dextrin, indigestible dextrin, starch derivatives, pullulan, pectin, alginic acid, polysaccharides, dietary fiber, monosaccharides, Examples include oligosaccharides, functional oligosaccharides, sugars such as sugar alcohol, proteins such as casein, gelatin, collagen, albumin, myosin, polypeptides, oligopeptides, amino acids, fats and oils, fatty acids, minerals, and the like. Furthermore, agricultural and aquatic products, for example, seeds such as rice, barley, wheat, corn, acne, sweet potato, soybean, ginkgo, almond, etc.
[0021]
The trehalose contained in the trehalose-containing molded product that can be molded together with other substances in this way is usually a relatively unstable functional substance such as the aforementioned vitamin, lipid, protein, medicinal substance, or physiologically active substance. In order to improve the stability of the active ingredient, it is desirable that the trehalose content is high. Generally, in the case of a molded article covering the surface, the content is relatively small, so that it is uniformly mixed and fixed as a whole. In such cases, the content is relatively high. Since it is necessary to mold into an arbitrary shape, the thermoplastic trehalose molding is usually about 1.0% or more, preferably about 2.0% or more, in terms of anhydride relative to other substances. Desirably, it is about 5.0% or more, more desirably about 10% or more. As the shape of the molded product, molded products having various shapes such as grains, rods, plates, sheets, films, tubes, laminates, sponges, points, lines, surfaces, and solids are appropriately selected.
[0022]
As a method of molding these molded products, an appropriate method can be adopted depending on the target shape. Known molding methods such as stamping molding, cutting molding, injection molding, extrusion molding, blow molding, plate molding, cast molding, compression molding, pressure molding, calendar molding, laminate molding, film molding, rotational molding, spray molding Adhesive molding, expansion molding, foam molding and the like can be advantageously performed.
[0023]
In this way, the trehalose-containing molded product obtained by converting into another shape is, for example, a food / beverage product, a cosmetic product, a pharmaceutical product, an agricultural / fishery product, depending on other materials used together with the functional material or active ingredient contained therein. It is suitable for molded articles used as articles, slowly disintegrating plastics, biodegradable molded articles, household articles and the like.
[0024]
Hereinafter, the present invention will be described by experiments.
[0025]
[Experiment 1]
<Effects of sugar solution boiling temperature (moisture) on solution adhesion and its storage stability>
Prepare non-reducing saccharides, ie anhydrous maltitol crystals or water containing trehalose 2 as saccharides, take one of these saccharides in a hand pan, add water to it, heat it, Solutions were prepared and the sugar solutions were heated and boiled to boil the sugar solutions. When the saccharide solution reached 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, and 190 ° C, a glass rod having a diameter of 4 mm was placed almost perpendicular to the saccharide solution. It was inserted from the liquid level to a depth of 3 cm, held as it was for about 3 seconds, and then gently pulled up. The weight of the saccharide solution attached to the glass rod was calculated by subtracting the weight of only the glass rod from the weight of the glass rod attached to the saccharide solution. Each boiled liquid was sampled in a small molding machine (depositor) and cooled to room temperature, and a sample of a molded product having a length of 20 mm, a width of 15 mm, and a thickness of 5 mm was obtained. Using the sample on the day of manufacture, moisture was measured. The water content was measured by a conventional method by the diatomaceous earth method (temperature 80 ° C., dried overnight under reduced pressure of 50 mmHg or less).
[0026]
Further, the same sample was put in a petri dish, and the presence or absence of fixing property was observed after being left in a room at a relative humidity of about 70% and a temperature of about 25 ° C. for 10 days.
[0027]
The sticking property was determined by examining the degree to which the sample absorbed moisture and sticking to the petri dish, and was divided into two stages, with and without, as a measure of storage stability. The results are shown in Table 1.
[0028]
[Table 1]
As is apparent from Table 1, in the case of trehalose, the weight of the trehalose solution adhering to the glass rod unexpectedly from a temperature of 120 ° C. (water content of the solution of about 12%) to 160 ° C. (water content of the solution of about 3.0%). It has been found that when the temperature is exceeded, the moisture content decreases, in other words, the concentration decreases to 190 ° C., although the concentration increases. That is, the adhesion of the trehalose solution is remarkably increased at a temperature of 130 ° C. (water content of about 8.3%) or higher, and peaks at a temperature of about 150 ° C. to 160 ° C. (water content of the solution is about 4.4 to 3.0%). It was found that when the temperature reached 160 ° C. (the water content of the solution was less than about 3.0%), the adhesive force gradually decreased.
[0030]
In addition, in the case of the control maltitol, a slight increase and decrease in adhesion amount (an increase from 120 ° C. to 150 ° C. and a subsequent decrease to 190 ° C.) were observed. It was found to be very small compared to trehalose. From the above, it was found that when the trehalose solution is boiled, the adhesive force rapidly increases up to a temperature of 160 ° C., which adversely affects the workability at the time of molding. On the other hand, when this trehalose solution is boiled to a high temperature of 165 ° C. or higher (water content of about 2.4% or less), the adhesion is reduced, the fluidity is remarkably improved, and the workability when handling the trehalose solution is extremely easy. It also turned out to be. In the case of trehalose, unlike maltitol, it has been found that the molded product has little change over time even when stored at room temperature with a relative humidity of 70%, is excellent in moisture resistance, and has good storage stability.
[0031]
[Experiment 2]
<Adhesion reduction method>
550 parts by weight of trehalose 2 hydrous crystals are put into a stainless steel hand pan, and there are 50 parts by weight of safflower oil, 50 parts by weight of salad oil, 150 parts by weight of anhydrous maltitol, or lactitol 1 Any one selected from 158 parts by weight of hydrous crystals was added, 450 parts by weight of water was further added, and then the saccharide was completely dissolved while heating. Furthermore, heating was continued and boiled to boil the carbohydrate solution. When the sugar solution reaches 120 ° C., 130 ° C., 140 ° C., 150 ° C., 160 ° C., 170 ° C., and 180 ° C., the sugar solution adhering to the glass rod is treated in the same manner as in Experiment 1. The weight was measured. Moreover, according to the method similar to Experiment 1 using each boiled liquid, the molding was manufactured and the water | moisture content was measured using the material on the day of the manufacture. The results are shown in Table 2. The trehalose content in the carbohydrate solution was calculated in terms of anhydride and is shown in Table 2.
[0032]
[Table 2]
As is apparent from Table 2, the increase in adhesion force from 120 ° C. to 160 ° C. in the case of trehalose alone, especially from 130 ° C. (water content of solution: about 8.3%) to 160 ° C. (water content of solution: about 3. It was found that the sudden increase in adhesion force until 0%) was significantly suppressed and drastically decreased in any of the coexistence with safflower oil, salad oil, maltitol, and lactitol. In particular, the adhesion peak at a temperature of about 150 ° C. (water content of about 4.4%) to 160 ° C. (water content of about 3.0%) is remarkably reduced in all cases, and the adhesion force is drastically reduced. There was found.
[0034]
Furthermore, it was found that the adhesive force at a high temperature exceeding 160 ° C. is lower in the coexistence of these substances having the ability to reduce the adhesive force than in the case of trehalose alone.
[0035]
From the above, the rapid increase in adhesion force from 130 ° C. (water content of solution about 8.3%) to 160 ° C. (water content of solution about 3.0%) observed during boiling of trehalose solution is By coexisting substances having an ability to reduce adhesion, such as oils such as safflower oil and salad oil, and sugars such as maltitol and lactitol, the temperature is about 150 ° C. (4.4%) to 160 ° C. (about 3.0% of the water content of the solution), the peak of adhesion is remarkably reduced. Further, even when cooking at a high temperature exceeding 160 ° C., these substances are attached to the trehalose solution. It was found that the adhesion force was further reduced and the fluidity was remarkably improved, and it was found that the workability during molding of the thermoplastic trehalose molded product could be remarkably improved.
[0036]
Hereinafter, the thermoplastic trehalose molded product of the present invention will be described in Example A, and a trehalose-containing molded product will be described in Example B as an example of its use.
[0037]
[Example A-1 Short rod-shaped molded product]
110 parts by weight of high-purity trehalose hydrated crystal product (Hayashibara Shoji Co., Ltd., registered trademark “Treha”) is placed in a dissolution tank, 90 parts by weight of water is added and dissolved by heating. After reducing the adhesion of the solution to a water content of about 0.9%, it is molded in an extruder and allowed to cool to room temperature. A rod-like thermoplastic resin with a diameter of about 2 mm and a length of about 4 mm. A trehalose molding was obtained. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C. to make it flowable, and it can be changed into a molded product having an optional shape, or it can be used together with other materials having various functions to finish a molded product with an optional shape. Can be implemented. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste. Furthermore, this paste can be used in an amorphous state or as a powdered base to be crystallized. Utilization can also be advantageously performed.
[0038]
Example A-2 Ellipsoidal molded product
A high-purity trehalose hydrous crystal product was dissolved by heating in the same manner as in Example A-1, and this was heated and concentrated. When the liquid temperature at which the adhesive force started to increase was higher than 110 ° C., about 5% of trehalose in terms of anhydride. % Olive oil was added, and the concentration of the solution was reduced by reducing the adhesive force of the solution, and the solution was boiled to a temperature of about 170 ° C. (water content of about 2.0%). A thermoplastic trehalose molding was obtained. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C to make it flowable, and can be changed into a molded product of any other shape, or it can be used together with other materials having various functions to finish a molded product of a desired shape. It can be carried out advantageously. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste, or the paste can be used in an amorphous state or used as a powdered base for crystallization. It can also be advantageously carried out.
[0039]
[Example A-3 Short square columnar molded product]
A high-purity trehalose hydrous crystal product was dissolved by heating in the same manner as in Example A-1, and this was concentrated by heating. When the liquid temperature at which the adhesive strength began to increase exceeded 110 ° C., about 3 with respect to trehalose in terms of anhydride. % Propylene glycol was added to reduce the adhesive force of the solution and continue to heat and concentrate until it was boiled to a solution temperature of about 165 ° C. (water content of about 2.4%). A thermoplastic trehalose molded product having a short square column shape of about 10 mm was obtained. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C or more to make it flowable, and it can be changed into a molded product of any other shape, or it can be used together with other substances having various functions to finish a molded product of a desired shape. Can also be implemented advantageously. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste. Furthermore, this paste can be used in an amorphous state or as a powdered base to be crystallized. Utilization can also be advantageously performed.
[0040]
Example A-4 Hemispherical Molded Product
According to the method disclosed in JP-A-8-73482, a mutant strain of Rhizobium species M-11 (FERM BP-4130) was cultured in a nutrient medium for about 70 hours with a fermenter. After culturing, sterilization filtration is performed using an SF membrane, and about 100 l of the culture filtrate is collected. Further, the filtrate is concentrated on a UF membrane, and a non-reducing saccharide-forming enzyme (about 410 units / ml) and trehalose-free enzyme are collected. About 5 l of concentrated enzyme solution containing (about 490 units / ml) was recovered. Corn starch is converted to starch milk having a concentration of about 33%, and α-amylase is allowed to act on this to obtain a liquefied solution of DE of about 4, and then the non-reducing saccharide-forming enzyme and trehalose-free enzyme prepared by the above method are used. The concentrated enzyme solution containing 0.02 ml per gram of starch, 500 units of isoamylase per gram of starch and 5 units of cyclomaltodextrin / glucanotransferase were added per gram of starch, and reacted at pH 6.2 and a temperature of 40 ° C. for 48 hours. This reaction solution was deactivated by heating, and then 10 units of glucoamylase was added per gram of substrate, followed by reaction at pH 5.0 and a temperature of 50 ° C. for 10 hours. The reaction solution contained 85.6% trehalose per solid. This reaction solution was inactivated by heating, and purified by decoloring, desalting and concentrating according to a conventional method to obtain syrup having a concentration of 45%. This trehalose-rich low-reducing saccharide syrup is hydrogenated, decolorized, desalted, purified and concentrated according to conventional methods, and contains about 85% trehalose in terms of anhydride and the rest mainly contains sorbitol. I got syrup. This is heated and concentrated, and boiled to a solution temperature of about 180 ° C. (water content of about 1.3%) to reduce the adhesion of the solution. This is dropped into salad oil through a thin tube and solidified by cooling, and a hemisphere with a bottom diameter of about 8 mm A thermoplastic trehalose molded product was obtained. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C to make it flowable, and can be changed into a molded product of an arbitrary shape, or it can be used with other substances having various functions to finish a molded product of an arbitrary shape. Can be implemented. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste, or the paste can be used in an amorphous state or used as a powdered base for crystallization. It can also be advantageously carried out.
[0041]
Example A-5 Fibrous molding
The trehalose hydrated crystals are heated to about 200 to 210 ° C. (water content of about 0.5% or less) in an electric furnace and melted, and the resulting solution is allowed to flow out from the take-out port provided at the bottom of the electric furnace. Air was blown to obtain a fibrous material having a thickness of about 0.1 to 0.2 mm, which was further crushed to obtain a short fibrous material having a length of about 20 mm or less. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C to make it flowable, and can be changed into a molded product of an arbitrary shape, or it can be used with other substances having various functions to finish a molded product of an arbitrary shape. Can be implemented. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste, or the paste can be used in an amorphous state or used as a powdered base for crystallization. It can also be advantageously carried out.
[0042]
[Example A-6 Short rod-shaped product]
The thermoplastic trehalose molded product obtained by the method of Example A-3 was further heated to about 120 ° C. and passed through an extruder to obtain a short rod-shaped thermoplastic trehalose molded product having a diameter of about 2 mm and a length of about 4 mm. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C to make it flowable, and can be changed into a molded product of an arbitrary shape, or it can be used with other substances having various functions to finish a molded product of an arbitrary shape. Can be implemented. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste. Furthermore, this paste can be used in an amorphous state or as a powdered base to be crystallized. Utilization can also be advantageously performed.
[0043]
[Example A-7 Ellipsoidal molded product]
Take 100 parts by weight of high-purity trehalose hydrous crystal product and 10% by weight of high-purity maltitol anhydrous crystal product (Hayashibara Shoji Co., Ltd., registered trademark “Mabit”) in a dissolution tank, add 90 parts by weight of water and dissolve with heating Add 0.2 parts by weight of an emulsifier (sucrose stearate), heat concentrate, boil to a solution temperature of 150 ° C. (water content of about 4.3%), apply this to a stamping machine, and heat about 15 mm in length and an elliptical spherical shape A plastic trehalose molded product was obtained, which is a colorless, transparent or translucent, substantially amorphous molded product, which has good storage stability in the indoor environment and has thermoplasticity. It can be reheated to a product temperature of about 90 to 160 ° C. to make it flowable, and can be changed into a molded product having any other shape, and can be used together with other materials having various functions. shape Finishing into a molded product can also be carried out advantageously, and this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste, or the paste can be used in an amorphous state, Alternatively, it can be advantageously used as a powdered base to be crystallized.
[0044]
[Example A-8 Short rod-shaped molded product]
Take 95 parts by weight of high-purity trehalose hydrous crystal product and 18 parts by weight of paratinite in a dissolution tank, add 63 parts by weight of water and heat to dissolve, put this in a concentrator, boil to 125 ° C under normal pressure, then under reduced pressure. While maintaining this temperature, the solution was heated and concentrated, boiled to about 1.0% water, formed in an extruder as in Example A-1, allowed to cool to room temperature, and about 2 mm in diameter and length. About 4 mm short rod-shaped thermoplastic trehalose molding was obtained. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C. to make it flowable, and it can be changed into a molded product having an optional shape, or it can be used together with other materials having various functions to finish a molded product with an optional shape. Can be implemented. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste. Furthermore, this paste can be used in an amorphous state or as a powdered base to be crystallized. Utilization can also be advantageously performed.
[0045]
[Example A-9 Short rod-shaped molded product]
After mixing 80 parts by weight of a high-purity trehalose hydrous crystal product and 20 parts by weight of a high-purity maltitol anhydrous crystal product into powder, this is put into a salad oil (about 180 ° C.) about 20 times the weight of the powder and heated. Then, it was melted to a moisture content of about 1.3%, taken out, and applied to a cutting molding machine to obtain a short rod-shaped thermoplastic trehalose molded product having a diameter of about 5 mm and a length of about 8 mm. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C. to make it flowable, and it can be changed into a molded product having an optional shape, or it can be used together with other materials having various functions to finish a molded product with an optional shape. Can be implemented. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste. Furthermore, this paste can be used in an amorphous state or as a powdered base to be crystallized. Utilization can also be advantageously performed.
[0046]
[Example A-10 Disc-shaped molded product]
85 parts by weight of high-purity trehalose hydrated crystals and 15 parts by weight of reduced starch syrup (trade name “HS-300” sold by Hayashibara Corporation) are uniformly mixed, and this has a plurality of indentations with a diameter of about 8 mm and a depth of about 5 mm. The product is packed in a Teflon mold, heated in a microwave oven, melted, boiled to a moisture content of about 2.0%, and then allowed to cool to a disk-shaped heat having a diameter of about 8 mm and a thickness of about 3 mm. A plastic trehalose molding was obtained. This product is a colorless, transparent or translucent, substantially amorphous molded product, has good storage stability in the indoor environment, and has thermoplasticity. It can be reheated to 230 ° C. to make it flowable, and it can be changed into a molded product having an optional shape, or it can be used together with other materials having various functions to finish a molded product with an optional shape. Can be implemented. In addition, this product can be dissolved in a relatively small amount of hot water to prepare a trehalose-containing paste. Furthermore, this paste can be used in an amorphous state or as a powdered base to be crystallized. Utilization can also be advantageously performed.
[0047]
[Example B-1 Cotton-like molded product]
0.05 parts by weight of lemon-concentrated fruit juice was uniformly sprayed and adhered to 1 part by weight of the thermoplastic trehalose molded product obtained by the method of Example A-7, dried, and then applied to a cotton candy making machine to give about 100 parts. Cotton confectionery was produced by heating and melting at a temperature higher than 0 ° C. Unlike the conventional cotton candy that uses sugar, its volume tends to shrink over time, and it has the disadvantage that it does not add sourness. A flavored cotton candy containing trehalose.
[0048]
Example B-2 Coated molding
100 parts by weight of flour, 2 parts by weight of yeast, 5 parts by weight of sugar, 1 part by weight of maltose and 0.1 part by weight of inorganic food are kneaded with water according to a conventional method, and the medium seeds are fermented at 26 ° C. for 2 hours. Aging for 30 minutes, the dough obtained was rolled by hand. The thermoplastic trehalose molded product obtained by the method of Example A-4 was partially pressed into this surface of bread dough in terms of anhydride, and then partially baked at about 180 ° C. according to a conventional method. This product is a unique bread in which a tasteful trehalose-containing coated molded product is melted and deformed on the surface, and it is a high-quality bread that has good hue and sash, moderate elasticity and mild sweetness.
[0049]
Example B-3 Coated molding
60 parts by weight of butter, 20 parts by weight of sugar, 20 parts by weight of maltose and 10 parts by weight of powder of water containing trehalose 2 are kneaded well, and 40 parts by weight of chicken eggs are added thereto to form a cream. Further, 140 parts by weight of flour, 10 parts by weight of corn starch and 3 parts by weight of pullulan were added and mixed, and the resulting cookie dough was squeezed on a top plate with a chrysanthemum and formed into a flower pattern. The thermoplastic trehalose molded product obtained by the method of −5 was attached to the cookie dough with about 1% in terms of anhydride, and baked in an oven at about 170 ° C. for 15 minutes. This product was well-bonded with a trehalose-containing coated molded product that had been melt-deformed and the cookie dough, and was well bonded, and also had good flavor and mouthfeel.
[0050]
Example B-4 Granular molded product
A mixed powder of 15 parts by weight of the thermoplastic trehalose molded product obtained by the method of Example A-2, 2 parts by weight of plain yogurt and 10 parts by weight of anhydrous trehalose powder was heated to about 100 ° C. and passed through a twin-screw extruder. A trehalose-containing granular molding was produced. This product is a yogurt-flavored sweetened product, used as a confectionery material for premixes, frozen confectionery, cakes, etc., as a therapeutic nutrient for tube liquid foods, and for example, margarine whipped cream, spreads, cheesecake, jelly It can be advantageously used, for example, by adding it to a yogurt-flavored product.
[0051]
[Example B-5 Trapezoidal molded product]
30 parts by weight of a thermoplastic trehalose molded product obtained by the method of Example A-3, 1 part by weight of α-glucosyl-L-ascorbic acid, 1 part by weight of α-glucosyl hesperidin, 1 part by weight of sodium sulfate and an appropriate amount of a coloring agent, 1 part by weight of alcohol water in which a fragrance was dissolved was heated to about 100 ° C. and subjected to a pressure molding machine to produce a trehalose-containing trapezoidal shaped product. This product is about 10 g each, and is suitable for bathing as a skin beautifying agent or fair skin agent. As in the case of bathing, the product can be advantageously used by dissolving in facial cleansing water or lotion.
[0052]
Example B-6 Ellipsoidal molded product
500 parts by weight of thermoplastic trehalose molding obtained by the method of Example A-2, 270 parts by weight of powdered egg yolk, 209 parts by weight of skim milk powder, 4.4 parts by weight of sodium chloride, 1.85 parts by weight of potassium chloride, 4 parts of magnesium sulfate A pressure molding machine in which a mixture of parts by weight, 0.01 parts by weight thiamine, 0.1 parts by weight sodium ascorbate, 0.6 parts by weight vitamin E acetate and 0.04 parts by weight nicotinamide is heated to about 100 ° C. To produce a trehalose-containing oval spherical shaped product. This product is suitable as a nutritional product, and is used by dissolving in the mouth with about 5 g per sphere, and is advantageously used as a nutritional agent for treating sick people, and for maintaining and enhancing the health of healthy people. The
[0053]
[Example B-7 Granular molded product]
A mixture of 10 parts by weight of the thermoplastic trehalose molded product obtained by the method of Example A-1 and 1 part by weight of sodium carbonate powder is heated to about 100 ° C. and subjected to a twin screw extruder to produce a trehalose-containing granular molded product. did. This product can be widely used in various applications as a pH adjuster that is easy to handle without fear of scattering of sodium carbonate powder.
[0054]
[Example B-8 Short tubular molding]
A mixture of 100 parts by weight of a thermoplastic trehalose molded product obtained by the method of Example A-2, 200 parts by weight of fish meal, 20 parts by weight of pregelatinized starch, 3 parts by weight of pullulan and 10 parts by weight of water was heated to about 110 ° C. A short tubular molded product was formed by passing through an extruder, immersed in an about 10% shellac alcohol solution, immediately lifted and dried with hot air to produce a trehalose-containing short tubular molded product. This product is a feed that hardly pollutes water, and is suitable for aquaculture, ornamental, seafood, shellfish, etc., regardless of whether it is freshwater or seawater.
[0055]
[Example B-9 Flowerpot]
A mixture of 100 parts by weight of the thermoplastic trehalose molded product obtained by the method of Example A-6, 15 parts by weight of glycerin and 50 parts by weight of waste paper pulp is heated to about 150 ° C., and then subjected to an injection molding machine to form a flower pot, and a molten wax And was allowed to cool to produce a trehalose-containing flower pot. Since this product is gradually disintegrating and biodegradable, it is suitable as a plant pot for transplantation and can be transplanted without removing the pot, so there is no planting pain.
[0056]
[Example B-10 Short rod-shaped product]
A mixture of 60 parts by weight of the thermoplastic trehalose molded product obtained by the method of Example A-1, 30 parts by weight of coral powder, 0.1 part by weight of α-glucosyl rutin, and 2 parts by weight of corn steep liquor was heated to about 110 ° C. It was heated and subjected to an extrusion molding machine to obtain a short rod-shaped trehalose-containing plant activator molded product. This product does not require a container, is easy to handle, and dissolves and disintegrates at an appropriate rate when used, so it is suitable as a long-lasting plant activator.
[0057]
[Example B-11 Golf Tee]
A mixture of 10 parts by weight of the thermoplastic trehalose molded product, 4 parts by weight of acid clay and 0.5 part by weight of pullulan obtained by the method of Example A-4 was heated to about 160 ° C. and subjected to an injection molding machine to form a golf tee. Soaked in about 10% shellac alcohol solution and dried to obtain a product. This product is broken into small lumps by shots, gradually collapses with rainwater, and biodegraded. Therefore, the beauty of the golf course is not impaired and the environment is not destroyed. Appropriate trehalose spraying also activates grass growth on the golf course.
[0058]
Example B-12 Film-like molded product
92 parts by weight of low density polyethylene, 8 parts by weight of a thermoplastic trehalose molded product obtained by the method of Example A-3, 0.05 parts by weight of calcium stearate, 0.5 parts by weight of enzyme-treated rutin and 0.5 parts by weight of tea extract Part of the mixture is heated to about 120 ° C. and subjected to a pressure molding machine to form a short rod-shaped molded product, which is then heated to about 130 ° C. according to a conventional method and then subjected to an extrusion molding machine (inflation method) to produce a film-shaped molded product. did. This product can be advantageously used as a film for maintaining the freshness of fresh foods such as flowers, vegetables, fruits, meat and fish.
[0059]
[Example B-13 rectangular parallelepiped molded product]
150 parts by weight of a thermoplastic trehalose molded product obtained by the method of Example A-7 was heated to about 100 ° C., and 13 parts by weight of gelatin was heated and dissolved in 18 parts by weight of water. Appropriate amounts of colorant, fragrance and trehalose hydrated crystals were mixed, put into an extrusion molding machine, and cooled to obtain a sheet-like molded product. This was cut into a rectangular parallelepiped molded product. This product is suitable as a gummy candy having a smooth feeling of trehalose hydrated crystals and moderate elasticity, and having a good flavor.
[0060]
[Example B-14 Expanded molding]
Trehalose-containing boiled liquid 2.0 prepared by boiling to about 1/20 volume of a large paper cup with 1 part by weight of popcorn and a solution temperature of 150 ° C. (water content of about 4.3%) by the method of Example A-7 A thermoplastic trehalose molded product in which popcorn was encapsulated at the bottom of a paper cup was formed by allowing it to cool in a proportion by weight. This molded product is suitable as a popcorn product for microwave ovens, has no hygroscopic property, is stable, and has a high quality value. This was placed in a microwave oven, and the molded product was heated to about 180 ° C. and expanded to obtain a trehalose-containing molded product coated and fixed with popcorn. This product has good flavor and is suitable as a snack or snack food.
[0061]
In addition to food, this product has low hygroscopicity indoors, good stability, and excellent heat insulating properties, buffer properties, and sound absorbing properties. Are also advantageously used. In addition, unlike synthetic plastics, this product does not become high temperature, does not damage the combustion furnace, and is a biodegradable and environmentally friendly molded product.
[0062]
【The invention's effect】
As described above, the thermoplastic trehalose molded product of the present invention has good thermoplasticity, is excellent in moisture resistance, heat resistance, acid resistance, alkali resistance, storage stability, and is easy to handle. It has the feature that it can be repeatedly molded using.
[0063]
In the production of the thermoplastic trehalose molded product, it is also possible to advantageously reduce the adhesion of the trehalose solution and improve the workability during molding.
[0064]
The thermoplastic trehalose molded product of the present invention can be heated to flow, and a molded product having an arbitrary shape can be easily produced. In this molding, it is also convenient to mix various functional substances and active ingredients such as food and drink materials, cosmetic materials, pharmaceutical materials, agricultural and livestock materials, plastic molding materials and the like.
[0065]
The molded product thus obtained can be easily molded into an arbitrary shape, and trehalose stabilizes functional substances and active ingredients that are relatively unstable. Therefore, it can be said to be a slowly disintegrating and biodegradable molded product and a molded product that is friendly to the global environment.
[0066]
Therefore, the influence which this invention has is wide, and the industrial significance given to industries, such as the food industry, the cosmetics industry, the pharmaceutical industry, the agriculture and fisheries industry, the plastics industry, and the household goods industry, is very large.
Claims (9)
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| JP2006249029A (en) * | 2005-03-11 | 2006-09-21 | Kanebo Ltd | Fibrous cosmetic, sheet-like cosmetic, cosmetic composition and makeup method |
| JP5507253B2 (en) * | 2007-10-19 | 2014-05-28 | 株式会社林原 | "Naki" suppressed lactosucrose-containing hard candy and method for producing the same |
| JP4832407B2 (en) * | 2007-11-19 | 2011-12-07 | 花王株式会社 | Collagen-containing composition |
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