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JP3693385B2 - Water dispersible composition - Google Patents
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JP3693385B2 - Water dispersible composition - Google Patents

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JP3693385B2
JP3693385B2 JP15046295A JP15046295A JP3693385B2 JP 3693385 B2 JP3693385 B2 JP 3693385B2 JP 15046295 A JP15046295 A JP 15046295A JP 15046295 A JP15046295 A JP 15046295A JP 3693385 B2 JP3693385 B2 JP 3693385B2
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water
composition
less
weight
fine cellulose
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JPH093243A (en
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悦雄 鎌田
桂一 依田
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Asahi Kasei Chemicals Corp
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Asahi Kasei Chemicals Corp
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Description

【0001】
【産業上の利用分野】
本発明は、水分散性組成物及び食品組成物に関する。即ち、本発明の水分散性組成物はセルロースコロイドを形成し得る乾燥組成物であって、食品、医薬品、化粧品、塗料、セラミックス、樹脂、触媒、その他工業用品等の分野において、懸濁安定剤、乳化安定剤、増粘安定剤等の安定剤、組織付与剤、クラウディー剤、白度向上、流動性改良、研磨剤、食物繊維、油脂代替物等の目的で利用可能な水中に再分散し得る微細セルロース含有水分散性組成物であり、また、該水分散性組成物を含有する食品組成物は、乳化等の安定性が著しく高い。
【0002】
【従来の技術】
特開平7ー102113号公報には、微細セルロース及びカルボキシメチルセルロースナトリウム(以下、CMC−Naという)を含有する水分散性の複合体に関する記載がある。また、特開平6ー335365号公報には、微細セルロース及びCMC−Naからなる水分散性の複合体を含有する食品組成物に関する記載がある。これらの複合体は水に再分散したとき、10μm以上の粒子の割合が40%以下で、コロイド分画が65%以上である。しかしCMC−Naの物性に関しては何ら記載がなく、また、その添加量も、具体的には2〜5重量%程度である。
【0003】
従来の微細セルロースを含有する複合体は、懸濁安定剤、乳化安定剤、増粘安定剤等の安定剤としての機能が必ずしも十分ではなかった。特に、酸性領域で微細セルロースの凝集が起こりやすいため安定剤としての機能が十分に発揮されない場合があった。そのため、果汁飲料、乳酸菌飲料等の酸性食品に用いることが困難であった。
【0004】
【発明が解決しようとする課題】
本発明は、酸性領域においても微細セルロースの凝集を起こさず、安定に分散することによって、懸濁安定剤、乳化安定剤、増粘安定剤、組織付与剤、クラウディー剤、白度向上、流動性改良、研磨剤、食物繊維、油脂代替物として優れた機能を有する微細セルロース含有水分散性組成物を提供することを目的とするものであり、また、酸性領域においても懸濁安定性、乳化安定性等に優れた食品組成物を提供することを目的とするものである。
【0005】
【課題を解決するための手段】
本発明は、微細セルロース100重量部に対して、置換度が0.6〜2.0であって、1%濃度における粘度が500センチポアズ以下であるCMC−Naを15〜100重量部含有する乾燥組成物であって、該組成物を水に再分散した時の平均粒径が8μm以下で、10μm以上の粒子の割合が40%以下で、コロイド分画が65%以上である水分散性組成物、及び、果汁飲料、乳酸菌飲料等の酸性飲料、またはマヨネーズ、ドレッシング、ゼリー、ジャム等の酸性食品を含有する食品組成物であって、酸性領域での懸濁、乳化等の安定性が向上した食品組成物に関する。
【0006】
以下、詳細に本発明を説明する。
再分散した微細セルロース含有水分散性組成物の食感を左右する要因は二つあって、ザラツキは、主に、粒度分布における10μm以上の粒子の割合が重要な要因であり、また、舌に感じるなめらかさは、実用特性であるコロイド分画が重要な要因である。
【0007】
セルロース粒子のザラツキの主要因は10μm以上の粗大粒子の量にある。本発明の水分散性組成物を水に再分散させた場合、該粗大粒子の割合が40%を超えるとザラツキ感が生じる。したがって、平均粒径が8μm以下であって、10μm以上の粗大粒子の割合が40%以下であることが必要である。本発明の目的を効果的に達成するためには、平均粒径が6μm以下であって、10μm以上の粗大粒子の割合が20%以下であることが好ましい。更に好ましくは、平均粒径が4μm以下であって、10μm以上の粗大粒子の割合が10%以下である。
【0008】
また、舌で感じるなめらかさは、コロイド性セルロースを計測する実用特性であるコロイド分画と一致する。即ち、水分散性組成物の水分散物において、なめらかな組織を得るためには水分散性組成物を水に分散した時の指標として、コロイド分画が65%以上であることが必要である。さらに、コロイド分画が80%以上であることが好ましい。
【0009】
ここで「コロイド分画」とは、微細セルロース及び水分散性組成物の水分散液に一定の遠心力をかけた時、沈降することなく浮遊、分散している分散相の固形分の重量割合(%)である。即ち、水系分散液において沈降することなく安定に分散し得るコロイダル部分の割合であり、分散性及び安定性の実用上の能力を示す。また、「平均粒径」、「10μm以上の粒子の割合」はそれぞれ、レーザー法粒度分布測定装置により求められる積算体積50%の粒径、体積分布における割合(%)である。具体的には、後述の実施例の項に記載する種々の物性測定法のうち<平均粒径、10μm以上の粒子の割合>および<コロイド分画>に記載の方法にて得られる測定値のことである。
【0010】
本発明に用いる微細セルロースは、平均粒径が8μm以下、10μm以上の粒子の割合が40%以下であり、コロイド分画が50%以上であることが好ましい。更に好ましくは、平均粒径が6μm以下、10μm以上の粒子の割合が20%以下である。特に好ましくは、平均粒径が4μm以下で、10μm以上の粒子の割合が10%以下である。平均粒径は小さいほど良いが、その下限は、磨砕、粉砕の技術および装置により自ずから限度があり、現在のところでは通常0、05μm程度と考えられる。また、コロイド分画は大きいほど良く、その上限は100%である。
【0011】
この微細セルロースは、木材パルプ、精製リンター等のセルロース系素材を酸加水分解、アルカリ酸化分解、酵素分解、スチームエクスプロージョン分解等、あるいはそれらの組み合わせにより解重合処理して平均重合度30〜375のセルロースとし、次いで機械的なシェアをかけ湿式磨砕することによって得ることができる。更に、この湿式磨砕した物を遠心沈降によりコロイダル部分を分画処理して得ることもできる。
【0012】
湿式磨砕機械として好適なものは、媒体ミル類、例えば湿式振動ミル、湿式遊星振動ミル、湿式ボールミル、湿式ロールミル、湿式コボールミル、湿式ビーズミル、湿式ペイントシェーカー等の他、高圧ホモジナイザー等がある。高圧ホモジナイザーとしては約500Kg/cm2 以上の高圧で、スラリーを微細オリフィスに導き高流速で対面衝突させるタイプが効果的である。これらのミルを使用した場合の最適磨砕濃度は機種により異なるが、概ね、媒体ミルで3〜15%、高圧ホモジナイザーで5〜20%の固形分濃度が適している。
【0013】
本発明の目的のためにはこれらの機種を単独で用いることもできるが、二種以上の機種を組み合わせて用いることも出来る。これらの機種は種々の用途における粘性要求等により適宜選択すれば良い。
本発明で用いるCMC−Naは、置換度が0.6〜2.0、1%濃度における粘度が500センチポアズ以下であることが必要である。本発明に用いるCMC−Naは、水中への微細セルロースの分散を迅速に行わせると共に、セルロースの分散、懸濁等の安定性を更に高め、かつ保護コロイドとしての機能を果たすことによりコロイド分画の向上に寄与する。つまり、一般に結晶セルロースの安定性は、結晶セルロース表面が負に帯電することによる電気的な反発力によってもたらされるが、カルボキシル基を持つCMC−Naがセルロース表面に吸着することによってその機能は向上する。本発明の水分散性組成物は、特定のCMC−Naを特定量使用することにより、特に酸性領域での安定性が高いのが特徴である。また、塩濃度の高い食品においても、高い安定性を示す。
【0014】
置換度が0.6未満では、水分散性組成物を酸性領域で分散させた時の安定性が十分でない。また、置換度が2.0を超えても同様に酸性領域での安定性が悪化する。また、2.0を超える置換度を持つCMC−Naは、製造が難しく実用的で無いという面もある。置換度としては、好ましくは0.7〜1.5であり、特に好ましくは0.8〜1.3である。また、1%濃度における粘度が500センチポアズを超えると飲料等に用いた時、粘度の上昇により喉越しなどの食感が悪くなるので好ましくない。好ましくは200センチポアズである。特に好ましくは50センチポアズである。通常使用しうる市販品では、粘度の下限は1センチポアズ程度である。
【0015】
CMC−Naの配合量は、微細セルロース100重量部に対して、15〜100重量部である。15重量部未満では水分散性組成物が酸性領域で十分に安定剤として機能しない。また、100重量部を超えると粘度の上昇による食感の低下とともに、微細セルロース含量の低下に伴い安定剤としての機能が低下し好ましくない。特に好ましくは15〜50重量部である。
【0016】
微細セルロース及びCMC−Naの他に、水中への微細セルロースの再分散性を改良するために、以下に挙げる水溶性ガム類、親水性物質、油脂類を配合しても良い。
水溶性ガム類とは、水膨潤性が高くセルロースとの水中における相溶性が良好な水溶性のガム類であり、ローカストビーンガム、グアーガム、カゼイン及びカゼインナトリウム、タマリンドシードガム、カラヤガム、キトサン、アラビアガム、寒天、カラギーナン、アルギン酸及びその塩、ペクチン、アゾトバクター・ビネランジーガム、サイリウムシードガム、キサンタンガム、カードラン、プルラン、デキストラン、ジェランガム、ゼラチン、セルロース誘導体、澱粉誘導体等が挙げられる。好ましくは、キサンタンガム、カラギーナン、ペクチン、カラヤガム、ゼラチン、アラビアガムである。これらの水溶性ガム類は2種以上組み合わせてもかまわない。
【0017】
親水性物質とは、冷水への溶解性が高く粘性を殆どもたらさない有機物質であり、澱粉加水分解物、デキストリン類、ブドウ糖、ソルボース、乳糖、ポリデキストロース、フラクトオリゴ糖等の単糖類、オリゴ糖類を含む水溶性糖類、マルチトール、ソルビット等の糖アルコール類等が適している。中でも澱粉加水分解物、デキストリン類、ブドウ糖、乳糖、ポリデキストロース、ソルビットが適している。これらの親水性物質は2種以上組み合わせてもかまわない。
【0018】
水溶性ガム類及び親水性物質を大量に配合すると、CMC−Naの保護コロイド性を損なうので、それらの合計量はCMC−Na配合量の半量以下程度にした方が良い。コロイド分画は、微細セルロース単独で測定するときは微細セルロースのコロイダルな性能そのものを表しているが、CMC−Naと複合化した場合、微細セルロースの元のコロイド分画値より高い値を与えるようになる。即ち、この水分散性組成物の再分散体の組織のなめらかさは、原料微細セルロースと同等もしくはそれ以上に改良されている。
【0019】
油脂類とは、80〜150℃の温度範囲のいずれかにおいて液体状を示し、水に自由に溶解しない物質である。上記の温度範囲としては、好ましくは100〜150℃である。具体例としては、大豆油、ヤシ油、とうもろこし油、パーム油、サラダ油、ゴマ油、菜種油、カカオ脂、ヒマシ油、鯨油、ラード、硬化油、中鎖脂肪酸トリグリセリド、乳脂肪等の動植物油類、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、蔗糖脂肪酸エステル、ソルビタン脂肪酸エステル等の界面活性剤類、オレイン酸、ラウリン酸、パルミチン酸、ステアリン酸等の脂肪酸類及びそれらのエステル類、ラウリルアルコール等の高級アルコール類、カルナウバロウ等のワックス類、パラフィンワックス等の炭化水素類、ポリジメチルシロキサン等のシリコーンオイル類から選ばれる1種叉は2種以上の組み合わせからなる。界面活性剤の場合、親水性のものより疎水性のものが好ましく、HLB値として13以下が好ましい。油脂類はそのまま加えることができるが、動植物油等に界面活性剤、水等を加えて均質化することによって得られる乳化物の形態にした後に添加してもかまわない。また、油脂類を含有しているマーガリン、生クリーム等の形態で配合してもかまわない。油脂類の配合量は、微細セルロース100重量部に対して、20重量部以下程度にした方が良い。20重量部を超えると、組成物を水中で撹拌しても内部への水の浸透が起こり難くなるため、再分散性が低下するので好ましくない。好ましくは10重量部以下である。特に好ましくは5重量部以下である。
【0020】
その他の成分の配合については、組成物の水中での分散を阻害しない程度に配合することは自由である。
本発明の水分散性組成物は、まず磨砕して得た平均粒径が8μm以下、10μm以上の粒子の割合が40%以下、コロイド分画が50%以上である微細セルロースをCMC−Na、必要により水溶性ガム類、親水性物質、油脂類等と混合してスラリーとなし、次いでこれを乾燥させることによって得られる。また、解重合処理したセルロースを予めCMC−Na等と混合し、湿式媒体ミルあるいは高圧ホモジナイザー等で磨砕してスラリーとする方法も可能である。いずれの場合も、CMC−Na等との混合、分散に当たっては、特にCMC−Na、水溶性ガム類を十分溶解させること、及びCMC−Na他と混合する際、微細セルロースを分散液中で均一に分散させなければならない。このためには微細セルロースとCMC−Naその他を混合する時に、全重量の75%以上の水の存在下に充分撹拌し均一に混合することが好ましい。この際、予めCMC−Naその他を適当量の水に分散した後に、微細セルロースを加えて混合することがより効果的である。加熱処理は、CMC−Na等の溶解を促進するための効果的な方法である。
【0021】
乾燥は、水分散性組成物の性能を左右する大きな要因である。水分散性組成物の水への再分散性を確保するためには、該組成物はその内部に網目状の無数の微細な亀裂や空洞を有していることが好ましい。この亀裂が導水性の細孔となることによって、CMC−Naの溶解、微細セルロースの分散を促進する。この亀裂は0.05〜0.5μm程度の隙間であって、細孔同士の間隔は最大で3μm程度に抑えることが好ましい。この構造を与える乾燥方法としては、凍結乾燥、噴霧乾燥等を採用することも出来るが、フィルム状にて乾燥することが好ましい。凍結乾燥法は生産効率が悪く、噴霧乾燥法は大きな装置を必要とする上に製品の品質制御が困難で乾燥製品の再分散性能がバラツキ易い欠点がある。噴霧乾燥機を使用する場合はこのバラツキを少なくするため噴霧粒径を小さく保ち、かつ乾燥速度をできるだけ速やかに行うことが必要である。
【0022】
微細セルロース含有水分散性組成物の分散性が最も良い方法としては、フィルム状にて乾燥する方法が優れている。フィルム状にて乾燥する方法とは、即ち、微細セルロースとCMC−Naその他の混合スラリーを、ガラス、ステンレス、アルミニウム、ニッケル・クロムメッキ鋼板等の基材上にキャスティングして乾燥する方法である。基材は予め加熱されていても良く、またキャスティング後、赤外線、熱風、高周波等にて加熱しても良い。乾燥温度は200℃以下、キャスティングの厚みはスラリーの厚みとして10mm以下が好ましい。スラリー濃度はフィルム状に展開できる濃度であれば良く、特に制限はないが実用的には5%から20%程度の固形分濃度の範囲が作業が容易で良好な乾燥物が得られる。また、工業的にはスチールベルトドライヤー、ドラムドライヤー、ディスクドライヤー等の乾燥機が採用出来る。このフィルム状にて乾燥された製品は、いわゆるフィルム状のものから箔状、薄片状、鱗片状、線条状、粉末状のものまで含まれる。
【0023】
水分散性組成物の製品水分は、全重量の1〜20%であることが好ましい。水分が高いとハンドリング性不良、べたつき、腐敗の問題があるためで、製品水分は20%以下、好ましくは15%以下、特に好ましくは10%以下がよい。また、製品水分が1%未満では、過剰乾燥のため該組成物の再分散性が悪化するため好ましくない。特に好ましくは1.5%以上である。
【0024】
以上の様にして得られた水分散性組成物は、1〜20%の水分を含む微細な細孔構造を持つ乾燥製品であり、これを水中で撹拌した時容易に分散し、平均粒径8μm以下、10μm以上の粒子の割合が40%以下、コロイド分画が65%以上の性能を有し、セルロースが均一に分散したなめらかな組織を持つザラツキの無い安定なコロイド分散体を形成する。特に酸性領域で微細セルロースが凝集を起こさないため、安定なコロイド分散体となり、安定剤等として優れた機能を奏する点が特徴である。
【0025】
本発明の食品組成物は、上記の水分散性組成物、即ち、微細セルロース100重量部に対して、置換度が0.6〜2.0であって、1%濃度における粘度が500センチポアズ以下であるCMC−Naを15〜100重量部含有する乾燥組成物であって、該組成物を水に再分散した時の平均粒径が8μm以下、10μm以上の粒子の割合が40%以下であり、かつコロイド分画が65%以上である水分散性組成物と、果汁飲料、乳酸菌飲料等の酸性飲料、またはマヨネーズ、ドレッシング、ゼリー、ジャム等の酸性食品を含有することを特徴とする食品組成物である。該水分散性組成物が懸濁安定剤、乳化安定剤、増粘安定剤、泡安定剤、クラウディー剤、組織付与剤、流動性改善剤、保形剤、離水防止剤、生地改質剤、粉末化基剤として使用されているものであり、更に上記食品全般において食物繊維基剤、油脂代替等の低カロリー化基剤等として使用されているものである。特に、果汁飲料、乳酸菌飲料等の酸性飲料、マヨネーズ、ドレッシング、ゼリー、ジャム等の酸性食品及び塩分の高い食品において顕著な効果が発揮される。
【0026】
食品組成物の製法は、常法に従って、主原料あるいは着色料、香料、酸味料、増粘剤等の他の成分と同時に、上記水分散性組成物を水に分散すれば良い。水分散性組成物を予め水に分散した後、添加してもかまわない。水分散性組成物の水中での再分散方法は、食品等の製造工程で通常使用される各種の分散・乳化・磨砕機等を用いることができる。例えば、プロペラ撹拌機、高速ミキサー、ホモミキサー、カッター等の各種ミキサー、ボールミル、コロイドミル、ビーズミル、ライカイ機等のミル類、高圧ホモジナイザー及びマイクロフルイダイザー、ナノマイザー等の超高圧ホモジナイザーに代表される分散・乳化機、プラネタリーミキサー、ニーダー、エクストルーダー、タービュライザー等に代表される混練機等が使用できる。2種以上の分散機を組み合わせて使用してもかまわない。また、加温しながら行った方が分散は容易である。
【0027】
例えば、果汁飲料の場合、市販のオレンジジュースに水分散性組成物を混合した後、ホモミキサーで分散する、あるいは水分散性組成物をホモミキサーで水中に分散させた後、オレンジジュースと混合することによって、果汁中のパルプ分等の沈降を防止することが出来る。食品組成物への水分散性組成物の添加量は食品の種類によって異なるため、それぞれ最適の添加量を選択することが必要である。例えば、飲料の場合は0.02〜3重量%程度が好ましい。特に好ましくは、0.1〜1重量%である。ドレッシング、ゼリー、ジャム等であれば0.02〜10重量%が好ましい。特に好ましくは0.1〜3重量%である。
【0028】
本発明の水分散性組成物は、コロイド分画が著しく向上したものであり、食品、医薬品、化粧品、塗料、セラミックス、樹脂、工業品等における懸濁安定剤、乳化安定剤、増粘安定剤、クラウディー剤等均一な分散性及びその長期な安定性が求められる分野において効果を発揮する。その中でも食品、特に酸性食品において、凝集、沈降を起こすことなく安定な分散状態を呈し、例えば、カルシウムの沈降防止などにも寄与する。また、安定剤としての性能が著しく向上すると共に、ザラツキの問題が解消され、滑らかさが向上するため、広い用途にわたって使用することが可能である。
【0029】
【実施例】
次に、実施例によって本発明をさらに詳細に説明する。
なお、測定は以下のとおり行った。
<コロイド分画>
(1)サンプルを固形分で0.75gを、蒸留水を入れたエースホモジナイザー(日本精機製AM−T)に入れ全量を300gとする。
(2)15000rpmで2分間分散する。
(3)分散液10mlを正確に秤量瓶にとり重量を精秤する。
(4)残りの分散液を遠沈管に移し2000rpmで15分間遠心分離する(国産遠心器製H−300型)。その上澄み液10mlを正確に秤量瓶にとり重量を精秤する。
(5)(3)、(4)の秤量瓶を105℃の乾燥器で10時間蒸発乾固する。
(6)(3)の固形分重量を精秤する。その値をAgとする。
(7)(4)の固形分重量を精秤する。その値をBgとする。
(8)微細セルロース以外の成分(水溶性ガム、親水性物質、油脂類の合計)の補正を行う。
微細セルロース以外の成分量:S%とすると、
コロイド分画(%)=(B−AS/100)×100/A(1−S/100)
<平均粒径、10μm以上の粒子の割合>
(1)サンプルを固形分で3.0gを、蒸留水を入れたエースホモジナイザー(日本精機製AM−T)に入れ全量を300gとする。
(2)15000rpmで5分間分散する。
(3)堀場レーザー回折式粒度分布測定装置(LA−500)を用いて粒度分布を測定する。平均粒径は積算体積50%の粒径であり、10μm以上の粒子の割合は体積分布における割合(%)で表す。
<水分の測定>
(1)サンプル約2gを秤量瓶に入れ、精秤する。
(2)秤量瓶を熱風乾燥機に入れ、105℃で5時間乾燥する。
(3)サンプル重量を測定し、減量から水分(%)を求める。
<CMC−Na粘度>
(1)CMC−Naを固形分で3g秤量する。
(2)TKホモミキサー(特殊機化工業製)に蒸留水297gを入れ8000rpmで撹拌しながら、CMC−Naを徐々に入れる。
(3)2分間撹拌後、25℃に1夜静置する。
(4)B型回転粘度計を用いて60rpmで測定する。
<CMC−Na置換度>
(1)CMC−Na約3gにメタノール90ml、3N塩酸10mlを加え、15分間沸騰させる。
(2)液を吸引濾過した後、80%メタノール200ml、メタノール50mlで洗浄する。
(3)残渣を乾燥させた後、約1gを精秤し、80%メタノール15mlを加える。
(4)次に0.1N水酸化ナトリウム50mlを加えて溶かす。
(5)次に、フェノールフタレイン指示薬を加えた後、0.1N塩酸で滴定する。
(6)同様に空試験を行い、以下の式を用いて置換度を求める。
【0030】
置換度=(162×A)/(10000−80A)
但し、A=(B−S)f×0.1/X
B:空試験の0.1N塩酸量(ml)
S:試料の0.1N塩酸量(ml)
f:0.1N塩酸の力価係数
X:残渣重量(g)
【0031】
【実施例1】
市販DPパルプを細断後、10%塩酸中で105℃20分間加水分解して得られた酸不溶性残渣をろ過、洗浄した後、固形分10%のセルロース分散液を調製した。この加水分解セルロースの平均粒径は17μmであった。このセルロース分散液を媒体撹拌湿式粉砕装置(コトブキ技研工業株式会社製アペックスミル、AM−1型)で、媒体として直径1mmφのジルコニアビーズを用いて、撹拌翼回転数1800rpm、セルロース分散液の供給量0.4l/minの条件で2回通過で粉砕処理を行い、微細セルロースAのペースト状物を得た。この微細セルロースAのコロイド分画は73%、積算体積50%の粒径は3.1μm、10μm以上の粒子の割合は2.3%であった。
【0032】
次に、固形分当たり微細セルロースA100重量部、CMC−Na(置換度0.90、粘度7センチポアズ)25重量部となるように混合し、総固形分濃度が11%のペースト状分散液を調整した。この分散液をドラムドライヤー(楠木機械製作所製KDD−1型)で、水蒸気圧力2Kg/cm2 、回転数0.6rpmで乾燥し、スクレーパーで掻き取って取り出した。続いて、カッティングタイプの粉砕機であるフラッシュミル(不二パウダル製)で粗砕して1000μm以下とし、薄片状、鱗片状の水分散性組成物Aを得た。水分散性組成物Aの水分は3.5%で、コロイド分画は92%、積算体積50%の粒径が3.4μm、10μm以上の粒子の割合は3.8%であった。
【0033】
粒度測定用の分散液にクエン酸を添加してpHを3.2に調製し、二日放置したところ分散液は安定な分散状態を保っていた。また、粒度測定用の分散液に食塩を3%濃度になるように添加し2日放置したが、分散液は安定な分散状態を保っていた。
また、水分散性組成物Aの5重量%水分散体はザラツキの無い滑らかな食感を有しており、この水分散体を顕微鏡で観察した結果、セルロース粒子は均一に分散しており粗大な凝集体は見られなかった。なお、「滑らかさ」は口に入れた瞬間のとろける感触を、「ザラツキ」は後口として舌の上に残る異物感を評価したものである。
【0034】
【実施例2】
固形分当たり実施例1の微細セルロースA100重量部、CMC−Na(置換度1.25、粘度25センチポアズ)40重量部となるように混合し、総固形分濃度が8%のペースト状分散液を調整した。この分散液をドラムドライヤー(KDD−1型)で、水蒸気圧力3Kg/cm2 、回転数0.8rpmで乾燥した。続いて、カッティングタイプの粉砕機であるフラッシュミル(不二パウダル製)で粗砕して1000μm以下とし、薄片状、鱗片状の水分散性組成物Bを得た。水分散性組成物Bの水分は4.3%で、コロイド分画は94%、積算体積50%の粒径が3.2μm、10μm以上の粒子の割合は3.0%であった。
【0035】
実施例1と同様に、クエン酸、食塩を添加し放置したところ、分散液は安定であった。
【0036】
【実施例3】
市販DPパルプを細断後、10%塩酸中で105℃で20分間加水分解して得られた酸不溶性残渣をろ過、洗浄した後、固形分13%のセルロース分散液を調製した。このセルロース分散液を高圧破砕装置(ナノマイザー株式会社製ナノマイザーLA−31型)で、1300Kg/cm2 、3回通過で破砕処理を行い、微細セルロースBのペースト状物を得た。この微細セルロースBのコロイド分画は82%、積算体積50%の粒径は5.6μm、10μm以上の粒子の割合は15.5%であった。
【0037】
固形分当たり微細セルロースB100重量部、CMC−Na(置換度0.72、粘度100センチポイズ)30重量部、サラダ油(日清製油製)0.5重量部を混合し、総固形分濃度が10重量%の分散液を調整した。この分散液を実施例1と同様の方法で乾燥した。続いて、衝撃式粉砕機(日本精機製作所製)で粉砕して150μm以下とし、粉末状の水分散性組成物Cを得た。水分散性組成物Cの水分は3.7%で、コロイド分画は83%、平均粒径は5.5μm、10μm以上の粒子の割合は16.8%であり、その5重量%水分散体はザラツキの無い滑らかな食感を有していた。
【0038】
また、実施例1と同様に、クエン酸、食塩を添加し放置したところ、分散液は安定であった。
【0039】
【実施例4】
固形分当たり実施例1の微細セルロースA100重量部、CMC−Na(置換度1.2、粘度150センチポイズ)15重量部、カラギーナン(CS−67、三栄源FFI製)5重量部を混合して、総固形分濃度が5%の分散液を調整した。これを撹拌しながら80℃30分間の加熱処理を行った後排出温度80℃で噴霧乾燥を行い、水分散性組成物Dを得た。
【0040】
水分散性組成物Dの水分は3.2%で、積算体積50%の粒径が3.2μm、10μm以上の粒子の割合は2.4%、コロイド分画は96%であった。
また、実施例1と同様に、クエン酸、食塩を添加し放置したところ、分散液は安定であった。
【0041】
【実施例5】
固形分当たり実施例3の微細セルロースB100重量部、CMC−Na(置換度0.90、粘度7センチポイズ)80重量部、キサンタンガム5重量部、澱粉加水分解物20重量部、サラダ油2重量部を混合して、総固形分濃度が8%の分散液を調整した。ドラム回転数を1.5rpmにする以外は実施例1と同じように操作し、水分散性組成物Eを得た。水分散性組成物Eの水分は4.6%で、積算体積50%の粒径が5.4μm、10μm以上の粒子の割合は15.2%、コロイド分画は92%であった。
【0042】
また、実施例1と同様に、クエン酸、食塩を添加し放置したところ、分散液は安定であった。
【0043】
【実施例6〜8】
水分散性組成物A〜Cをそれぞれ9gとり、水291gを添加後、エースホモジナイザーを用いて15000rpmで5分間分散させる。各分散液60gと市販オレンジジュース天然果汁(カゴメ製)300gをTKホモミキサーを用いて7000rpmで2分間混合し、オレンジジュース飲料を作製した(水分散性組成物添加量は0.5%)。
【0044】
飲料を2日間冷蔵庫中で放置し、観察及び試飲を行った。その結果、いずれも凝集等はほとんど見られず、安定な分散状態を示した。また、ざらつき、糊っぽさは感じられず、喉越しも良かった。
【0045】
【実施例9〜10】
水分散性組成物D、Eを用い、分散液を40gとする以外は、実施例6と同様に操作し、オレンジジュース飲料を作製した(水分散性組成物添加量は0.35%)。
飲料を2日間冷蔵庫中で放置し、観察及び試飲を行った。その結果、いずれも凝集等はほとんど見られず、安定な分散状態を示した。また、ざらつき、糊っぽさは感じられず、喉越しも良かった。
【0046】
【実施例11〜15】
水分散性組成物A〜Eをそれぞれ1.5gとり、水268.5g、ドリンクヨーグルト「ビヒダス」(森永乳業製)を添加後、エースホモジナイザーを用いて15000rpmで5分間分散させる。その後、クエン酸溶液でpHを3.8に調製し、ライト感覚の乳酸菌飲料を作製した(水分散性組成物添加量は0.5%)。
【0047】
飲料を2日間冷蔵庫中で放置し、観察及び試飲を行った。
その結果、いずれも凝集等はほとんど見られず、安定な分散状態を示した。また、ざらつき、糊っぽさは感じられず、喉越しも良かった。
【0048】
【比較例1】
CMC−Naを5重量部、澱粉加水分解物を20重量部とする以外は実施例1と同じ方法で操作し、組成物Fを得た。
組成物Fの水分は2.8%で、コロイド分画は84%、積算体積50%の粒径が4.5μm、10μm以上の粒子の割合は14%であった。
【0049】
実施例1と同様に、クエン酸、食塩を添加し放置したところ、セルロース粒子の沈降及び凝集が見られた。
【0050】
【比較例2】
CMC−Na(置換度0.55、粘度20センチポイズ)を使用する以外は、実施例1と同じ方法で操作し、組成物Gを得た。
組成物Gの水分は3.8%、コロイド分画は88%、積算体積50%の粒径が3.6μm、10μm以上の粒子の割合は3.3%であった。
【0051】
実施例1と同様に、クエン酸、食塩を添加し放置したところ、セルロース粒子の沈降及び凝集が見られた。
【0052】
【比較例3】
CMC−Na(置換度0.72、粘度1200センチポイズ)を使用する以外は、実施例2と同じ方法で操作し、組成物Hを得た
組成物Hの水分は4.2%、コロイド分画は86%、積算体積50%の粒径が3.4μm、10μm以上の粒子の割合は3.9%であった。
【0053】
その5重量%水分散体を口に含むと粘性が高く、糊っぽさが感じられた。
【0054】
【比較例4】
実施例1のセルロース分散液を媒体撹拌湿式粉砕装置(コトブキ技研工業株式会社製アペックスミル、AM−1型)で、媒体として直径1mmφのジルコニアビーズを用いて、撹拌翼回転数1800rpm、セルロース分散液の供給量0.4l/minの条件で1回通過で粉砕処理を行い、セルロースのペースト状物を得た。このセルロースのコロイド分画は45%、積算体積50%の粒径は7.2μm、10μm以上の粒子の割合は33%であった。
【0055】
このセルロースを用いて、実施例1と同じように操作して組成物Iを得た。組成物Iの水分は3.8%、コロイド分画は60%、積算体積50%の粒径が7.0μm、10μm以上の粒子の割合は31%であり、その5重量%水分散体を口に含むとやや肌理が粗くザラツキが感じられた。
【0056】
【比較例5】
実施例1のセルロース分散液を高圧破砕装置(ナノマイザー株式会社製ナノマイザーLA−31型)で、1300Kg/cm2 、1回通過で破砕処理を行い、セルロースのペースト状物を得た。このセルロースのコロイド分画は52%、積算体積50%の粒径は10.6μm、10μm以上の粒子の割合は51.5%であった。
【0057】
このセルロースを用いて、実施例1と同じように操作して組成物Jを得た。組成物Jの水分は3.1%、コロイド分画は55%、積算体積50%の粒径が11.7μm、10μm以上の粒子の割合は55%であり、その5重量%水分散体を口に含むと肌理が粗くザラツキが感じられた。
【0058】
【比較例6】
CMC−Naを300重量部とする以外は実施例1と同じ方法で操作し、組成物Kを得た。
組成物Kの水分は4.8%で、コロイド分画は88%、積算体積50%の粒径が3.5μm、10μm以上の粒子の割合は6%であった。
【0059】
その5重量%水分散体を口に含むと粘性が高く、糊っぽさが感じられた。
【0060】
【比較例7】
分散液の代わりに水60gを使用する以外は実施例6と同様に操作し、オレンジジュース飲料を得た。
2日間放置した結果、果汁中の繊維分と見られる凝集が発生し、その一部は沈降し、安定な分散液とならなかった。
【0061】
【比較例8】
組成物Fを用いて実施例6と同様に操作し、オレンジジュース飲料を得た。
2日間放置した結果、果汁中の繊維分及び微細セルロースと見られる凝集が発生し、その一部は沈降し、安定な分散液とならなかった。
【0062】
【比較例9】
水270gと「ビヒダス」30gをエースホモミキサーを用いて15000rpmで5分間混合した後、2日間放置した。
乳脂肪あるいは乳タンパクと考えられる沈降のため離水を起こし、安定な分散液とならなかった。
【0063】
【比較例10】
組成物Gを用いて実施例11と同様に操作し、乳酸菌飲料を得た。
2日間放置した結果、微細セルロース及び乳脂肪あるいは乳タンパクと考えられる沈降のため離水を起こし、安定な分散液とならなかった。
【0064】
【発明の効果】
本発明の水分散性組成物は、コロイド分画が著しく向上したものであり、食品、医薬品、化粧品、塗料、セラミックス、樹脂、工業品等における懸濁安定剤、乳化安定剤、増粘安定剤、クラウディー剤等均一な分散性及びその長期な安定性が求められる分野において効果を発揮する。特に酸性領域においても微細セルロースの凝集を起こさず、安定に分散することによって、懸濁安定剤、乳化安定剤、増粘安定剤、組織付与剤、クラウディー剤、白度向上、流動性改良、研磨剤、食物繊維、油脂代替物として機能し、食感の面からもざらつき感が無く、滑らかな食感を付与できる。また、該水分散性組成物を含有する食品組成物は、特に酸性領域においても懸濁安定性、乳化安定性等に優れると同時に食感も優れる。
[0001]
[Industrial application fields]
The present invention relates to a water-dispersible composition and a food composition. That is, the water-dispersible composition of the present invention is a dry composition capable of forming a cellulose colloid, and is a suspension stabilizer in the fields of food, pharmaceuticals, cosmetics, paints, ceramics, resins, catalysts, and other industrial products. , Re-dispersed in water that can be used for stabilizers such as emulsion stabilizers, thickening stabilizers, tissue-imparting agents, cloudy agents, whiteness improvement, fluidity improvement, abrasives, dietary fiber, oil and fat substitutes, etc. The water-dispersible composition containing fine cellulose, and the food composition containing the water-dispersible composition has remarkably high stability such as emulsification.
[0002]
[Prior art]
JP-A-7-102113 discloses a water-dispersible composite containing fine cellulose and sodium carboxymethylcellulose (hereinafter referred to as CMC-Na). JP-A-6-335365 discloses a food composition containing a water-dispersible complex composed of fine cellulose and CMC-Na. When these composites are redispersed in water, the proportion of particles of 10 μm or more is 40% or less and the colloidal fraction is 65% or more. However, there is no description about the physical properties of CMC-Na, and the addition amount is specifically about 2 to 5% by weight.
[0003]
Conventional composites containing fine cellulose have not always had sufficient functions as stabilizers such as suspension stabilizers, emulsion stabilizers, and thickening stabilizers. In particular, since the aggregation of fine cellulose is likely to occur in the acidic region, the function as a stabilizer may not be sufficiently exhibited. Therefore, it was difficult to use for acidic foods, such as a fruit juice drink and a lactic acid bacteria drink.
[0004]
[Problems to be solved by the invention]
The present invention does not cause agglomeration of fine cellulose even in the acidic region, and stably disperses, whereby a suspension stabilizer, an emulsion stabilizer, a thickening stabilizer, a tissue imparting agent, a cloudy agent, whiteness improvement, flow It is intended to provide a fine cellulose-containing water-dispersible composition having excellent functions as a property improvement, abrasive, dietary fiber, and oil / fat substitute, and also has suspension stability and emulsification in the acidic region. An object of the present invention is to provide a food composition excellent in stability and the like.
[0005]
[Means for Solving the Problems]
  The present invention relates to CMC-Na having a substitution degree of 0.6 to 2.0 and a viscosity at 1% concentration of 500 centipoise or less with respect to 100 parts by weight of fine cellulose.15-100A dry composition containing parts by weight, wherein the average particle size when the composition is redispersed in water is 8 μm or less, the proportion of particles of 10 μm or more is 40% or less, and the colloidal fraction is 65% or more. An aqueous dispersible composition, andContains acidic beverages such as fruit juice beverages and lactic acid bacteria beverages, or acidic foods such as mayonnaise, dressing, jelly, and jamThe present invention relates to a food composition having improved stability such as suspension and emulsification in an acidic region.
[0006]
Hereinafter, the present invention will be described in detail.
There are two factors that affect the texture of the re-dispersed fine cellulose-containing water-dispersible composition. The graininess is mainly due to the proportion of particles of 10 μm or more in the particle size distribution. The smoothness to be felt is an important factor due to the practical properties of colloidal fractionation.
[0007]
The main factor for the roughness of the cellulose particles is the amount of coarse particles of 10 μm or more. When the water-dispersible composition of the present invention is re-dispersed in water, a rough feeling is produced when the proportion of the coarse particles exceeds 40%. Therefore, it is necessary that the average particle diameter is 8 μm or less and the ratio of coarse particles of 10 μm or more is 40% or less. In order to effectively achieve the object of the present invention, it is preferable that the average particle size is 6 μm or less and the ratio of coarse particles of 10 μm or more is 20% or less. More preferably, the average particle size is 4 μm or less, and the ratio of coarse particles of 10 μm or more is 10% or less.
[0008]
Also, the smoothness felt with the tongue is consistent with the colloidal fraction, which is a practical characteristic for measuring colloidal cellulose. That is, in order to obtain a smooth structure in an aqueous dispersion of an aqueous dispersible composition, it is necessary that the colloidal fraction is 65% or more as an index when the aqueous dispersible composition is dispersed in water. . Furthermore, the colloidal fraction is preferably 80% or more.
[0009]
  here"Colloidal fractionation"Is the weight ratio (%) of the solid content of the dispersed phase that is suspended and dispersed without settling when a certain centrifugal force is applied to the aqueous dispersion of the fine cellulose and the water-dispersible composition. That is, it is the ratio of the colloidal portion that can be stably dispersed without settling in the aqueous dispersion, and shows the practical ability of dispersibility and stability. Also,“Average particle size”, “Percentage of particles of 10 μm or more”Are respectively the particle size of the integrated volume 50% and the ratio (%) in the volume distribution obtained by the laser particle size distribution measuring apparatus.Specifically, among the various physical property measurement methods described in the Examples section below, the measurement values obtained by the methods described in <Average particle diameter, ratio of particles of 10 μm or more> and <Colloid fraction> That is.
[0010]
The fine cellulose used in the present invention preferably has an average particle size of 8 μm or less, a ratio of particles of 10 μm or more is 40% or less, and a colloidal fraction is 50% or more. More preferably, the ratio of particles having an average particle diameter of 6 μm or less and 10 μm or more is 20% or less. Particularly preferably, the average particle size is 4 μm or less and the proportion of particles of 10 μm or more is 10% or less. The smaller the average particle size, the better, but the lower limit is naturally limited by grinding and pulverization techniques and equipment, and is currently considered to be usually about 0,05 μm. Also, the larger the colloidal fraction, the better. The upper limit is 100%.
[0011]
This fine cellulose is obtained by depolymerizing cellulosic materials such as wood pulp and refined linter by acid hydrolysis, alkali oxidative decomposition, enzymatic decomposition, steam explosion decomposition, etc., or a combination thereof and having an average polymerization degree of 30 to 375. It can be obtained by cellulose and then wet milling with mechanical shear. Furthermore, the colloidal part can also be obtained by subjecting the wet ground material to centrifugal sedimentation.
[0012]
Suitable examples of the wet grinding machine include medium mills such as a wet vibration mill, a wet planetary vibration mill, a wet ball mill, a wet roll mill, a wet coball mill, a wet bead mill, a wet paint shaker, and a high-pressure homogenizer. About 500Kg / cm as a high-pressure homogenizer2A type in which the slurry is guided to the fine orifice at the above high pressure and collides with each other at a high flow rate is effective. The optimum grinding concentration when these mills are used varies depending on the model, but in general, a solid content concentration of 3 to 15% for a medium mill and 5 to 20% for a high-pressure homogenizer is suitable.
[0013]
For the purposes of the present invention, these models can be used alone, or two or more types can be used in combination. These models may be appropriately selected according to the viscosity requirements in various applications.
CMC-Na used in the present invention is required to have a substitution degree of 0.6 to 2.0 and a viscosity at 1% concentration of 500 centipoise or less. CMC-Na used in the present invention rapidly disperses fine cellulose in water, further enhances the stability of cellulose dispersion, suspension, etc., and functions as a protective colloid. It contributes to the improvement. That is, in general, the stability of crystalline cellulose is brought about by an electrical repulsive force caused by negatively charging the crystalline cellulose surface, but its function is improved by adsorbing CMC-Na having a carboxyl group to the cellulose surface. . The water-dispersible composition of the present invention is characterized by high stability particularly in the acidic region by using a specific amount of specific CMC-Na. In addition, it exhibits high stability even in foods with a high salt concentration.
[0014]
When the degree of substitution is less than 0.6, the stability when the water-dispersible composition is dispersed in the acidic region is not sufficient. Moreover, even if a substitution degree exceeds 2.0, stability in an acidic region will deteriorate similarly. In addition, CMC-Na having a substitution degree exceeding 2.0 is difficult to manufacture and is not practical. The degree of substitution is preferably 0.7 to 1.5, and particularly preferably 0.8 to 1.3. On the other hand, when the viscosity at 1% concentration exceeds 500 centipoise, when used in beverages or the like, the texture rises over the throat due to the increase in viscosity, which is not preferable. 200 centipoise is preferred. Particularly preferred is 50 centipoise. In commercially available products that can be used normally, the lower limit of the viscosity is about 1 centipoise.
[0015]
  The amount of CMC-Na is 100 parts by weight of fine cellulose,15-100Parts by weight.15If the amount is less than parts by weight, the water-dispersible composition does not sufficiently function as a stabilizer in the acidic region. Moreover, when it exceeds 100 weight part, the function as a stabilizer falls with the fall of the fine cellulose content with the fall of the food texture by a raise of a viscosity, and is unpreferable. Particularly preferred is 15 to 50 parts by weight.
[0016]
In addition to fine cellulose and CMC-Na, in order to improve the redispersibility of fine cellulose in water, the following water-soluble gums, hydrophilic substances and fats and oils may be blended.
Water-soluble gums are water-soluble gums with high water swellability and good compatibility with water in cellulose. Locust bean gum, guar gum, casein and sodium casein, tamarind seed gum, karaya gum, chitosan, arabian Examples thereof include gum, agar, carrageenan, alginic acid and salts thereof, pectin, Azotobacter vinelanzi gum, psyllium seed gum, xanthan gum, curdlan, pullulan, dextran, gellan gum, gelatin, cellulose derivatives, starch derivatives and the like. Xanthan gum, carrageenan, pectin, karaya gum, gelatin, and gum arabic are preferable. Two or more of these water-soluble gums may be combined.
[0017]
A hydrophilic substance is an organic substance that is highly soluble in cold water and hardly causes viscosity. It contains starch hydrolysates, dextrins, glucose, sorbose, lactose, polydextrose, fructooligosaccharides and other monosaccharides and oligosaccharides. Suitable water-soluble sugars include sugar alcohols such as maltitol and sorbit. Among them, starch hydrolysates, dextrins, glucose, lactose, polydextrose and sorbit are suitable. Two or more of these hydrophilic substances may be combined.
[0018]
If a large amount of water-soluble gums and hydrophilic substances are blended, the protective colloid properties of CMC-Na are impaired, so the total amount thereof should be about half or less of the amount of CMC-Na blended. The colloidal fraction represents the colloidal performance itself of fine cellulose when measured with fine cellulose alone, but when combined with CMC-Na, it gives a higher value than the original colloidal fraction value of fine cellulose. become. That is, the smoothness of the structure of the redispersed body of the water-dispersible composition is improved to be equal to or higher than that of the raw fine cellulose.
[0019]
Oils and fats are substances that are liquid in any temperature range of 80 to 150 ° C. and are not freely soluble in water. The temperature range is preferably 100 to 150 ° C. Specific examples include soybean oil, coconut oil, corn oil, palm oil, salad oil, sesame oil, rapeseed oil, cacao butter, castor oil, whale oil, lard, hydrogenated oil, medium chain fatty acid triglyceride, milk fat and other animal and vegetable oils, glycerin Surfactants such as fatty acid esters, polyglycerin fatty acid esters, lecithin, sucrose fatty acid esters, sorbitan fatty acid esters, fatty acids such as oleic acid, lauric acid, palmitic acid, stearic acid and their esters, and higher grades such as lauryl alcohol It consists of one kind or a combination of two or more kinds selected from alcohols, waxes such as carnauba wax, hydrocarbons such as paraffin wax, and silicone oils such as polydimethylsiloxane. In the case of a surfactant, a hydrophobic one is preferable to a hydrophilic one, and an HLB value of 13 or less is preferable. Fats and oils can be added as they are, but they may be added after making the form of an emulsion obtained by adding a surfactant, water or the like to animal and vegetable oils and homogenizing them. Moreover, you may mix | blend with forms, such as margarine and fresh cream containing fats and oils. The blending amount of fats and oils should be about 20 parts by weight or less with respect to 100 parts by weight of fine cellulose. If it exceeds 20 parts by weight, even if the composition is stirred in water, it is difficult for water to penetrate into the interior, so that the redispersibility is lowered, which is not preferable. The amount is preferably 10 parts by weight or less. The amount is particularly preferably 5 parts by weight or less.
[0020]
Regarding the blending of the other components, it is free to blend to such an extent that the dispersion of the composition in water is not inhibited.
The water-dispersible composition of the present invention is obtained by first crushing fine cellulose having a mean particle size of 8 μm or less and a particle size of 10 μm or more obtained by grinding to 40% or less and a colloidal fraction of 50% or more. If necessary, it can be mixed with water-soluble gums, hydrophilic substances, oils and fats to form a slurry, and then dried. In addition, a method in which the depolymerized cellulose is previously mixed with CMC-Na or the like, and ground by a wet medium mill or a high-pressure homogenizer to obtain a slurry is also possible. In any case, when mixing and dispersing with CMC-Na, etc., especially when CMC-Na and water-soluble gums are sufficiently dissolved, and when mixing with CMC-Na and others, fine cellulose is homogeneous in the dispersion. Must be dispersed. For this purpose, when mixing fine cellulose, CMC-Na, and the like, it is preferable to sufficiently stir in the presence of 75% or more of the total weight of water and mix uniformly. At this time, it is more effective to disperse CMC-Na and others in an appropriate amount of water in advance and then add and mix fine cellulose. The heat treatment is an effective method for promoting dissolution of CMC-Na or the like.
[0021]
Drying is a major factor that affects the performance of the water-dispersible composition. In order to ensure the redispersibility of the water-dispersible composition in water, the composition preferably has innumerable fine cracks and cavities in a network. The cracks become water-conducting pores that promote CMC-Na dissolution and fine cellulose dispersion. This crack is a gap of about 0.05 to 0.5 μm, and the interval between the pores is preferably suppressed to about 3 μm at the maximum. As a drying method giving this structure, freeze drying, spray drying, or the like can be adopted, but it is preferable to dry in a film form. The freeze-drying method has a low production efficiency, and the spray-drying method requires a large apparatus and has a drawback that the quality control of the product is difficult and the re-dispersion performance of the dried product tends to vary. When using a spray dryer, it is necessary to keep the spray particle size small and to perform the drying speed as quickly as possible in order to reduce this variation.
[0022]
As a method having the best dispersibility of the fine cellulose-containing water-dispersible composition, a method of drying in a film form is excellent. The method of drying in the form of a film is a method in which fine cellulose and CMC-Na or other mixed slurry is cast on a substrate such as glass, stainless steel, aluminum, nickel / chromium plated steel plate and dried. The substrate may be preheated, or may be heated with infrared rays, hot air, high frequency, etc. after casting. The drying temperature is preferably 200 ° C. or less, and the casting thickness is preferably 10 mm or less as the thickness of the slurry. The slurry concentration is not particularly limited as long as it can be developed into a film, and practically, a solid content concentration range of about 5% to 20% is easy to work and a good dried product can be obtained. Industrially, a dryer such as a steel belt dryer, a drum dryer, or a disk dryer can be employed. The product dried in the form of a film includes a so-called film-like product, a foil-like shape, a flake-like shape, a scale-like shape, a linear shape, and a powder-like shape.
[0023]
The product moisture of the water dispersible composition is preferably 1 to 20% of the total weight. When the moisture is high, there are problems of poor handleability, stickiness, and decay, and the product moisture is 20% or less, preferably 15% or less, and particularly preferably 10% or less. Further, if the product moisture is less than 1%, the redispersibility of the composition deteriorates due to excessive drying, which is not preferable. Particularly preferably, it is 1.5% or more.
[0024]
The water-dispersible composition obtained as described above is a dry product having a fine pore structure containing 1 to 20% of water, and is easily dispersed when stirred in water, and has an average particle size. A stable colloidal dispersion having a smooth texture in which the proportion of particles of 8 μm or less and 10 μm or more is 40% or less and the colloidal fraction is 65% or more and a smooth structure in which cellulose is uniformly dispersed is formed. In particular, since fine cellulose does not agglomerate in the acidic region, it becomes a stable colloidal dispersion and is characterized by an excellent function as a stabilizer or the like.
[0025]
  The food composition of the present invention has a degree of substitution of 0.6 to 2.0 and a viscosity at 1% concentration of 500 centipoise or less with respect to the above-mentioned water-dispersible composition, that is, 100 parts by weight of fine cellulose. CMC-Na15-100A dry composition containing parts by weight, wherein when the composition is redispersed in water, the average particle size is 8 μm or less, the proportion of particles of 10 μm or more is 40% or less, and the colloidal fraction is 65% or more. A water dispersible composition which isContains acidic beverages such as fruit juice beverages and lactic acid bacteria beverages, or acidic foods such as mayonnaise, dressing, jelly, and jamIt is a food composition characterized by this. The water-dispersible composition is a suspension stabilizer, an emulsion stabilizer, a thickening stabilizer, a foam stabilizer, a cloudy agent, a tissue imparting agent, a fluidity improving agent, a shape retention agent, a water separation preventing agent, and a dough modifying agent. In addition, it is used as a powdered base, and is further used as a low calorie base for dietary fiber bases, fats and oil substitutes and the like in the above-mentioned foods in general. In particular, remarkable effects are exhibited in acidic beverages such as fruit juice beverages and lactic acid bacteria beverages, acidic foods such as mayonnaise, dressing, jelly and jam, and foods with high salt content.
[0026]
The food composition may be produced by dispersing the water-dispersible composition in water at the same time as the main ingredients or other components such as a colorant, a fragrance, a sour agent, and a thickener, according to a conventional method. The water dispersible composition may be added after being previously dispersed in water. As a method for redispersing the water-dispersible composition in water, various dispersing / emulsifying / grinding machines or the like that are usually used in the production process of foods and the like can be used. For example, various types of mixers such as propeller stirrers, high-speed mixers, homomixers, cutters, mills such as ball mills, colloid mills, bead mills, reika machines, dispersions represented by ultrahigh pressure homogenizers such as high-pressure homogenizers, microfluidizers, and nanomizers A kneader represented by an emulsifier, a planetary mixer, a kneader, an extruder, a turbulizer, or the like can be used. Two or more types of dispersers may be used in combination. In addition, dispersion is easier if performed while heating.
[0027]
For example, in the case of a fruit juice beverage, a water-dispersible composition is mixed with commercially available orange juice and then dispersed with a homomixer, or a water-dispersible composition is dispersed with water with a homomixer and then mixed with orange juice. In this way, sedimentation of pulp and the like in the fruit juice can be prevented. Since the amount of the water-dispersible composition added to the food composition varies depending on the type of food, it is necessary to select an optimum amount added for each. For example, in the case of a beverage, about 0.02 to 3% by weight is preferable. Most preferably, it is 0.1 to 1 weight%. In the case of dressing, jelly, jam, etc., 0.02 to 10% by weight is preferable. Most preferably, it is 0.1 to 3 weight%.
[0028]
The water-dispersible composition of the present invention has a remarkably improved colloidal fraction, and is a suspension stabilizer, emulsion stabilizer, thickening stabilizer in foods, pharmaceuticals, cosmetics, paints, ceramics, resins, industrial products, etc. It is effective in fields where uniform dispersibility and long-term stability such as cloudy agents are required. Among them, foods, particularly acidic foods, exhibit a stable dispersion state without causing aggregation and sedimentation, and contribute to, for example, prevention of calcium sedimentation. Moreover, since the performance as a stabilizer improves remarkably, the problem of roughness is solved and the smoothness is improved, it can be used over a wide range of applications.
[0029]
【Example】
Next, the present invention will be described in more detail with reference to examples.
The measurement was performed as follows.
<Colloid fractionation>
(1) Put 0.75 g of the sample in solid content in an ace homogenizer (Nippon Seiki AM-T) containing distilled water to make the total amount 300 g.
(2) Disperse at 15000 rpm for 2 minutes.
(3) Accurately weigh 10 ml of the dispersion in a weighing bottle.
(4) The remaining dispersion is transferred to a centrifuge tube and centrifuged at 2000 rpm for 15 minutes (H-300 manufactured by Japan-made centrifuge). 10 ml of the supernatant is accurately placed in a weighing bottle and accurately weighed.
(5) The weighing bottles of (3) and (4) are evaporated to dryness in a dryer at 105 ° C. for 10 hours.
(6) The solid content weight of (3) is precisely weighed. The value is Ag.
(7) The solid content weight of (4) is precisely weighed. Let that value be Bg.
(8) Correction of components other than fine cellulose (total of water-soluble gum, hydrophilic substance, fats and oils).
Ingredients other than fine cellulose: S%
Colloid fraction (%) = (B−AS / 100) × 100 / A (1−S / 100)
<Ratio of particles having an average particle size of 10 μm or more>
(1) Put 3.0 g of the sample in solid content into an ace homogenizer (Nippon Seiki AM-T) containing distilled water to make the total amount 300 g.
(2) Disperse at 15000 rpm for 5 minutes.
(3) The particle size distribution is measured using a Horiba laser diffraction particle size distribution measuring device (LA-500). An average particle diameter is a particle diameter of 50% of integrated volume, and the ratio of the particle | grains 10 micrometers or more is represented by the ratio (%) in volume distribution.
<Measurement of moisture>
(1) About 2 g of a sample is put in a weighing bottle and precisely weighed.
(2) The weighing bottle is put into a hot air dryer and dried at 105 ° C. for 5 hours.
(3) The sample weight is measured, and the moisture (%) is obtained from the weight loss.
<CMC-Na viscosity>
(1) Weigh 3 g of CMC-Na in solid content.
(2) Add 297 g of distilled water to a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and gradually add CMC-Na while stirring at 8000 rpm.
(3) After stirring for 2 minutes, leave at 25 ° C. overnight.
(4) Measure at 60 rpm using a B-type rotational viscometer.
<CMC-Na substitution degree>
(1) Add 90 ml of methanol and 10 ml of 3N hydrochloric acid to about 3 g of CMC-Na, and boil for 15 minutes.
(2) The solution is filtered with suction and washed with 200 ml of 80% methanol and 50 ml of methanol.
(3) After the residue is dried, about 1 g is precisely weighed and 15 ml of 80% methanol is added.
(4) Next, add 50 ml of 0.1N sodium hydroxide and dissolve.
(5) Next, after adding a phenolphthalein indicator, titrate with 0.1N hydrochloric acid.
(6) A blank test is performed in the same manner, and the degree of substitution is obtained using the following equation.
[0030]
Degree of substitution = (162 × A) / (10000-80A)
However, A = (B−S) f × 0.1 / X
B: 0.1N hydrochloric acid amount for blank test (ml)
S: 0.1N hydrochloric acid amount of sample (ml)
f: 0.1N hydrochloric acid titer coefficient
X: Residue weight (g)
[0031]
[Example 1]
After shredding commercially available DP pulp, the acid-insoluble residue obtained by hydrolysis in 10% hydrochloric acid at 105 ° C. for 20 minutes was filtered and washed, and then a cellulose dispersion having a solid content of 10% was prepared. The average particle size of the hydrolyzed cellulose was 17 μm. This cellulose dispersion was mixed with a medium stirring wet pulverizer (Apex Mill, manufactured by Kotobuki Giken Kogyo Co., Ltd., AM-1 type), using zirconia beads with a diameter of 1 mmφ as a medium, the rotation speed of stirring blades 1800 rpm, and the amount of cellulose dispersion supplied A fine cellulose A paste was obtained by pulverizing twice by passing under conditions of 0.4 l / min. The colloidal fraction of this fine cellulose A was 73%, the particle size of the cumulative volume 50% was 3.1 μm, and the proportion of particles of 10 μm or more was 2.3%.
[0032]
Next, 100 parts by weight of fine cellulose A per solid content and 25 parts by weight of CMC-Na (substitution degree 0.90, viscosity 7 centipoise) are mixed to prepare a paste-like dispersion having a total solid content concentration of 11%. did. This dispersion liquid was subjected to a water vapor pressure of 2 kg / cm with a drum dryer (KDD-1 type manufactured by Kashiwagi Seisakusho).2Then, it was dried at a rotation number of 0.6 rpm, and scraped off with a scraper. Subsequently, the mixture was roughly pulverized with a flash mill (made by Fuji Paudal), which is a cutting type pulverizer, to a thickness of 1000 μm or less to obtain a flaky and scaly water-dispersible composition A. The water dispersible composition A had a water content of 3.5%, a colloidal fraction of 92%, a particle volume of an integrated volume of 50% of 3.4 μm, and a ratio of particles of 10 μm or more was 3.8%.
[0033]
Citric acid was added to the dispersion for particle size measurement to adjust the pH to 3.2, and when left for two days, the dispersion kept a stable dispersion state. Further, sodium chloride was added to the dispersion for particle size measurement so as to have a concentration of 3% and left for 2 days, but the dispersion kept a stable dispersion state.
Further, the 5% by weight aqueous dispersion of the water-dispersible composition A has a smooth texture without roughness. As a result of observing the aqueous dispersion with a microscope, the cellulose particles are uniformly dispersed and coarse. No agglomerates were found. “Smoothness” is a feeling of melting at the moment when it is put in the mouth, and “Roughness” is an evaluation of a feeling of a foreign object remaining on the tongue as a rear mouth.
[0034]
[Example 2]
100 parts by weight of fine cellulose A of Example 1 per solid content and 40 parts by weight of CMC-Na (substitution degree 1.25, viscosity 25 centipoise) were mixed, and a paste-like dispersion having a total solid content concentration of 8% was mixed. It was adjusted. This dispersion was subjected to a water vapor pressure of 3 kg / cm with a drum dryer (KDD-1 type).2And dried at a rotation speed of 0.8 rpm. Subsequently, the mixture was roughly crushed with a flash mill (made by Fuji Powder), which is a cutting type pulverizer, to a thickness of 1000 μm or less to obtain a flaky and scaly water-dispersible composition B. The water-dispersible composition B had a water content of 4.3%, a colloidal fraction of 94%, a particle size of an integrated volume of 50% of 3.2 μm, and a ratio of particles of 10 μm or more was 3.0%.
[0035]
As in Example 1, citric acid and sodium chloride were added and allowed to stand, and the dispersion was stable.
[0036]
[Example 3]
After shredding commercially available DP pulp, the acid-insoluble residue obtained by hydrolysis in 10% hydrochloric acid at 105 ° C. for 20 minutes was filtered and washed, and then a cellulose dispersion having a solid content of 13% was prepared. This cellulose dispersion was 1300 Kg / cm with a high-pressure crusher (Nanomizer LA-31, manufactured by Nanomizer Co., Ltd.).2Crushing treatment was performed by passing three times to obtain a pasty product of fine cellulose B. The colloidal fraction of this fine cellulose B was 82%, the particle size of the cumulative volume 50% was 5.6 μm, and the proportion of particles of 10 μm or more was 15.5%.
[0037]
100 parts by weight of fine cellulose B per solid content, 30 parts by weight of CMC-Na (degree of substitution 0.72, viscosity 100 centipoise), 0.5 parts by weight of salad oil (Nisshin Oil Co., Ltd.) are mixed, and the total solid content concentration is 10 weights % Dispersion was prepared. This dispersion was dried in the same manner as in Example 1. Subsequently, the mixture was pulverized with an impact pulverizer (manufactured by Nippon Seiki Seisakusho) to 150 μm or less to obtain a powdery water-dispersible composition C. The water-dispersible composition C has a water content of 3.7%, a colloidal fraction of 83%, an average particle size of 5.5 μm, and the proportion of particles of 10 μm or more is 16.8%, and its 5% by weight water dispersion The body had a smooth texture without roughness.
[0038]
Further, in the same manner as in Example 1, when the citric acid and sodium chloride were added and allowed to stand, the dispersion was stable.
[0039]
[Example 4]
100 parts by weight of fine cellulose A of Example 1 per solid content, 15 parts by weight of CMC-Na (substitution degree 1.2, viscosity 150 centipoise), 5 parts by weight of carrageenan (CS-67, manufactured by Saneigen FFI) are mixed, A dispersion having a total solid content concentration of 5% was prepared. The mixture was heat-treated at 80 ° C. for 30 minutes while stirring, and then spray-dried at a discharge temperature of 80 ° C. to obtain a water-dispersible composition D.
[0040]
The water-dispersible composition D had a moisture content of 3.2%, a particle size with an integrated volume of 50% of 3.2 μm, a proportion of particles with a particle size of 10 μm or more was 2.4%, and the colloidal fraction was 96%.
Further, in the same manner as in Example 1, when the citric acid and sodium chloride were added and allowed to stand, the dispersion was stable.
[0041]
[Example 5]
100 parts by weight of fine cellulose B of Example 3 per solid content, 80 parts by weight of CMC-Na (substitution degree 0.90, viscosity 7 centipoise), 5 parts by weight of xanthan gum, 20 parts by weight of starch hydrolyzate, and 2 parts by weight of salad oil are mixed. Then, a dispersion having a total solid content concentration of 8% was prepared. A water-dispersible composition E was obtained in the same manner as in Example 1 except that the drum rotation speed was 1.5 rpm. The water-dispersible composition E had a water content of 4.6%, a particle size of 50% cumulative volume of 5.4 μm, a proportion of particles of 10 μm or more was 15.2%, and the colloidal fraction was 92%.
[0042]
Further, in the same manner as in Example 1, when the citric acid and sodium chloride were added and allowed to stand, the dispersion was stable.
[0043]
Examples 6 to 8
9 g of each of the water-dispersible compositions A to C is taken, and after adding 291 g of water, it is dispersed for 5 minutes at 15000 rpm using an ace homogenizer. 60 g of each dispersion and 300 g of commercially available orange juice natural fruit juice (manufactured by Kagome) were mixed at 7000 rpm for 2 minutes using a TK homomixer to prepare an orange juice beverage (the amount of water-dispersible composition added was 0.5%).
[0044]
The beverage was left in the refrigerator for 2 days for observation and tasting. As a result, almost no aggregation or the like was observed, indicating a stable dispersion state. In addition, the graininess and pasteiness were not felt, and the throat was good.
[0045]
Examples 9 to 10
An orange juice beverage was prepared in the same manner as in Example 6 except that the water-dispersible compositions D and E were used and the dispersion was changed to 40 g (the amount of the water-dispersible composition added was 0.35%).
The beverage was left in the refrigerator for 2 days for observation and tasting. As a result, almost no aggregation or the like was observed, indicating a stable dispersion state. In addition, the graininess and pasteiness were not felt, and the throat was good.
[0046]
Examples 11 to 15
Take 1.5 g of each of the water-dispersible compositions A to E, add 268.5 g of water and drink yogurt “Bihidas” (manufactured by Morinaga Milk Industry), and then disperse at 15000 rpm for 5 minutes using an ace homogenizer. Thereafter, the pH was adjusted to 3.8 with a citric acid solution to prepare a light-sensitive lactic acid bacteria beverage (the amount of the water-dispersible composition added was 0.5%).
[0047]
The beverage was left in the refrigerator for 2 days for observation and tasting.
As a result, almost no aggregation or the like was observed, indicating a stable dispersion state. In addition, the graininess and pasteiness were not felt, and the throat was good.
[0048]
[Comparative Example 1]
A composition F was obtained in the same manner as in Example 1 except that 5 parts by weight of CMC-Na and 20 parts by weight of the starch hydrolyzate were used.
The water content of the composition F was 2.8%, the colloidal fraction was 84%, and the proportion of particles having an integrated volume of 50% having a particle size of 4.5 μm and 10 μm or more was 14%.
[0049]
In the same manner as in Example 1, when citric acid and sodium chloride were added and allowed to stand, sedimentation and aggregation of cellulose particles were observed.
[0050]
[Comparative Example 2]
A composition G was obtained by operating in the same manner as in Example 1, except that CMC-Na (degree of substitution 0.55, viscosity 20 centipoise) was used.
The water content of the composition G was 3.8%, the colloidal fraction was 88%, the proportion of particles having an integrated volume of 50% having a particle size of 3.6 μm and 10 μm or more was 3.3%.
[0051]
In the same manner as in Example 1, when citric acid and sodium chloride were added and allowed to stand, sedimentation and aggregation of cellulose particles were observed.
[0052]
[Comparative Example 3]
A composition H was obtained by operating in the same manner as in Example 2 except that CMC-Na (degree of substitution 0.72, viscosity 1200 centipoise) was used.
The water content of Composition H was 4.2%, the colloidal fraction was 86%, and the proportion of particles with an integrated volume of 50% having a particle size of 3.4 μm and 10 μm or more was 3.9%.
[0053]
When the 5% by weight aqueous dispersion was contained in the mouth, the viscosity was high and a stickiness was felt.
[0054]
[Comparative Example 4]
Using the zirconia beads having a diameter of 1 mmφ as the medium, the cellulose dispersion of Example 1 was mixed with a medium stirring wet pulverizer (Kotobuki Giken Co., Ltd. Apex Mill, AM-1 type), and the cellulose dispersion was stirred at 1800 rpm. Was pulverized once in a condition of 0.4 l / min to obtain a cellulose paste. The colloidal fraction of cellulose was 45%, the particle size of the cumulative volume 50% was 7.2 μm, and the proportion of particles of 10 μm or more was 33%.
[0055]
Using this cellulose, the same operation as in Example 1 was carried out to obtain Composition I. The water content of the composition I is 3.8%, the colloidal fraction is 60%, the particle size of the cumulative volume 50% is 7.0 μm, the proportion of the particles of 10 μm or more is 31%, and the 5% by weight aqueous dispersion is obtained. When it was included in the mouth, it was somewhat rough and rough.
[0056]
[Comparative Example 5]
1300 Kg / cm of the cellulose dispersion of Example 1 using a high-pressure crusher (Nanomizer LA-31, manufactured by Nanomizer Co., Ltd.)2A crushing process was performed in one pass to obtain a cellulose paste. The colloidal fraction of this cellulose was 52%, the particle size of 50% cumulative volume was 10.6 μm, and the proportion of particles of 10 μm or more was 51.5%.
[0057]
Using this cellulose, the same operation as in Example 1 was performed to obtain a composition J. The water content of the composition J is 3.1%, the colloidal fraction is 55%, the particle size of the integrated volume 50% is 11.7 μm, the proportion of the particles of 10 μm or more is 55%, and 5% by weight of the aqueous dispersion is obtained. When it was in the mouth, the texture was rough and rough.
[0058]
[Comparative Example 6]
A composition K was obtained in the same manner as in Example 1 except that CMC-Na was changed to 300 parts by weight.
The water content of the composition K was 4.8%, the colloidal fraction was 88%, and the proportion of particles having a cumulative volume of 50% having a particle size of 3.5 μm and 10 μm or more was 6%.
[0059]
When the 5% by weight aqueous dispersion was contained in the mouth, the viscosity was high and a stickiness was felt.
[0060]
[Comparative Example 7]
An orange juice beverage was obtained in the same manner as in Example 6 except that 60 g of water was used instead of the dispersion.
As a result of standing for 2 days, agglomeration, which was considered to be a fiber content in the fruit juice, occurred, a part of which settled and did not become a stable dispersion.
[0061]
[Comparative Example 8]
Using composition F, the same operation as in Example 6 was performed to obtain an orange juice beverage.
As a result of standing for 2 days, the aggregation of the fiber content and the fine cellulose seen in the fruit juice occurred, and some of them settled and did not become a stable dispersion.
[0062]
[Comparative Example 9]
270 g of water and 30 g of “Bihidas” were mixed for 5 minutes at 15000 rpm using an ace homomixer and left for 2 days.
Water settling due to sedimentation, which was considered to be milk fat or milk protein, did not result in a stable dispersion.
[0063]
[Comparative Example 10]
The composition G was used in the same manner as in Example 11 to obtain a lactic acid bacteria beverage.
As a result of standing for 2 days, water separation occurred due to sedimentation considered to be fine cellulose and milk fat or milk protein, and a stable dispersion was not obtained.
[0064]
【The invention's effect】
The water-dispersible composition of the present invention has a remarkably improved colloidal fraction, and is a suspension stabilizer, emulsion stabilizer, thickening stabilizer in foods, pharmaceuticals, cosmetics, paints, ceramics, resins, industrial products, etc. It is effective in fields where uniform dispersibility and long-term stability such as cloudy agents are required. Especially in the acidic region, it does not cause agglomeration of fine cellulose, and by dispersing stably, suspension stabilizer, emulsion stabilizer, thickening stabilizer, tissue imparting agent, cloudy agent, whiteness improvement, fluidity improvement, It functions as an abrasive, dietary fiber, and oil / fat substitute, has no texture, and can provide a smooth texture. In addition, the food composition containing the water-dispersible composition is excellent in suspension stability, emulsion stability, etc., particularly in the acidic region, as well as in texture.

Claims (1)

下記(A)の水分散性微細セルロース組成物と、下記(B)の酸性飲料または酸性食品を含有することを特徴とする食品組成物。
(A)平均粒径が8μm以下、10μm以上の粒子の割合が40%以下、コロイド分画が50%以上の微細セルロースと、置換度が0.6〜2.0であって、1%濃度における粘度が500センチポアズ以下であるカルボキシメチルセルロースナトリウムを、75%以上の水の存在下で撹拌・混合して均一なスラリーとなし、次いで、凍結乾燥、噴霧乾燥もしくはフィルム状にて乾燥することによって製造される組成物であって、微細セルロース100重量部に対して、カルボキシメチルセルロースナトリウムを15〜100重量部含有し、該組成物を水に再分散した時の平均粒径が8μm以下で、10μm以上の粒子の割合が40%以下で、コロイド分画が65%以上であることを特徴とする水分散性微細セルロース組成物
(B)果汁飲料、乳酸菌飲料等の酸性飲料、またはマヨネーズ、ドレッシング、ゼリー、ジャム等の酸性食品
A food composition comprising the following (A) water-dispersible fine cellulose composition and the following (B) acidic beverage or acidic food.
(A) Fine cellulose having an average particle size of 8 μm or less, a particle size of 10 μm or more, 40% or less, a colloidal fraction of 50% or more, a degree of substitution of 0.6 to 2.0, and a concentration of 1% Produced by stirring and mixing sodium carboxymethylcellulose having a viscosity of 500 centipoise or less in the presence of 75% or more of water into a uniform slurry, and then drying in freeze-drying, spray-drying or film form The composition comprises 15 to 100 parts by weight of sodium carboxymethylcellulose with respect to 100 parts by weight of fine cellulose, and the average particle size when the composition is redispersed in water is 8 μm or less and 10 μm or more The water-dispersible fine cellulose composition is characterized in that the proportion of the particles is 40% or less and the colloidal fraction is 65% or more
(B) Acidic beverages such as fruit juice beverages, lactic acid bacteria beverages, or acidic foods such as mayonnaise, dressing, jelly, jam, etc.
JP15046295A 1995-06-16 1995-06-16 Water dispersible composition Expired - Lifetime JP3693385B2 (en)

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