JP2008048602A - Thickening agent comprising water-dispersible cellulose and at least one kind of polysaccharide - Google Patents
Thickening agent comprising water-dispersible cellulose and at least one kind of polysaccharide Download PDFInfo
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- JP2008048602A JP2008048602A JP2004352169A JP2004352169A JP2008048602A JP 2008048602 A JP2008048602 A JP 2008048602A JP 2004352169 A JP2004352169 A JP 2004352169A JP 2004352169 A JP2004352169 A JP 2004352169A JP 2008048602 A JP2008048602 A JP 2008048602A
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- Prior art keywords
- water
- mass
- viscosity
- thickener
- cellulose
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Abstract
Description
微細な繊維状セルロースである水分散性セルロースと少なくとも１種の多糖類を含有し、増粘相乗効果を有することを特徴とする増粘剤に関する。 The present invention relates to a thickener comprising water-dispersible cellulose which is fine fibrous cellulose and at least one polysaccharide and having a thickening synergistic effect.
従来より食品や化粧品等の製品を増粘させるための増粘剤として、ガラクトマンナン、グルコマンナン、キサンタンガム等の多糖類が使用されている。これらの多糖類の多くはｐＨ、イオン濃度等により溶解性が左右され所望の機能が発揮できない場合が多いため、前もって増粘剤を水等に溶解させた溶液を製品に添加する場合が多い。この高濃度の多糖類溶液は粘ちょう性が高く取り扱いが難しいことや、一般的に食品や化粧品等に増粘剤を添加できる量は限られることから、少量で所望の増粘効果を発揮できる増粘剤が望まれている。 Conventionally, polysaccharides such as galactomannan, glucomannan, and xanthan gum have been used as thickeners for thickening products such as foods and cosmetics. Many of these polysaccharides are often affected by the pH, ion concentration, etc., so that the desired function cannot be exhibited. Therefore, a solution in which a thickener is dissolved in water or the like in advance is often added to the product. This high-concentration polysaccharide solution is highly viscous and difficult to handle, and generally the amount of thickeners that can be added to foods, cosmetics, etc. is limited, so the desired thickening effect can be achieved with a small amount. A thickener is desired.
植物細胞壁を原料とした微細な繊維状のセルロースとしては、微小繊維状セルロースやセルロースナノフィブリル等が知られている。これらの微細な繊維状のセルロースは、ある程度高い粘性が付与できるが、一般的な多糖類と比較して価格が高いので、単独で使用するのはコスト的に問題である。
微小繊維状セルロースと多糖類を含有する増粘剤としては特許文献１〜３などが知られている。これらに示されている効果は「ままこ防止」や「整腸作用」等であり、特定の多糖類と組み合わせて使用することで増粘相乗効果が得られることや増粘剤の添加量を軽減できることは記載されていない。
As the fine fibrous cellulose made from plant cell walls, microfibrous cellulose, cellulose nanofibrils, and the like are known. Although these fine fibrous celluloses can impart a certain degree of viscosity, they are expensive in comparison with general polysaccharides, so that they are problematic in terms of cost.
Patent Documents 1 to 3 and the like are known as thickeners containing fine fibrous cellulose and polysaccharides. The effects shown in these are “mamako prevention”, “intestinal regulation”, etc., and when used in combination with specific polysaccharides, a thickening synergistic effect can be obtained and the amount of thickener added can be reduced. It is not described that it can be reduced.
特許文献４および５には、約８０％以上の一次壁からなる細胞から得られたセルロースナノフィブリルとその他の添加剤を配合した組成物に関する開示があるが、添加剤配合の主目的は、あくまで乾燥物の再分散性改良や、セルロースナノフィブリルの機能補填である。 In Patent Documents 4 and 5, there is a disclosure relating to a composition in which cellulose nanofibrils obtained from cells having a primary wall of about 80% or more and other additives are blended. This is to improve the redispersibility of the dried product and to supplement the functions of cellulose nanofibrils.
特許文献６には水分散性乾燥組成物と多糖類を含むゲル形成性組成物に関する記述がある。しかしながら特許文献６の実施例に開示されている水分散性乾燥組成物の組成は、水分散性セルロースと水溶性高分子であるカルボキシメチルセルロース・ナトリウムの２成分だけから成り立っている。この水分散性乾燥組成物は、イオン交換水中で、「エースホモジナイザー」（日本精機株式会社製）のような強力な装置を使用して、工業的に非現実的な非常に強いせん断力で分散すれば、粒子が崩壊して、微細な繊維状のセルロースが水中に分散する。しかし工業的に実用的な分散条件、つまり水道水中で、工業的に通常使用される回転型のホモジナイザー（例えば特殊機化工業株式会社製、「Ｔ．Ｋ．ホモミクサー」）程度のせん断力で分散を施しても、粒子が充分に崩壊せず、分散が不十分であるために、多糖類と併用しても増粘剤としての機能が十分に発現しない。 Patent Document 6 describes a gel-forming composition containing a water-dispersible dry composition and a polysaccharide. However, the composition of the water-dispersible dry composition disclosed in the examples of Patent Document 6 is composed of only two components: water-dispersible cellulose and water-soluble polymer carboxymethylcellulose sodium. This water-dispersible dry composition is dispersed in ion-exchanged water using a strong device such as “ACE Homogenizer” (manufactured by Nippon Seiki Co., Ltd.) with a very strong shear force that is industrially impractical. Then, the particles are disintegrated and fine fibrous cellulose is dispersed in water. However, it is dispersed in industrially practical dispersion conditions, that is, with a shearing force equivalent to that of a rotary homogenizer that is usually used industrially (for example, “TK homomixer” manufactured by Tokushu Kika Kogyo Co., Ltd.) in tap water. Even if it is applied, since the particles are not sufficiently disintegrated and the dispersion is insufficient, the function as a thickener is not sufficiently exhibited even when used in combination with polysaccharides.
それに対して後述する本発明の増粘剤の構成成分として使用される水分散性乾燥組成物は、水分散性セルロースと、水溶性高分子と、親水性物質の全てを必須成分として含有する。この３成分全てを含有させてはじめて、実用的な分散条件でも粒子が崩壊し、良好な分散性を示す。その結果、多糖類と併用したときに、増粘剤としての機能が十分に発現する。 On the other hand, the water-dispersible dry composition used as a constituent of the thickener of the present invention described later contains all of water-dispersible cellulose, a water-soluble polymer, and a hydrophilic substance as essential components. Only when all the three components are contained, the particles disintegrate even under practical dispersion conditions, and exhibits good dispersibility. As a result, when used in combination with polysaccharides, the function as a thickener is sufficiently developed.
また特許文献６の水分散性乾燥組成物と多糖類を含むゲル形成性組成物を添加し、水分散液を静置しておくと真性のゲル（ｔｒｕｅ ｇｅｌ）を形成するとされている。それに対して本発明の増粘剤は、ゲル化させない、つまり増粘剤を添加する水分散液や液状組成物の流動性は維持し、真性のゲルを形成させないという点で、異なるものである。ゲル化すると、流動性を失って形態が液状でなくなるため、水分散液や液状組成物としての機能や物性を失ってしまうことになり、非常に問題である。
本発明は微細な繊維状セルロースである水分散性セルロースと、多糖類を含有させることで、増粘相乗効果を付与し、少量で所望の増粘効果を得ることができる増粘剤を提供することを目的とする。 The present invention provides a thickening agent capable of providing a thickening synergistic effect and obtaining a desired thickening effect in a small amount by containing a water-dispersible cellulose which is fine fibrous cellulose and a polysaccharide. For the purpose.
本発明者は、植物細胞壁を原料とする微細な繊維状セルロースである水分散性セルロースと、特定の多糖類を含有させることで、課題を解決し、本発明をなすに至った。すなわち本発明は以下の通りである。 The present inventor has solved the problem and made the present invention by containing water-dispersible cellulose, which is fine fibrous cellulose made from plant cell walls, and a specific polysaccharide. That is, the present invention is as follows.
（１）植物細胞壁を原料とする、微細な繊維状のセルロースであって、水中で安定に懸濁する成分（長径：０．５〜３０μｍ、短径：２〜６００ｎｍ、長径／短径比：２０〜４００）を１０質量％以上含有し、かつ、０．５質量％水分散液とした時の損失正接が１未満であることを特徴とする水分散性セルロースと、ガラクトマンナン、グルコマンナン、アルギン酸ナトリウムから選択される少なくとも１種の多糖類を含有する組成物であって、水分散性セルロース：多糖類＝１：９〜９：１の質量比で含有することを特徴とする増粘剤。 (1) Fine fibrous cellulose made from plant cell walls as a raw material, and stably suspended in water (major axis: 0.5 to 30 μm, minor axis: 2 to 600 nm, major axis / minor axis ratio: 20 to 400) in an amount of 10% by mass or more, and a loss tangent when the aqueous dispersion is 0.5% by mass is less than 1, water dispersible cellulose, galactomannan, glucomannan, A composition containing at least one polysaccharide selected from sodium alginate, wherein the thickener contains water-dispersible cellulose: polysaccharide = 1: 9 to 9: 1. .
（２）水中で安定に懸濁する成分を１０質量％以上含有する（１）に記載の水分散性セルロースを５０〜９０質量％と、水溶性高分子５〜４５質量％と、親水性物質５〜４５質量％を含むことを特徴とする水分散性乾燥組成物と、（１）記載の多糖類から選択される少なくとも１種の多糖類を含有する組成物であって、水分散性乾燥組成物：多糖類＝１：９〜９：１の質量比で含有することを特徴とする増粘剤。 (2) 50 to 90% by mass of the water-dispersible cellulose according to (1), containing 10% by mass or more of a component that is stably suspended in water, 5 to 45% by mass of a water-soluble polymer, and a hydrophilic substance A water-dispersible dry composition comprising 5 to 45% by mass, and a composition containing at least one polysaccharide selected from the polysaccharides according to (1), wherein the water-dispersible dry composition Composition: Polysaccharides = 1: 9 to 9: 1 A thickening agent characterized by containing.
（３）（１）または（２）の多糖類がガラクトマンナン、グルコマンナンからなる群より選択されることを特徴とする（１）または（２）記載の増粘剤。 (3) The thickener according to (1) or (2), wherein the polysaccharide of (1) or (2) is selected from the group consisting of galactomannan and glucomannan.
（４）（１）〜（３）のいずれかに記載の増粘剤を添加することにより配合された液状組成物。 (4) A liquid composition formulated by adding the thickener according to any one of (1) to (3).
（５）（１）〜（３）のいずれかに記載の増粘剤を添加することにより配合される、ｐＨ３〜８または食塩濃度０．００１〜２０％である液状食品組成物。 (5) A liquid food composition having a pH of 3 to 8 or a salt concentration of 0.001 to 20%, which is blended by adding the thickener according to any one of (1) to (3).
本発明は、微細な繊維状セルロースである水分散性セルロースと多糖類を含有させることで、増粘相乗効果を付与し、少量で所望の増粘効果を得ることができる増粘剤を提供することができる。 The present invention provides a thickener capable of providing a thickening synergistic effect and obtaining a desired thickening effect in a small amount by containing water-dispersible cellulose, which is fine fibrous cellulose, and a polysaccharide. be able to.
以下、本発明について、特にその好ましい形態を中心に、具体的に説明する。本発明の水分散性セルロースは植物細胞壁を原料とする。具体的には、低コストで安定的に原料を入手することができて、工業的に使用が可能なものが好ましく、木材（針葉樹、広葉樹）、コットンリンター、ケナフ、マニラ麻（アバカ）、サイザル麻、ジュート、サバイグラス、エスパルト草、バガス、稲わら、麦わら、葦、竹などの天然セルロースを主成分とするパルプが使用される。綿花、パピルス草、ビート、こうぞ、みつまた、ガンピなども使用が可能だが、原料の安定的な確保が困難であること、セルロース以外の成分の含有量が多いこと、ハンドリングが難しいことなどの理由で好ましくない場合がある。再生セルロースを原料とした場合、充分な性能が発揮されないので、再生セルロースは本発明の原料としては含まれない。 Hereinafter, the present invention will be specifically described focusing on its preferred form. The water-dispersible cellulose of the present invention is made from plant cell walls. Specifically, materials that can be stably obtained at low cost and can be used industrially are preferred, such as wood (conifers, hardwoods), cotton linters, kenaf, Manila hemp (Abaca), sisal hemp Pulp mainly composed of natural cellulose such as jute, survivorgrass, esparto grass, bagasse, rice straw, straw, straw and bamboo is used. Cotton, papyrus grass, beet, ridges, honey, and ganpi can also be used, but reasons such as difficulty in securing stable raw materials, high content of components other than cellulose, and difficulty in handling May not be preferable. When regenerated cellulose is used as a raw material, sufficient performance is not exhibited, so regenerated cellulose is not included as a raw material of the present invention.
好ましい原料の具体的例は、木材パルプ、コットンリンターパルプ、バガスパルプ、麦わらパルプ、稲わらパルプ、竹パルプなどである。特に好ましいのはイネ科植物の細胞壁を起源としたセルロース性物質であり、具体的にはバガスパルプ、麦わらパルプ、稲わらパルプ、竹パルプである。 Specific examples of preferable raw materials are wood pulp, cotton linter pulp, bagasse pulp, wheat straw pulp, rice straw pulp, bamboo pulp and the like. Particularly preferred are cellulosic substances originating from the cell walls of gramineous plants, specifically bagasse pulp, wheat straw pulp, rice straw pulp and bamboo pulp.
本発明で使用される微細な繊維状のセルロースの結晶化度は特に定めるものではないが、Ｘ線回折法（Ｓｅｇａｌ法）で測定されるところの結晶化度が、５０％より大きいことが好ましく、５５％以上であればさらに好ましい。本発明物質はセルロース以外の成分を含有するが、それらの成分は非晶性であり、非晶性としてカウントされる。 The crystallinity of the fine fibrous cellulose used in the present invention is not particularly defined, but the crystallinity as measured by the X-ray diffraction method (Segal method) is preferably greater than 50%. 55% or more is more preferable. The substance of the present invention contains components other than cellulose, but these components are amorphous and are counted as amorphous.
本発明で使用されるセルロースは「微細な繊維状」である。本明細書中で「微細な繊維状」とは、光学顕微鏡および電子顕微鏡にて観察および測定されるところの、長さ（長径）が０．５μｍ〜１ｍｍ程度、幅（短径）が２ｎｍ〜６０μｍ程度、長さと幅の比（長径／短径）が５〜４００程度であることを意味する。
本発明の水分散性セルロースまたは水分散性乾燥組成物は、水中で安定に懸濁する成分を含有する。
The cellulose used in the present invention is “fine fibrous”. In the present specification, “fine fibrous” refers to a length (major axis) of about 0.5 μm to 1 mm and a width (minor axis) of 2 nm to as observed and measured with an optical microscope and an electron microscope. It means that the ratio of length to width (major axis / minor axis) is about 5 to 400, about 60 μm.
The water-dispersible cellulose or water-dispersible dry composition of the present invention contains a component that is stably suspended in water.
具体的には、０．１質量％濃度の水分散液状態として、これを１０００Ｇで５分間遠心分離した時においても、沈降することなく水中に安定に懸濁しているという性質を有する成分であり、高分解能走査型電子顕微鏡（ＳＥＭ）にて観察・測定される長さ（長径）が０．５〜３０μｍであり、幅（短径）が２〜６００ｎｍであり、長さと幅の比（長径／短径比）が２０〜４００である繊維状のセルロースからなる。好ましくは、幅が１００ｎｍ以下であり、より好ましくは５０ｎｍである。 Specifically, it is a component having the property of being stably suspended in water without settling even when it is centrifuged at 1000 G for 5 minutes in the form of a 0.1% by weight aqueous dispersion. The length (major axis) observed and measured with a high-resolution scanning electron microscope (SEM) is 0.5 to 30 μm, the width (minor axis) is 2 to 600 nm, and the ratio of length to width (major axis) / Minor axis ratio) is composed of fibrous cellulose having a ratio of 20 to 400. Preferably, the width is 100 nm or less, more preferably 50 nm.
本発明の増粘剤の構成成分として使用される水分散セルロースまたは水分散性乾燥組成物は、この「水中で安定に懸濁する成分」を１０質量％以上含有する。この成分の含有量が１０質量％未満であると、前述の機能が十分に発揮されない。含有量は多いほど好ましいが、好ましくは３０質量％以上、より好ましくは５０％以上である。なお、この成分の含有量は特に断らない限り、全セルロース中の存在比率を表すものであり、水溶性成分が含まれている場合であってもそれが含まれないように測定・算出される。 The water-dispersed cellulose or water-dispersible dry composition used as a constituent of the thickener of the present invention contains 10% by mass or more of this “component that is stably suspended in water”. When the content of this component is less than 10% by mass, the above-described function is not sufficiently exhibited. The larger the content, the better. However, it is preferably 30% by mass or more, and more preferably 50% or more. Unless otherwise specified, the content of this component represents the abundance ratio in the total cellulose, and is measured and calculated so that it is not included even if a water-soluble component is included. .
本発明の水分散性セルロースまたは水分散性乾燥組成物は、０．５質量％濃度の水分散液において、歪み１０％、周波数１０ｒａｄ／ｓの条件で測定される損失正接（ｔａｎδ）が１未満であり、好ましくは０．６未満である。０．６未満であるとそれらの性能はさらに秀でたものとなる。損失正接が１以上であると、後述する他の多糖類との増粘相乗効果が劣る。
本発明の水分散性セルロースまたは水分散性乾燥組成物の損失正接を１未満にするためには、植物細胞壁由来のミクロフィブリルを短く切断することなく取り出す必要がある。しかしながら現在の技術では全く「短繊維化」させることなく、「微細化」だけを行うことはできない。（ここで言う「短繊維化」とは繊維を短く切断すること、あるいは短くなった繊維の状態を意味する。また「微細化」とは引き裂くなどの作用を与えて繊維を細くすること、または細くなった繊維の状態を意味する。）つまり損失正接を１未満にするためには、セルロース繊維の「短繊維化」を最低限に抑えつつ「微細化」を進行させることが重要である。そのための好ましい方法を以下に示すが、これらの方法に何ら限定するものではない。
セルロース繊維の「短繊維化」を最低限に抑えつつ「微細化」を進行させるために、原料として選択する植物細胞壁を起源とするセルロース性物質は、平均重合度４００〜１２０００で、かつ、α−セルロース含量（％）が６０〜１００質量％のものが好ましく、より好ましくはα−セルロース含量（％）が６０〜８５質量％のものである。
またセルロース繊維の「短繊維化」を最低限に抑えつつ「微細化」を進行させるために使用する装置としては高圧ホモジナイザーが好ましい。高圧ホモジナイザーの具体例としては、エマルジフレックス（ＡＶＥＳＴＩＮ，Ｉｎｃ．）、アルティマイザーシステム（株式会社スギノマシン）、ナノマイザーシステム（ナノマイザー株式会社）、マイクロフルイダイザー（ＭＦＩＣ Ｃｏｒｐ．）、バルブ式ホモジナイザー（三和機械株式会社、Ｉｎｖｅｎｓｙｓ ＡＰＶ社、Ｎｉｒｏ Ｓｏａｖｉ社、株式会社イズミフードマシナリー）などがある。高圧ホモジナイザーの処理圧力としては３０ＭＰａ以上が好ましく、より好ましくは６０〜４１４ＭＰａである。
The water-dispersible cellulose or water-dispersible dry composition of the present invention has a loss tangent (tan δ) of less than 1 measured in a 0.5% by weight aqueous dispersion at a strain of 10% and a frequency of 10 rad / s. And preferably less than 0.6. If it is less than 0.6, the performance is further improved. When the loss tangent is 1 or more, the thickening synergistic effect with other polysaccharides described later is inferior.
In order to make the loss tangent of the water-dispersible cellulose or water-dispersible dry composition of the present invention less than 1, it is necessary to take out microfibrils derived from plant cell walls without cutting them short. However, with the current technology, it is not possible to perform only “miniaturization” without “short fiber” at all. (In this case, “short fiber” means that the fiber is cut short, or the state of the shortened fiber. Also, “miniaturization” means that the fiber is thinned by giving an action such as tearing, or In other words, in order to make the loss tangent less than 1, it is important to advance the “miniaturization” while minimizing the “short fiber” of the cellulose fiber. Although the preferable method for that is shown below, it does not limit to these methods at all.
The cellulosic substance originating from the plant cell wall selected as a raw material in order to advance the “miniaturization” while minimizing the “short fiber” of the cellulose fiber has an average degree of polymerization of 400 to 12000, and α The cellulose content (%) is preferably 60 to 100% by mass, more preferably the α-cellulose content (%) is 60 to 85% by mass.
Further, a high-pressure homogenizer is preferable as an apparatus used for advancing “miniaturization” while minimizing “shortening” of cellulose fibers. Specific examples of the high-pressure homogenizer include Emulflex (AVESTIN, Inc.), Optimizer System (Sugino Machine Co., Ltd.), Nanomizer System (Nanomizer Co., Ltd.), Microfluidizer (MFIC Corp.), Valve Homogenizer ( Sanwa Machinery Co., Ltd., Invensys APV, Niro Soavi, Izumi Food Machinery Co., Ltd.). The processing pressure of the high-pressure homogenizer is preferably 30 MPa or more, more preferably 60 to 414 MPa.
本発明に使用する多糖類はガラクトマンナン、グルコマンナン、アルギン酸ナトリウムからなる群、好ましくはガラクトマンナンとグルコマンナンからなる群から少なくとも１種が選択される。 The polysaccharide used in the present invention is at least one selected from the group consisting of galactomannan, glucomannan and sodium alginate, preferably from the group consisting of galactomannan and glucomannan.
本発明で使用されるガラクトマンナンとは、β−Ｄ−マンノースがβ−１，４結合した主鎖と、α−Ｄ−ガラクトースがα−１，６結合した側鎖からなる構造を有する多糖類である。ガラクトマンナンの例としては、グアーガム、ローカストビーンガム、タラガム等があり、マンノースとグルコースの比率は、グアーガムで約２：１、ローカストビーンガムで約４：１、タラガムで約３：１である。 The galactomannan used in the present invention is a polysaccharide having a structure composed of a main chain in which β-D-mannose is β-1,4 bonded and a side chain in which α-D-galactose is α-1,6 bonded. It is. Examples of galactomannans include guar gum, locust bean gum, tara gum, etc. The ratio of mannose to glucose is about 2: 1 for guar gum, about 4: 1 for locust bean gum, and about 3: 1 for tara gum.
本発明で使用されるグルコマンナンは、Ｄ−グルコースとＤ−マンノースがβ−１，４結合した構造を有し、グルコースとマンノースの比率が約２：３の多糖類であるが、精製度が低いと独特の刺激臭があるので、精製度の高いものを使用することが望ましい。 The glucomannan used in the present invention is a polysaccharide having a structure in which D-glucose and D-mannose are linked by β-1,4, and the ratio of glucose to mannose is about 2: 3. If it is low, there is a unique irritating odor, so it is desirable to use a highly purified one.
本発明で使用されるアルギン酸ナトリウムとは、アルギン酸がナトリウムで中和された水溶性の多糖類である。アルギン酸はβ−Ｄ−マンヌロン酸（Ｍと略する）とα−Ｌ−グルロン酸（Ｇと略する）からなる１，４結合のブロック共重合体である。Ｍからなるブロック（Ｍ−Ｍ−Ｍ−Ｍ）と、Ｇからなるブロック（Ｇ−Ｇ−Ｇ−Ｇ）と、両残基が交互に入り交じっているブロック（Ｍ−Ｇ−Ｍ−Ｇ）、という３つのセグメントから成り立っている。 The sodium alginate used in the present invention is a water-soluble polysaccharide in which alginic acid is neutralized with sodium. Alginic acid is a 1,4-bond block copolymer consisting of β-D-mannuronic acid (abbreviated as M) and α-L-guluronic acid (abbreviated as G). A block composed of M (MMMGM), a block composed of G (GGGGG), and a block in which both residues are alternately mixed (MGGG) , And consists of three segments.
本発明の増粘相乗効果とは、水分散性セルロース（または水分散性乾燥組成物）と少なくとも１種の多糖類を含有することで、特異的に発現する相乗効果のことである。具体的には、請求項１〜３に記載の増粘剤を使用した、以下の増粘剤水分散液あるいは液状組成物の粘度（粘度Ｚ）が、理論粘度αを上回る場合、つまり「粘度Ｚ＞理論粘度α」の関係にある場合、増粘相乗効果を有すると判定する。 The thickening synergistic effect of the present invention is a synergistic effect that is specifically expressed by containing water-dispersible cellulose (or a water-dispersible dry composition) and at least one polysaccharide. Specifically, when the viscosity (viscosity Z) of the following thickener aqueous dispersion or liquid composition using the thickener according to claims 1 to 3 exceeds the theoretical viscosity α, that is, “viscosity” If Z> theoretical viscosity α ”, it is determined to have a thickening synergistic effect.
ここで、 粘度Ｘ：粘度Ｚの調製に用いた増粘剤に含まれる多糖類を、粘度Ｚの増粘剤と同量添加した場合の、水分散液あるいは液状組成物の粘度
粘度Ｙ：粘度Ｚの調製に用いた増粘剤に含まれる、水分散性セルロース（または水分散性乾燥組成物）を、粘度Ｚの増粘剤と同量添加した場合の、水分散液あるいは液状組成物の粘度
粘度Ｚ：請求項１〜３記載の増粘剤の、水分散液あるいは液状組成物の粘度理論粘度
Here, viscosity X: the viscosity of the aqueous dispersion or liquid composition when the same amount of the polysaccharide contained in the thickener used for the preparation of viscosity Z is added to the thickener of viscosity Z. Viscosity Y: viscosity A water-dispersed liquid composition or a liquid composition when water-dispersible cellulose (or water-dispersible dry composition) contained in the thickener used for the preparation of Z is added in the same amount as the thickener with viscosity Z. Viscosity Viscosity Z: Theoretical viscosity of an aqueous dispersion or liquid composition of the thickener according to claims 1 to 3
α：粘度Ｘ、粘度Ｙから推定される粘度理論値であり、次式から推定されるものである。
理論粘度α＝〔β×粘度Ｘ＋γ×粘度Ｙ〕／（β＋γ）
β：粘度Ｚを求める時に使用した、増粘剤水分散液あるいは液状組成物中に含まれる、多糖類の量（質量％）
γ：粘度Ｚを求める時に使用した、増粘剤水分散液あるいは液状組成物中に含まれる、水分散性セルロース（または水分散性乾燥組成物）の量（質量％）
β＋γ：粘度Ｚを求める時に使用した、増粘剤水分散液あるいは液状組成物に含まれる、増粘剤の量（質量％）
α: Theoretical viscosity value estimated from viscosity X and viscosity Y, estimated from the following equation.
Theoretical viscosity α = [β × viscosity X + γ × viscosity Y] / (β + γ)
β: Amount of polysaccharide (mass%) contained in the aqueous thickener dispersion or liquid composition used to determine viscosity Z
γ: Amount (mass%) of water-dispersible cellulose (or water-dispersible dry composition) contained in the thickener aqueous dispersion or liquid composition used for determining the viscosity Z
β + γ: The amount (% by mass) of the thickener contained in the aqueous thickener dispersion or liquid composition used to determine the viscosity Z
本発明の増粘剤には、増粘剤の他に、デンプン類、油脂類、蛋白質類、ペプチド、アミノ酸類、食塩、各種リン酸塩等の塩類、界面活性剤、乳化剤、酸味料、甘味料、香料、色素、ｐＨ調整剤、消泡剤、ミネラル、食物繊維、調味料、酸、アルカリ、アルコール等の成分が適宜配合されていても良い。またペクチン、キサンタンガムのように、増粘相乗効果を付与しない多糖類が適宜配合されていても良い。 In addition to the thickener, the thickener of the present invention includes starches, fats and oils, proteins, peptides, amino acids, salt, various phosphate salts, surfactants, emulsifiers, acidulants, sweetness Ingredients such as a fragrance, a fragrance, a pigment, a pH adjuster, an antifoaming agent, a mineral, a dietary fiber, a seasoning, an acid, an alkali, and an alcohol may be appropriately blended. Moreover, polysaccharides that do not impart a thickening synergistic effect, such as pectin and xanthan gum, may be appropriately blended.
本発明の増粘剤の構成成分として使用される水分散性乾燥組成物は、水分散性セルロースを５０〜９０質量％と、水溶性高分子５〜４５質量％と、親水性物質５〜４５質量％からなる乾燥物である。好ましくは水分散性セルロース：カルボキシメチルセルロース・ナトリウム：親水性物質＝６０〜７５：５〜２０：１５〜２５質量％の範囲であり、さらに好ましくは、６２〜７３：７〜１８：１７〜２３質量％の範囲からなる乾燥物であり、顆粒状、粒状、粉末状、鱗片状、小片状、シート状を呈する。この組成物は水中に投入し、機械的な剪断力を与えた時、粒子が崩壊し、微細な繊維状のセルロースが水中に分散するようになることが特徴である。水分散性セルロースが５０質量％未満になると、セルロースの比率が低くなって効果が発揮されない。９０質量％以上になると、相対的にその他の成分の配合比率が下がるので、水中の充分な分散性を確保することができない。 The water-dispersible dry composition used as a constituent of the thickener of the present invention comprises 50-90% by mass of water-dispersible cellulose, 5-45% by mass of a water-soluble polymer, and 5-45% of a hydrophilic substance. It is a dry product consisting of mass%. Preferably water-dispersible cellulose: carboxymethylcellulose sodium: hydrophilic substance = 60-75: 5-20: 15-25% by mass, more preferably 62-73: 7-18: 17-23 mass % Dried product, which is granular, granular, powdery, scaly, small, or sheet-like. This composition is characterized in that when it is put into water and given mechanical shearing force, the particles are disintegrated and fine fibrous cellulose is dispersed in water. When the water-dispersible cellulose is less than 50% by mass, the cellulose ratio is lowered and the effect is not exhibited. If it is 90% by mass or more, the blending ratio of other components is relatively lowered, so that sufficient dispersibility in water cannot be ensured.
本発明に使用される前記水分散性乾燥組成物の成分である水溶性高分子とは、乾燥時におけるセルロース同士の角質化を防止する作用を有するものであり、具体的にはアラビアガム、アラビノガラクタン、アルギン酸およびその塩、カードラン、ガッティーガム、カラギーナン、カラヤガム、寒天、キサンタンガム、グアーガム、酵素分解グアーガム、クインスシードガム、ジェランガム、ゼラチン、タマリンドシードガム、難消化性デキストリン、トラガントガム、ファーセルラン、プルラン、ペクチン、ローカントビーンガム、水溶性大豆多糖類、カルボキシメチルセルロース・ナトリウム、メチルセルロース、ポリアクリル酸ナトリウムなどから選ばれた１種または２種以上の物質が使用される。中でも、カルボキシメチルセルロース・ナトリウムが好ましい。このカルボキシメチルセルロース・ナトリウムとしては、カルボキシメチル基の置換度が０．５〜１．５、好ましくは０．５〜１．０、さらに好ましくは０．６〜０．８である。また１質量％水溶液の粘度は５〜９０００ｍＰａ・ｓ程度、好ましくは１０００〜８０００ｍＰａ・ｓ程度、さらに好ましくは２０００〜６０００ｍＰａ・ｓ程度のものである。 The water-soluble polymer that is a component of the water-dispersible dry composition used in the present invention has an action of preventing keratinization of celluloses during drying. Specifically, gum arabic and arabi Nogalactan, alginic acid and its salts, curdlan, gati gum, carrageenan, caraya gum, agar, xanthan gum, guar gum, enzyme-degraded guar gum, quince seed gum, gellan gum, gelatin, tamarind seed gum, indigestible dextrin, tragacanth gum, farcellulan One or two or more substances selected from pullulan, pectin, locust bean gum, water-soluble soybean polysaccharide, sodium carboxymethylcellulose, methylcellulose, sodium polyacrylate and the like are used. Of these, sodium carboxymethylcellulose is preferable. As this carboxymethylcellulose sodium, the substitution degree of the carboxymethyl group is 0.5 to 1.5, preferably 0.5 to 1.0, more preferably 0.6 to 0.8. The viscosity of the 1% by mass aqueous solution is about 5 to 9000 mPa · s, preferably about 1000 to 8000 mPa · s, and more preferably about 2000 to 6000 mPa · s.
本発明に使用される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ず、常温で固体の物質であり、デキストリン類、水溶性糖類（ブドウ糖、果糖、庶糖、乳糖、異性化糖、キシロース、トレハロース、カップリングシュガー、パラチノース、ソルボース、還元澱粉糖化飴、マルトース、ラクツロース、フラクトオリゴ糖、ガラクトオリゴ糖、キシロオリゴ糖等）、糖アルコール類（キシリトール、マルチトール、マンニトール、ソルビトール等）、より選ばれた１種または２種以上の物質である。水溶性高分子は前述の通り、セルロースの角質化を防ぐ効果があるが、物質によっては乾燥組成物内部への導水性が劣るため、水中での機械的剪断力を強く、長い時間与える必要が生じる場合がある。親水性物質は主としてこの導水性を強化する機能があり、具体的には乾燥組成物の水崩壊性を促進させる。この作用としては特にデキストリン類が強いため、デキストリン類を用いるのが好ましい。本発明に使用されるデキストリン類とは、澱粉を酸、酵素、熱で加水分解することによって生じる部分分解物のことであり、グルコース残基が主としてα−１，４結合およびα−１，６結合からなり、ＤＥ（ｄｅｘｔｒｏｓｅ ｅｑｕｉｖａｌｅｎｔ）として２〜４２程度、好ましくは２０〜４２程度のものが使用される。ブドウ糖や低分子オリゴ糖が除去された分枝デキストリンも使用することができる。 The hydrophilic substance used in the present invention is a substance that is highly soluble in cold water, hardly causes viscosity, and is solid at room temperature, dextrins, water-soluble saccharides (glucose, fructose, sucrose, lactose, isomerization) From sugar, xylose, trehalose, coupling sugar, palatinose, sorbose, reduced starch saccharified starch, maltose, lactulose, fructooligosaccharide, galactooligosaccharide, xylooligosaccharide, etc., sugar alcohols (xylitol, maltitol, mannitol, sorbitol, etc.) One or more selected substances. As described above, the water-soluble polymer has an effect of preventing the keratinization of cellulose, but depending on the substance, the water permeability to the inside of the dry composition is inferior, so it is necessary to provide a strong mechanical shear force in water for a long time. May occur. The hydrophilic substance mainly has a function of enhancing the water conductivity, and specifically promotes water disintegration of the dry composition. Since dextrins are particularly strong as this action, it is preferable to use dextrins. The dextrins used in the present invention are partial degradation products generated by hydrolyzing starch with acid, enzyme, and heat, and glucose residues are mainly α-1,4 bonds and α-1,6. It consists of a bond, and a DE (dextrose equivalent) of about 2 to 42, preferably about 20 to 42 is used. Branched dextrin from which glucose and low-molecular oligosaccharides have been removed can also be used.
本発明に使用する水分散性乾燥組成物には水分散性セルロースと水溶性高分子と親水性物質以外に、デンプン類、油脂類、蛋白質類、食塩、各種リン酸塩等の塩類、乳化剤、酸味料、甘味料、香料、色素等の食品に使用できる成分を適宜配合されていても良い。本発明に使用される水分散性乾燥組成物は、前述の通り、水中に投入し、機械的な剪断力を与えた時、構成単位
（粒子）が崩壊し、微細な繊維状のセルロースが水中に分散するようになる。このとき「機械的な剪断力」とは、０．５質量％水分散液を、回転型のホモジナイザーで、最大でも１５０００ｒｐｍで１５分間分散するようなものであり、温度は８０℃以下で処理することを意味する。このようにして得られた水分散液は、乾燥前の状態、すなわち、「水中で安定に懸濁する成分」が全セルロース分に対して１０質量％以上存在する。そして、この水分散液の０．５質量％における損失正接は１未満である。水分散性セルロース中の「水中で安定に懸濁する成分」の含有量と損失正接の測定条件は後述する。水分散性セルロースは前述したとおり、長径は０．５〜３０μｍ、短径は２〜６００ｎｍである。長径／短径比は２０〜４００である。好ましくは、幅が１００ｎｍ以下であり、より好ましくは５０ｎｍである。
In addition to water-dispersible cellulose, water-soluble polymer and hydrophilic substance, the water-dispersible dry composition used in the present invention includes starches, fats and oils, proteins, salt, salts such as various phosphates, emulsifiers, Ingredients that can be used in foods such as acidulants, sweeteners, fragrances, and pigments may be appropriately blended. As described above, when the water-dispersible dry composition used in the present invention is poured into water and given a mechanical shearing force, the structural unit (particles) is disintegrated and fine fibrous cellulose is dissolved in the water. To be distributed. At this time, the “mechanical shearing force” means that a 0.5 mass% aqueous dispersion is dispersed with a rotary homogenizer at a maximum of 15 000 rpm for 15 minutes, and the temperature is 80 ° C. or less. Means that. The aqueous dispersion thus obtained has a state before drying, that is, “a component that is stably suspended in water” of 10% by mass or more based on the total cellulose content. The loss tangent at 0.5% by mass of this aqueous dispersion is less than 1. The measurement conditions for the content of the “component stably suspended in water” in the water-dispersible cellulose and the loss tangent will be described later. As described above, the water-dispersible cellulose has a major axis of 0.5 to 30 μm and a minor axis of 2 to 600 nm. The major axis / minor axis ratio is 20 to 400. Preferably, the width is 100 nm or less, more preferably 50 nm.
本発明の液状組成物とは、室温で液状あるいはペースト状の形態をとるものであり、液状食品組成物、液状化粧品組成物、液状医薬品組成物、液状工業用組成物等が含まれる。これらの液状組成物は、スプレー、チュアパック、レトルト食品、冷凍食品、電子レンジ用食品等のように、形態または用時調製の加工手法が異なっていても本発明に含まれる。
液状食品組成物の例としては、「コーヒー、紅茶、抹茶、ココア、汁粉、ジュース、豆乳、アルコール等の嗜好飲料」、「生乳、加工乳、乳酸菌飲料等の乳成分含有飲料」、「カルシウム強化飲料等の栄養強化飲料並びに食物繊維含有飲料等を含む各種の飲料類」、「コーヒーホワイトナー、ホイッピングクリーム、カスタードクリーム、ソフトクリーム等の乳製品類」、「スープ類」、「シチュー類」、「ソース、タレ、ドレッシング等の調味料類」、「練りがらしに代表される各種練り調味料」、「フルーツソース、フルーツプレパレーションに代表される果肉加工品」、「経管流動食等の流動食類」、「液状あるいはペースト状のサプリメント類」および「液状あるいはペースト状のペットフード類」等があげられる。医薬品組成物の例としては、「シロップ薬」や「医薬品に区分される経管流動食等の流動食類」等があげられる。液状化粧品組成物の例としては、化粧水、乳液、コールドクリーム、バニシングクリーム、マッサージクリーム、エモリエントクリーム、クレンジングクリーム、モイスチャークリーム、ハンドクリーム、美容液、パック、ファンデーション、サンスクリーン化粧料、サンタン化粧料美白乳液、各種ローションなどの皮膚用化粧料と、シャンプー、リンス、ヘアコンディショナー、リンスインシャンプー、ヘアスタイリング剤（ヘアフォームやジェル状整髪料等）、ヘアトリートメント剤（ヘアクリームやトリートメントローション等）、染毛剤やローションタイプの育毛剤あるいは養毛剤などの毛髪用化粧料、さらにはハンドクリーナーのような洗浄剤、プレシェーブローション、アフターシェーブローション、芳香剤や歯磨剤、軟膏、貼布剤等があげられる。液状工業用組成物の例としては、顔料、ペンキ、インク類等があげられる。液状食品組成物は、通常、ｐＨ３〜８、食塩濃度０．００１〜２０％で供給されるため、このような条件下で効果を発現することが求められる。
The liquid composition of the present invention takes a liquid or paste form at room temperature, and includes liquid food compositions, liquid cosmetic compositions, liquid pharmaceutical compositions, liquid industrial compositions and the like. These liquid compositions are also included in the present invention even if they have different forms or processing methods at the time of use, such as sprays, Chua packs, retort foods, frozen foods, foods for microwave ovens, and the like.
Examples of liquid food compositions are “coffee, tea, matcha, cocoa, juice, juice, soy milk, alcoholic beverages, etc.”, “milk, processed milk, lactic acid bacteria beverages”, “calcium fortification” Various beverages including fortified beverages such as beverages and dietary fiber-containing beverages ”,“ dairy products such as coffee whitener, whipping cream, custard cream, soft cream ”,“ soups ”,“ stews ” "Seasonings such as sauces, sauces, dressings", "Various kneading seasonings typified by kneading", "Fruit processed products typified by fruit sauce and fruit preparation", “Food products”, “Liquid or pasty supplements”, “Liquid or pasty pet foods” and the like. Examples of the pharmaceutical composition include “syrup medicine” and “liquid food such as tube liquid food classified into pharmaceutical products”. Examples of liquid cosmetic compositions include lotions, emulsions, cold creams, burnishing creams, massage creams, emollient creams, cleansing creams, moisture creams, hand creams, essences, packs, foundations, sunscreen cosmetics, suntan cosmetics. Skin cosmetics such as whitening milk lotion and various lotions, shampoos, rinses, hair conditioners, rinse-in shampoos, hair styling agents (such as hair foam and gel hair conditioner), hair treatment agents (such as hair creams and treatment lotions), dyeings Hair cosmetics such as hair and lotion type hair restorers or hair nourishing agents, as well as detergents such as hand cleaners, pre-shave lotions, after-shave lotions, fragrances and dentifrices, ointments, patches Agent, and the like. Examples of liquid industrial compositions include pigments, paints, inks and the like. Since the liquid food composition is usually supplied at a pH of 3 to 8 and a salt concentration of 0.001 to 20%, it is required to exhibit an effect under such conditions.
本発明の増粘剤の液状組成物に対する添加量は、特に限定するものではないが、好ましくは０．００１質量％以上、１質量％未満、さらに好ましくは０．０５〜０．７質量％程度である。 The addition amount of the thickener of the present invention to the liquid composition is not particularly limited, but is preferably 0.001% by mass or more and less than 1% by mass, more preferably about 0.05 to 0.7% by mass. It is.
本発明のゲル化とは、水分散液あるいは液状組成物を静置しておくと、ゼリーやプリンのようなゲル、つまり真性のゲル（ｔｒｕｅ ｇｅｌ）を形成する機能のことで、静置後２４時間の時点で判断する。またゲル化した水分散液および液状組成物は流動性を持たない。 The gelation of the present invention is a function of forming a gel such as jelly or pudding, that is, a true gel when the aqueous dispersion or liquid composition is allowed to stand. Judge at 24 hours. Gelled aqueous dispersions and liquid compositions do not have fluidity.
次に実施例によって本発明をさらに詳細に説明する。なお本願発明にかかる物質の諸物性の評価は以下の手法に拠った。
＜セルロース性物質の平均重合度＞
ＡＳＴＭ Ｄｅｓｉｇｎａｔｉｏｎ： Ｄ １７９５−９０「Ｓｔａｎｄａｒｄ Ｔｅｓｔ Ｍｅｔｈｏｄ ｆｏｒ Ｉｎｔｒｉｎｓｉｃ Ｖｉｓｃｏｓｉｔｙ ｏｆ Ｃｅｌｌｕｌｏｓｅ」に準じて行う。
Next, the present invention will be described in more detail with reference to examples. The evaluation of various physical properties of the substance according to the present invention was based on the following method.
<Average degree of polymerization of cellulosic material>
ASTM Designation: D 1795-90 “Standard Test Method for Intrinsic Visibility of Cellulose”.
＜セルロース性物質のα−セルロース含有量＞
ＪＩＳ Ｐ ８１０１−１９７６（「溶解パルプ試験方法」５．５ αセルロース）に準じて行う。
<Α-cellulose content of cellulosic material>
It is performed according to JIS P 8101-1976 (“dissolving pulp test method” 5.5 α cellulose).
＜セルロース性物質の結晶化度＞
ＪＩＳ Ｋ ０１３１−１９９６（「Ｘ線回折分析通則」）に規定されるＸ線回析装置で得られたＸ線回折図の回折強度値から、Ｓｅｇａｌ 法により算出したもので次式によって定義される。
結晶化度（％）＝｛（Ｉｃ−Ｉａ）／Ｉｃ｝×１００
ここで、Ｉｃ：Ｘ線回析図の回折角２θ＝２２．５度での回折強度、Ｉａ：同じく回析角２θ＝１８．５度付近のベースライン強度（極小値強度）である。
<Crystallinity of cellulosic material>
It is calculated by the Segal method from the diffraction intensity value of the X-ray diffraction pattern obtained by the X-ray diffraction apparatus prescribed in JIS K 0131-1996 (“General Rules for X-ray Diffraction Analysis”) and is defined by the following equation: .
Crystallinity (%) = {(Ic−Ia) / Ic} × 100
Here, Ic is the diffraction intensity at the diffraction angle 2θ = 22.5 degrees in the X-ray diffraction diagram, and Ia is the baseline intensity (minimum value intensity) around the diffraction angle 2θ = 18.5 degrees.
＜セルロース繊維（粒子）の形状（長径、短径、長径／短径比）＞
セルロース繊維（粒子）のサイズの範囲が広いので、一種類の顕微鏡で全てを観察することは不可能である。そこで、繊維（粒子）の大きさに応じて光学顕微鏡、走査型顕微鏡（中分解能ＳＥＭ、高分解能ＳＥＭ）を適宜選択し、観察・測定する。
光学顕微鏡を使用する場合は、固形分濃度が０．２５質量％の水分散液となるようにサンプルと純水を量り取り、「エクセルオートホモジナイザー」（日本精機株式会社製）で、１５０００ｒｐｍで１５分間分散したものを、適当な濃度に調整し、それをスライドガラスにのせ、さらにカバーグラスをのせて観察する。
<Shape of cellulose fiber (particle) (major axis, minor axis, major axis / minor axis ratio)>
Since the range of the size of cellulose fibers (particles) is wide, it is impossible to observe all with one kind of microscope. Therefore, an optical microscope and a scanning microscope (medium resolution SEM, high resolution SEM) are appropriately selected according to the size of the fibers (particles), and observed and measured.
When using an optical microscope, the sample and pure water are weighed out so as to obtain an aqueous dispersion having a solid content concentration of 0.25% by mass, and “Excel Auto Homogenizer” (manufactured by Nippon Seiki Co., Ltd.) is used. The one dispersed for a minute is adjusted to an appropriate concentration, placed on a slide glass, and further covered with a cover glass and observed.
また、中分解能ＳＥＭ（日本電子株式会社製、「ＪＳＭ−５５１０ＬＶ」）を使用する場合は、サンプル水分散液を試料台にのせ、風乾した後、Ｐｔ−Ｐｄを約３ｎｍ蒸着して観察する。
高分解能ＳＥＭ（株式会社日立サイエンスシステムズ製、「Ｓ−５０００」）を使用する場合は、サンプル水分散液を試料台にのせ、風乾した後、Ｐｔ−Ｐｄを約１．５ｎｍ蒸着して観察する。
In addition, when using a medium resolution SEM (manufactured by JEOL Ltd., “JSM-5510LV”), a sample aqueous dispersion is placed on a sample stage and air-dried, and then Pt—Pd is deposited by about 3 nm and observed.
When using a high-resolution SEM (manufactured by Hitachi Science Systems, Inc., “S-5000”), place the sample aqueous dispersion on the sample stage, air dry, and then deposit Pt—Pd by about 1.5 nm for observation. .
セルロース繊維（粒子）の長径、短径、長径／短径比は撮影した写真から１５本（個）以上を選択し、測定した。繊維はほぼまっすぐから、髪の毛のようにカーブしているものがあったが、糸くずのように丸まっていることはなかった。短径（太さ）は、繊維１本の中でもバラツキがあったが、平均的な値を採用した。高分解能ＳＥＭは、短径が数ｎｍ〜２００ｎｍ程度の繊維の観察時に使用したのだが、一本の繊維が長すぎて、一つの視野に収まらなかった。そのため、視野を移動しつつ写真撮影を繰り返し、その後写真を合成して解析した。 The major axis, minor axis, and major axis / minor axis ratio of the cellulose fibers (particles) were measured by selecting 15 (pieces) or more from the photographed photographs. Some fibers were almost straight and curved like hair, but never round like lint. The minor axis (thickness) was varied among single fibers, but an average value was adopted. The high-resolution SEM was used when observing a fiber having a minor axis of several nm to 200 nm, but one fiber was too long to fit in one field of view. Therefore, photography was repeated while moving the field of view, and then the pictures were synthesized and analyzed.
＜「水中で安定に懸濁する成分」の含有量＞
以下の（１）〜（５）および（３’）〜（５’）より求める。
（１）セルロース濃度が０．１質量％の水分散液となるようにサンプルと純水を量り取り、エースホモジナイザー（日本精機株式会社製、ＡＭ−Ｔ型）で、１５０００ｒｐｍで１５分間分散する。
（２）サンプル液２０ｇを遠沈管に入れ、遠心分離機にて１０００Ｇで５分間遠心分離する。
（３）上層の液体部分を取り除き、沈降成分の質量（ａ）を測定する。
（４）次いで、沈降成分を絶乾し、固形分の質量（ｂ）を測定する。
（５）下記の式を用いて「水中で安定に懸濁する成分」の含有量（ｃ）を算出する。
ｃ＝５０００×（ｋ１＋ｋ２） ［質量％］
<Content of “component that is stably suspended in water”>
It calculates | requires from the following (1)-(5) and (3 ')-(5').
(1) The sample and pure water are weighed out so that the cellulose concentration is 0.1% by mass and dispersed with an ace homogenizer (manufactured by Nippon Seiki Co., Ltd., AM-T type) at 15000 rpm for 15 minutes.
(2) Put 20 g of sample solution into a centrifuge tube and centrifuge at 1000 G for 5 minutes in a centrifuge.
(3) The upper liquid portion is removed and the mass (a) of the sediment component is measured.
(4) Next, the sedimentation component is absolutely dried, and the mass (b) of the solid content is measured.
(5) The content (c) of the “component that is stably suspended in water” is calculated using the following formula.
c = 5000 × (k1 + k2) [mass%]
但し、ｋ１およびｋ２は下記の式を用いて算出して使用する。（ここで、ｋ１：上層の液体部分に含まれる「微細な繊維状のセルロース」の量、ｋ２：沈殿成分に含まれる「微細な繊維状のセルロース」の量、ｗ１：上層の液体部分に含まれる水の量、ｗ２：沈殿成分に含まれる水の量、ｓ２：沈殿成分に含まれる「水溶性高分子＋親水性物質」の量とする。）
ｋ１＝０．０２−ｂ＋ｓ２
ｋ２＝ｋ１×ｗ２／ｗ１
（水溶性高分子＋親水性物質）／セルロース
＝ｄ／ｆ ［配合比率］
ｗ１＝１９．９８−ａ＋ｂ−０．０２×ｄ／ｆ
ｗ２＝ａ−ｂ
ｓ２＝０．０２×ｄ×ｗ２／｛ｆ×（ｗ１＋ｗ２）｝
「水中で安定に懸濁する成分」の含有量が非常に多い場合は、沈降成分の重量が小さな値となるので、上記の方法では測定精度が低くなってしまう。その場合は（３）以降の手順を以下のようにして行う。
However, k1 and k2 are calculated using the following formula and used. (Where k1: amount of “fine fibrous cellulose” contained in the upper liquid portion, k2: amount of “fine fibrous cellulose” contained in the precipitation component, and w1: contained in the upper liquid portion. (W2: amount of water contained in the precipitation component, s2: amount of “water-soluble polymer + hydrophilic substance” contained in the precipitation component.)
k1 = 0.02−b + s2
k2 = k1 × w2 / w1
(Water-soluble polymer + hydrophilic substance) / cellulose = d / f [Blending ratio]
w1 = 19.98−a + b−0.02 × d / f
w2 = a−b
s2 = 0.02 × d × w2 / {f × (w1 + w2)}
When the content of “a component that is stably suspended in water” is very large, the weight of the sediment component becomes a small value, so that the measurement accuracy is lowered by the above method. In that case, the procedure after (3) is performed as follows.
（３’）上層の液体部分を取得し、質量（ａ’）を測定する。
（４’）次いで、上層成分を絶乾し、固形分の質量（ｂ’）を測定する。
（５’）下記の式を用いて「水中で安定に懸濁する成分」の含有量（ｃ）を算出する。
ｃ＝５０００×（ｋ１＋ｋ２） ［質量％］
(3 ′) The upper liquid portion is obtained and the mass (a ′) is measured.
(4 ′) Next, the upper layer component is completely dried, and the mass (b ′) of the solid content is measured.
(5 ′) The content (c) of “a component that is stably suspended in water” is calculated using the following formula.
c = 5000 × (k1 + k2) [mass%]
但し、ｋ１およびｋ２は下記の式を用いて算出して使用する。（ここで、ｋ１：上層の液体部分に含まれる「微細な繊維状のセルロース」の量、ｋ２：沈殿成分に含まれる「微細な繊維状のセルロース」の量、ｗ１：上層の液体部分に含まれる水の量、ｗ２：沈殿成分に含まれる水の量、ｓ２：沈殿成分に含まれる「水溶性高分子＋親水性物質」の量とする。）
ｋ１＝ｂ’−ｓ２×ｗ１／ｗ２
ｋ２＝ｋ１×ｗ２／ｗ１
（水溶性高分子＋親水性物質）／セルロース
＝ｄ／ｆ ［配合比率］
ｗ１＝ａ’−ｂ’
ｗ２＝１９．９８−ａ’＋ｂ’−０．０２×ｄ／ｆ
ｓ２＝０．０２×ｄ×ｗ２／｛ｆ×（ｗ１＋ｗ２）｝
もし、（３）の操作で上層の液体部分と沈降成分の境界が明瞭ではなく分離が難しい場合は適宜セルロース濃度を下げて操作を行う。
However, k1 and k2 are calculated using the following formula and used. (Where k1: amount of “fine fibrous cellulose” contained in the upper liquid portion, k2: amount of “fine fibrous cellulose” contained in the precipitation component, and w1: contained in the upper liquid portion. (W2: amount of water contained in the precipitation component, s2: amount of “water-soluble polymer + hydrophilic substance” contained in the precipitation component.)
k1 = b′−s2 × w1 / w2
k2 = k1 × w2 / w1
(Water-soluble polymer + hydrophilic substance) / cellulose = d / f [Blending ratio]
w1 = a′−b ′
w2 = 19.98−a ′ + b′−0.02 × d / f
s2 = 0.02 × d × w2 / {f × (w1 + w2)}
If the boundary between the liquid portion of the upper layer and the sediment component is not clear in the operation (3) and separation is difficult, the operation is performed with the cellulose concentration lowered appropriately.
＜損失正接（＝損失弾性率／貯蔵弾性率）＞
以下の（１）〜（３）の手順で求める。
（１）固形分濃度が０．５質量％の水分散液となるようにサンプルと純水を量り取り、「エクセルオートホモジナイザー」（日本精機株式会社製）で、１５０００ｒｐｍで１５分間分散する。
（２）２５℃の雰囲気中に３時間静置する。
（３）動的粘弾性測定装置にサンプル液を入れてから５分間静置後、以下の条件で測定し、周波数１０ｒａｄ／ｓにおける損失正接（ｔａｎδ）を求める。
装置：「ＡＲＥＳ」（Ｒｈｅｏｍｅｔｒｉｃ Ｓｃｉｅｎｔｉｆｉｃ，Ｉｎｃ．製、１００ＦＲＴＮ１型）
ジオメトリー：Ｄｏｕｂｌｅ Ｗａｌｌ Ｃｏｕｅｔｔｅ
温度：２５℃
歪み：１０％（固定）
周波数：１→１００ｒａｄ／ｓ（約１７０秒かけて上昇させる）
<Loss tangent (= loss elastic modulus / storage elastic modulus)>
It calculates | requires in the procedure of the following (1)-(3).
(1) The sample and pure water are weighed so as to obtain an aqueous dispersion having a solid content concentration of 0.5% by mass, and dispersed with “Excel Auto Homogenizer” (manufactured by Nippon Seiki Co., Ltd.) at 15000 rpm for 15 minutes.
(2) Leave in an atmosphere at 25 ° C. for 3 hours.
(3) After putting the sample liquid into the dynamic viscoelasticity measuring apparatus, the sample is allowed to stand for 5 minutes, and then measured under the following conditions to determine a loss tangent (tan δ) at a frequency of 10 rad / s.
Apparatus: “ARES” (Rheometric Scientific, Inc., 100FRTN1 type)
Geometry: Double Wall Couette
Temperature: 25 ° C
Distortion: 10% (fixed)
Frequency: 1 → 100 rad / s (Raise over about 170 seconds)
＜０．４％質量濃度水分散液の調製、ゲル化状態の確認、粘度測定＞
まず固形分が１質量％の水分散液となるようにサンプルと水を量り取り、「Ｔ．Ｋ．ホモミクサー」（特殊機化工業株式会社製）を使用して、８０００ｒｐｍで１０分間分散する。さらにこの１質量％のサンプル水分散液：水を４：６の比率で混合し、さらに５分間分散して、０．４質量％サンプル水溶液を調製する。この時の温度は特に規定するものではないが、サンプルの分散に適した温度を選択する。
<Preparation of 0.4% mass concentration aqueous dispersion, confirmation of gelation state, viscosity measurement>
First, a sample and water are weighed so that the solid content becomes an aqueous dispersion having a mass of 1% by mass, and dispersed using TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 8000 rpm for 10 minutes. Further, this 1% by mass sample aqueous dispersion: water is mixed at a ratio of 4: 6, and further dispersed for 5 minutes to prepare a 0.4% by mass sample aqueous solution. The temperature at this time is not particularly specified, but a temperature suitable for the dispersion of the sample is selected.
次にこの０．４質量％サンプル水溶液を、２つのビーカーに充填する。一方のビーカーに充填された０．４質量％サンプル水溶液を、２５℃の雰囲気中に２４時間静置した後に、ビーカーを傾けて、０．４質量％サンプル水溶液が流動化してこぼれ落ちれば、流動性を維持しており、ゲル化していないと判断する。ただしゲル化状態の確認が不要なサンプルについては、この操作を省略しても良い。またもう一方のビーカーに充填された０．４質量％サンプル水溶液を、２５℃の雰囲気中に３時間静置後、静置状態で回転粘度計（Ｂ形粘度計、東機産業株式会社製、「ＴＶ−１０形」）をセットし、６０秒後の粘度を読みとる。なお、ローター回転数は３ｒｐｍとし、ローターおよびアダプターは粘度によって適宜変更する。 Next, this 0.4 mass% sample aqueous solution is filled into two beakers. After the 0.4 mass% sample aqueous solution filled in one beaker is allowed to stand in an atmosphere at 25 ° C. for 24 hours, if the beaker is tilted and the 0.4 mass% sample aqueous solution is fluidized and spills, It is judged that it is not gelled. However, this operation may be omitted for samples that do not require confirmation of the gelation state. Moreover, after the 0.4 mass% sample aqueous solution with which the other beaker was filled was left still in a 25 degreeC atmosphere for 3 hours, in a stationary state, a rotational viscometer (B type viscometer, Toki Sangyo Co., Ltd. make, Set “TV-10” and read the viscosity after 60 seconds. The rotor rotation speed is 3 rpm, and the rotor and adapter are appropriately changed depending on the viscosity.
＜液状組成物（フルーツソース、ソフトヨーグルト、はっ酵乳飲料、焼き肉のたれ、シロップ薬、コーンスープ）のゲル化状態の確認、粘度測定＞
後述の実施例により調製された液状組成物を、各々２つのビーカーに充填する。一方のビーカーに充填された液状組成物を２４時間静置した後に、ビーカーを傾けて、液状組成物が流動化してこぼれ落ちれば、流動性を維持しており、ゲル化していないと判断する。ただしゲル化状態の確認が不要なサンプルについては、この操作を省略しても良い。またもう一方のビーカーに充填された液状組成物を、３時間静置後、静置状態で回転粘度計（Ｂ形粘度計、東機産業株式会社製、「ＴＶ−１０形」）をセットし、６０秒後の粘度を読みとる。なお、ローター回転数は３ｒｐｍとし、ローターおよびアダプターは粘度によって適宜変更する。
<Verification of gelled state of liquid composition (fruit sauce, soft yogurt, fermented milk drink, grilled meat, syrup, corn soup), viscosity measurement>
Each beaker is filled with a liquid composition prepared according to the examples described below. If the liquid composition filled in one beaker is allowed to stand for 24 hours, then the beaker is tilted, and if the liquid composition is fluidized and spills, it is determined that the fluidity is maintained and the gel is not gelled. However, this operation may be omitted for samples that do not require confirmation of the gelation state. The liquid composition filled in the other beaker is allowed to stand for 3 hours, and then set in a stationary state with a rotational viscometer (B-type viscometer, manufactured by Toki Sangyo Co., Ltd., “TV-10”). Read the viscosity after 60 seconds. The rotor rotation speed is 3 rpm, and the rotor and adapter are appropriately changed depending on the viscosity.
＜ｐＨ＞
ｐＨ計（東亜ディーケーケー株式会社製、「ＨＭ−５０Ｇ形」）で測定する。
<PH>
Measured with a pH meter (“HM-50G type” manufactured by Toa DKK Corporation).
以下、本発明を実施例と比較例を示して、具体的に説明するが、本発明はこれらに何ら限定されるものではない。実施例で使用する水分散性セルロース、水分散性乾燥組成物、グアーガム、グルコマンナン、キサンタンガムについて、次の（１）〜（６）に示す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to these at all. The water dispersible cellulose, water dispersible dry composition, guar gum, glucomannan and xanthan gum used in the examples are shown in the following (1) to (6).
（１）水分散性乾燥組成物Ａの調整：市販木材パルプ（平均重合度＝１７２０、α−セルロース含有量＝７８質量％）を、６×１６ｍｍ角の矩形に裁断し、固形分濃度が８０質量％になるように水を加えた。これを、水とパルプチップができるだけ分離しないよう注意して、カッターミル（カッティングヘッド／水平刃間隙：２．０３ｍｍ、インペラー回転数：３６００ｒｐｍ）に１回通した。 (1) Preparation of water-dispersible dry composition A: Commercially available wood pulp (average polymerization degree = 1720, α-cellulose content = 78 mass%) is cut into a 6 × 16 mm square and has a solid content concentration of 80 Water was added so that it might become mass%. This was passed once through a cutter mill (cutting head / horizontal blade gap: 2.03 mm, impeller rotation speed: 3600 rpm), taking care not to separate water and pulp chips as much as possible.
セルロース濃度が１．５質量％になるように、カッターミル処理品と水を量り取り、繊維の絡みがなくなるまで撹拌した。この水分散液を砥石回転型粉砕機（グラインダー回転数：１８００ｒｐｍ）で処理した。処理回数は２回で、グラインダークリアランスを１１０→８０μｍと変えて処理した。 The cutter mill-treated product and water were weighed out so that the cellulose concentration was 1.5% by mass, and stirred until there was no fiber entanglement. This aqueous dispersion was treated with a grindstone rotary grinder (grinder rotation speed: 1800 rpm). The number of treatments was 2, and the grinder clearance was changed from 110 to 80 μm.
次いで得られた水分散液をそのまま高圧ホモジナイザー（処理圧力：５５ＭＰａ）で１８パスし、水分散性セルロースＡスラリーを得た。光学顕微鏡で観察したところ、長径が１０〜４００μｍ、短径が１〜５μｍ、長径／短径比が１０〜３００の微細な繊維状セルロースが観察された。損失正接は０．６４だった。「水中で安定に懸濁する成分」の含有量は１５質量％だった。それを高分解能ＳＥＭで観察したところ、長径が１〜２０μｍ、短径が１０〜１５０ｎｍ、長径／短径比が３０〜３００のきわめて微細な繊維状のセルロースが観察された。 Next, the obtained aqueous dispersion was directly subjected to 18 passes with a high-pressure homogenizer (treatment pressure: 55 MPa) to obtain a water-dispersible cellulose A slurry. When observed with an optical microscope, fine fibrous cellulose having a major axis of 10 to 400 μm, a minor axis of 1 to 5 μm, and a major axis / minor axis ratio of 10 to 300 was observed. The loss tangent was 0.64. The content of “a component that is stably suspended in water” was 15% by mass. When observed with a high resolution SEM, very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 10 to 150 nm, and a major axis / minor axis ratio of 30 to 300 was observed.
水分散性セルロースＡ：カルボキシメチルセルロース・ナトリウム：デキストリン＝７０：１８：１２（重量部）となるように、水分散性セルロースＡスラリーにカルボキシメチルセルロース・ナトリウム（１質量％水溶液粘度：約３４００ｍＰａ・ｓ）とデキストリン（ＤＥ：約２３）を添加し、１５ｋｇを攪拌型ホモジナイザー（特殊機化工業株式会社製、「Ｔ．Ｋ．ＡＵＴＯ ＨＯＭＯ ＭＩＸＥＲ」）で、８０００ｒｐｍで３０分間撹拌・混合し、水分散性セルロースＡ’スラリーを得た。 Water-dispersible cellulose A: carboxymethylcellulose sodium: dextrin = 70:18:12 (parts by weight) Water-dispersible cellulose A slurry with carboxymethylcellulose sodium (1% by weight aqueous solution viscosity: about 3400 mPa · s) And dextrin (DE: about 23) were added, and 15 kg was stirred and mixed at 8000 rpm for 30 minutes with a stirring homogenizer (“TK AUTO MIXER” manufactured by Tokushu Kika Kogyo Co., Ltd.). Cellulose A ′ slurry was obtained.
次いでこの混合液をアプリケータにより厚さ２ｍｍでアルミニウム板状にキャストし、熱風乾燥機を使用し、１２０℃で４５分間乾燥してフィルムを得た。これをカッターミル（不二パウダル株式会社製）で、目開き１ｍｍの篩をほぼ全通する程度に粉砕し、水分散性乾燥組成物Ａを得た。
水分散性乾燥組成物Ａの結晶化度は６８％以上、損失正接は０．６４であり、「水中で安定に懸濁する成分」の含有量は２０質量％だった。それを高分解能ＳＥＭで観察したところ、長径が１〜２０μｍ、短径が１５〜１３０ｎｍ、長径／短径比が３０〜３００のきわめて微細な繊維状のセルロースが観察された。
Next, this mixed solution was cast into an aluminum plate shape with a thickness of 2 mm using an applicator, and dried at 120 ° C. for 45 minutes using a hot air dryer to obtain a film. This was pulverized with a cutter mill (manufactured by Fuji Powder Co., Ltd.) so that the sieve having an opening of 1 mm was almost completely passed through to obtain a water-dispersible dry composition A.
The degree of crystallinity of the water-dispersible dry composition A was 68% or more, the loss tangent was 0.64, and the content of “component stably suspended in water” was 20% by mass. When observed with a high-resolution SEM, very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 15 to 130 nm, and a major axis / minor axis ratio of 30 to 300 was observed.
（２）水分散性セルロースＢの調整：市販麦わらパルプ（平均重合度＝９３０、α−セルロース含有量＝６８質量％）を、６×１２ｍｍ角の矩形に裁断し、４質量％となるように水を加え、家庭用ミキサーで５分間撹拌した。これを高速回転型ホモジナイザー（ヤマト科学、「ＵＬＴＲＡ−ＤＩＳＰＥＲＳＥＲ」）で１時間分散した。
この水分散液を砥石回転型粉砕機（グラインダー回転数：１８００ｒｐｍ）で処理した。処理回数は２回で、グラインダークリアランスを６０→４０μｍと変えて処理した。
(2) Adjustment of water-dispersible cellulose B: Commercially available straw pulp (average polymerization degree = 930, α-cellulose content = 68% by mass) is cut into a 6 × 12 mm square to be 4% by mass. Water was added and stirred for 5 minutes with a home mixer. This was dispersed for 1 hour with a high-speed rotation type homogenizer (Yamato Scientific, “ULTRA-DISPERSER”).
This aqueous dispersion was treated with a grindstone rotary grinder (grinder rotation speed: 1800 rpm). The number of treatments was 2, and the grinder clearance was changed from 60 to 40 μm.
次いで得られた水分散液を水で希釈して２質量％にし、高圧ホモジナイザー（処理圧力：１７５ＭＰａ）で８パスし、水分散性セルロースＢスラリーを得た。結晶化度は７４％だった。光学顕微鏡で観察したところ、長径が１０〜７００μｍ、短径が１〜３０μｍ、長径／短径比が１０〜１５０の微細な繊維状のセルロースが観察された。損失正接は０．４３だった。「水中で安定に懸濁する成分」の含有量は８９質量％だった。それを高分解能ＳＥＭで観察したところ、長径が１〜２０μｍ、短径が６〜３００ｎｍ、長径／短径比が３０〜３５０のきわめて微細な繊維状のセルロースが観察された。 Next, the obtained aqueous dispersion was diluted with water to 2% by mass, and subjected to 8 passes with a high-pressure homogenizer (treatment pressure: 175 MPa) to obtain a water-dispersible cellulose B slurry. The crystallinity was 74%. When observed with an optical microscope, fine fibrous cellulose having a major axis of 10 to 700 μm, a minor axis of 1 to 30 μm, and a major axis / minor axis ratio of 10 to 150 was observed. The loss tangent was 0.43. The content of “a component that is stably suspended in water” was 89% by mass. When observed with a high-resolution SEM, very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 6 to 300 nm, and a major axis / minor axis ratio of 30 to 350 was observed.
（３）水分散性乾燥組成物Ｃの調整：市販バガスパルプ（平均重合度＝１３２０、α−セルロース含有量＝７７％）を、６×１６ｍｍ角の矩形に裁断し、固形分濃度が７７質量％になるように水を加えた。
これを、水とパルプチップができるだけ分離しないよう注意して、カッターミル（カッティングヘッド／水平刃間隙：２．０３ｍｍ、インペラー回転数：３６００ｒｐｍ）に１回通した。セルロース濃度が２質量％、そしてカルボキシメチルセルロース・ナトリウムの濃度が０．１１８質量％になるようにカッターミル処理品とカルボキシメチルセルロース・ナトリウム（１質量％水溶液粘度：約３４００ｍＰａ・ｓ）と水を量り取り、繊維の絡みがなくなるまで撹拌した。
(3) Preparation of water-dispersible dry composition C: Commercial bagasse pulp (average polymerization degree = 1320, α-cellulose content = 77%) was cut into a 6 × 16 mm square and the solid content concentration was 77% by mass. Water was added so that
This was passed once through a cutter mill (cutting head / horizontal blade gap: 2.03 mm, impeller rotation speed: 3600 rpm), taking care not to separate water and pulp chips as much as possible. Cutter mill processed product, carboxymethylcellulose sodium (1 mass% aqueous solution viscosity: about 3400 mPa · s) and water are weighed out so that the cellulose concentration is 2 mass% and the concentration of carboxymethylcellulose sodium is 0.118 mass%. The mixture was stirred until the fibers were tangled.
得られた水分散液をそのまま、高圧ホモジナイザー（処理圧力９０ＭＰａ）で９パスし、水分散性セルロースＣスラリーを得た。光学顕微鏡および中分解能ＳＥＭで観察したところ、長径が１０〜５００μｍ、短径が１〜２５μｍ、長径／短径比が５〜１９０の微細な繊維状のセルロースが観察された。損失正接は０．３２だった。「水中で安定に懸濁する成分」は９９質量％だった。「水中で安定に懸濁する成分」を高分解能ＳＥＭで観察したところ、長径が１〜２０μｍ、短径が１０〜４００ｎｍ、長径／短径比が２０〜３００のきわめて微細な繊維状のセルロースが観察された。 The obtained aqueous dispersion was directly subjected to 9 passes with a high-pressure homogenizer (treatment pressure 90 MPa) to obtain a water-dispersible cellulose C slurry. When observed with an optical microscope and medium resolution SEM, fine fibrous cellulose having a major axis of 10 to 500 μm, a minor axis of 1 to 25 μm, and a major axis / minor axis ratio of 5 to 190 was observed. The loss tangent was 0.32. The “component stably suspended in water” was 99% by mass. When the “component that is stably suspended in water” was observed with a high-resolution SEM, a very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 10 to 400 nm, and a major axis / minor axis ratio of 20 to 300 was obtained. Observed.
水分散性セルロースＣ：カルボキシメチルセルロース・ナトリウム：デキストリン：ナタネ油＝６８：１２：１９．７：０．３（重量部）となるように、水分散性セルロースＣスラリーにカルボキシメチルセルロース・ナトリウム（１質量％水溶液粘度：約３４００ｍＰａ・ｓ）とデキストリン（ＤＥ：約２８）を添加し、１５ｋｇを攪拌型ホモジナイザー（特殊機化工業株式会社製、「Ｔ．Ｋ．ＡＵＴＯ ＨＯＭＯ ＭＩＸＥＲ」）で、８０００ｒｐｍで１０分間撹拌・混合した後、前述の高圧ホモジナイザーで２０ＭＰａ、１パス処理し、水分散性セルロースＣ’スラリーを得た。 Water dispersible cellulose C: carboxymethylcellulose sodium: dextrin: rapeseed oil = 68: 12: 19.7: 0.3 (parts by weight) Water dispersible cellulose C slurry with carboxymethylcellulose sodium (1 mass) % Aqueous solution viscosity: about 3400 mPa · s) and dextrin (DE: about 28) were added, and 15 kg was stirred at 8000 rpm with a stirring homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd., “TK AUTO HOMO MIXER”). After stirring and mixing for a minute, 20 MPa and one pass treatment were performed with the above-described high-pressure homogenizer to obtain a water-dispersible cellulose C ′ slurry.
水分散性セルロースＣ’スラリーをドラムドライヤーにて乾燥し、スクレーパーで掻き取り、得られたものをカッターミル（不二パウダル株式会社製）で、目開き２ｍｍの篩をほぼ全通する程度に粉砕し、水分散性乾燥組成物Ｃを得た。水分散性セルロース組成物Ｃの結晶化度は５７％以上、損失正接は０．５２、「水中で安定に懸濁する成分」は１００質量％だった。「水中で安定に懸濁する成分」を高分解能ＳＥＭで観察したところ、長径が１〜１５μｍ、短径が１０〜３３０ｎｍ、長径／短径比が２０〜２５０のきわめて微細な繊維状のセルロースが観察された。 The water-dispersible cellulose C ′ slurry is dried with a drum dryer, scraped off with a scraper, and the obtained product is pulverized with a cutter mill (manufactured by Fuji Powdal Co., Ltd.) to almost pass through a 2 mm sieve. Thus, a water dispersible dry composition C was obtained. The crystallinity of the water-dispersible cellulose composition C was 57% or more, the loss tangent was 0.52, and the “component stably suspended in water” was 100% by mass. When the “component that is stably suspended in water” was observed with a high-resolution SEM, a very fine fibrous cellulose having a major axis of 1 to 15 μm, a minor axis of 10 to 330 nm, and a major axis / minor axis ratio of 20 to 250 was obtained. Observed.
（４）グアーガム（ユニテックフーズ株式会社製）
（５）グルコマンナン（清水化学株式会社製）
（６）キサンタンガム（大日本製薬株式会社製）
(4) Guar gum (Made by Unitech Foods)
(5) Glucomannan (Shimizu Chemical Co., Ltd.)
(6) Xanthan gum (Dainippon Pharmaceutical Co., Ltd.)
［実施例１］
まず固形分が１質量％の水分散液となるように上記のサンプルと水を量り取り、「Ｔ．Ｋ．ホモミクサー」（特殊機化工業株式会社製）を使用して、２５℃、８０００ｒｐｍで１０分間分散した。さらにこの１質量％のサンプル水分散液：水を４：６の比率で混合し、さらに５分間分散して、０．４質量％サンプル水溶液を調製し、２つのビーカーに充填した。一方のビーカーに充填された０．４質量％サンプル水分散液を、２５℃の雰囲気中に２４時間静置後、傾けたところ、流動化してビーカーからこぼれ落ち、ゲル化していなかった。
またもう一方のビーカーに充填された０．４質量％サンプル水溶液を、２５℃の雰囲気中に３時間静置後、静置状態で回転粘度計（Ｂ形粘度計、東機産業株式会社製、「ＴＶ−１０形」）をセットし、６０秒後の粘度を読みとった。なお、ローター回転数は３ｒｐｍとし、ローターおよびアダプターは粘度によって適宜変更した。増粘剤は、水分散性乾燥組成物Ａ：グアーガムを６：４の比率で含有するものを選択し、同様に０．４質量％水分散液としてその粘度Ｚ１を測定した。
[Example 1]
First, the above sample and water are weighed out so that the solid content becomes an aqueous dispersion of 1% by mass, and “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used at 25 ° C. and 8000 rpm. Dispersed for 10 minutes. Further, this 1% by mass sample aqueous dispersion: water was mixed at a ratio of 4: 6, and further dispersed for 5 minutes to prepare a 0.4% by mass sample aqueous solution, which was filled in two beakers. When the 0.4 mass% sample aqueous dispersion filled in one beaker was left to stand in an atmosphere at 25 ° C. for 24 hours and then tilted, it fluidized and spilled from the beaker and did not gel.
Moreover, after the 0.4 mass% sample aqueous solution with which the other beaker was filled was left still in a 25 degreeC atmosphere for 3 hours, in a stationary state, a rotational viscometer (B type viscometer, the Toki Sangyo Co., Ltd. make, “TV-10” was set, and the viscosity after 60 seconds was read. The rotor rotation speed was 3 rpm, and the rotor and adapter were appropriately changed depending on the viscosity. As the thickener, one containing a water-dispersible dry composition A: guar gum in a ratio of 6: 4 was selected, and the viscosity Z1 was similarly measured as a 0.4 mass% aqueous dispersion.
上記の方法で測定した０．４質量％グアーガム水分散液の粘度Ｘ１（３１２ｍＰａ・ｓ）と、０．４質量％水分散性乾燥組成物Ａ水分散液の粘度Ｙ１（１７８０ｍＰａ・ｓ）より、以下の式を用いて理論粘度を求めたところ、理論粘度α１は１１９３ｍＰａ・ｓとなった。
理論粘度α＝〔β×粘度Ｘ＋γ×粘度Ｙ〕／（β＋γ）
β：粘度Ｚ１を求める時に使用した、増粘剤水分散液あるいは液状組成物中に含まれる、多糖類の量（質量％）
γ：粘度Ｚ１を求める時に使用した、増粘剤水分散液あるいは液状組成物中に含まれる、水分散性セルロース（または水分散性乾燥組成物）の量（質量％）
β＋γ：粘度Ｚを求める時に使用した、増粘剤水分散液あるいは液状組成物に含まれる、増粘剤の量（質量％）
０．４質量％増粘剤水分散液の粘度Ｚ１（２２００ｍＰａ・ｓ）と、上記理論粘度α１（１１９３ｍＰａ・ｓ）の関係は、「粘度Ｚ１＞理論粘度α１」となり、この増粘剤は増粘相乗効果を有すると判定した。
From the viscosity X1 (312 mPa · s) of the 0.4 mass% guar gum aqueous dispersion measured by the above method and the viscosity Y1 (1780 mPa · s) of the 0.4 mass% water-dispersible dry composition A aqueous dispersion, When the theoretical viscosity was determined using the following equation, the theoretical viscosity α1 was 1193 mPa · s.
Theoretical viscosity α = [β × viscosity X + γ × viscosity Y] / (β + γ)
β: Amount (% by mass) of polysaccharide contained in the thickener aqueous dispersion or liquid composition used to determine viscosity Z1
γ: Amount (% by mass) of water-dispersible cellulose (or water-dispersible dry composition) contained in the thickener aqueous dispersion or liquid composition used for determining the viscosity Z1
β + γ: The amount (% by mass) of the thickener contained in the aqueous thickener dispersion or liquid composition used to determine the viscosity Z
The relationship between the viscosity Z1 (2200 mPa · s) of the 0.4 mass% thickener aqueous dispersion and the above theoretical viscosity α1 (1193 mPa · s) is “viscosity Z1> theoretical viscosity α1”. It was determined to have a viscous synergistic effect.
［実施例２］
増粘剤は、水分散性セルロースＢスラリー（２質量％濃度）を用いて、水分散性セルロースＢ：グアーガムを６：４の質量比で含有するものを選択した。０．４質量％増粘剤水分散液を、実施例１と同様の方法で調製し、評価した。この０．４質量％増粘剤水分散液は、流動性を維持し、ゲル化していなかった。
実施例１と同様の方法で得た０．４質量％グアーガム水分散液の粘度Ｘ２（３１２ｍＰａ・ｓ）と、０．４質量％水分散性セルロースＢ水分散液の粘度Ｙ２（８４９ｍＰａ・ｓ）より、理論粘度を求めたところ、理論粘度α２は６３４ｍＰａ・ｓとなった。
さらに０．４質量％増粘剤水分散液の粘度Ｚ２（１８５０ｍＰａ・ｓ）と、上記理論粘度α２（６３４ｍＰａ・ｓ）の関係は、「粘度Ｚ２＞理論粘度α２」となり、この増粘剤は増粘相乗効果を有すると判定した。
[Example 2]
As the thickener, water-dispersible cellulose B slurry (2% by mass concentration) was used, and a thickener containing water-dispersible cellulose B: guar gum at a mass ratio of 6: 4 was selected. A 0.4 mass% thickener aqueous dispersion was prepared and evaluated in the same manner as in Example 1. This 0.4 mass% thickener aqueous dispersion maintained fluidity and was not gelled.
Viscosity X2 (312 mPa · s) of 0.4 mass% guar gum aqueous dispersion obtained in the same manner as in Example 1, and viscosity Y2 (849 mPa · s) of 0.4 mass% water-dispersible cellulose B aqueous dispersion Further, when the theoretical viscosity was determined, the theoretical viscosity α2 was 634 mPa · s.
Furthermore, the relationship between the viscosity Z2 (1850 mPa · s) of the 0.4% by weight thickener aqueous dispersion and the theoretical viscosity α2 (634 mPa · s) is “viscosity Z2> theoretical viscosity α2”. It was determined to have a thickening synergistic effect.
［実施例３］
増粘剤は、水分散性乾燥組成物Ｃ：グアーガムを８：２の質量比で含有するものを選択した。０．４質量％増粘剤水分散液を、実施例１と同様の方法で調製し、評価した。この０．４質量％増粘剤水分散液は、流動性を維持し、ゲル化していなかった。
実施例１と同様の方法で得た０．４質量％グアーガム水分散液の粘度Ｘ３（３１２ｍＰａ・ｓ）と、０．４質量％水分散乾燥組成物Ｃの水分散液の粘度Ｙ３（２０１０ｍＰａ・ｓ）より、理論粘度を求めたところ、理論粘度α３は１６７０ｍＰａ・ｓとなった。さらに０．４質量％増粘剤水分散液の粘度Ｚ３（２７００ｍＰａ・ｓ）と、理論粘度α３（１６７０ｍＰａ・ｓ）の関係は、「粘度Ｚ３＞理論粘度α３」となり、この増粘剤は増粘相乗効果を有すると判定した。
[Example 3]
The thickener was selected to contain a water dispersible dry composition C: guar gum in a mass ratio of 8: 2. A 0.4 mass% thickener aqueous dispersion was prepared and evaluated in the same manner as in Example 1. This 0.4 mass% thickener aqueous dispersion maintained fluidity and was not gelled.
Viscosity X3 (312 mPa · s) of 0.4 mass% guar gum aqueous dispersion obtained in the same manner as in Example 1, and viscosity Y3 (2010 mPa · s) of aqueous dispersion of 0.4 mass% aqueous dispersion dry composition C When the theoretical viscosity was determined from s), the theoretical viscosity α3 was 1670 mPa · s. Furthermore, the relationship between the viscosity Z3 (2700 mPa · s) of the 0.4 mass% thickener aqueous dispersion and the theoretical viscosity α3 (1670 mPa · s) is “viscosity Z3> theoretical viscosity α3”. It was determined to have a viscous synergistic effect.
［実施例４］
増粘剤は、水分散性乾燥組成物Ｃ：グアーガムを６：４の質量比で含有するものを選択した。０．４質量％増粘剤水分散液を、実施例１と同様の方法で調製し、評価した。この０．４質量％増粘剤水分散液は、流動性を維持し、ゲル化していなかった。
実施例１と同様の方法で得た０．４質量％グアーガム水分散液の粘度Ｘ４（３１２ｍＰａ・ｓ）と、０．４質量％水分散乾燥組成物Ｃの水分散液の粘度Ｙ４（２０１０ｍＰａ・ｓ）より、理論粘度を求めたところ、理論粘度α４は１３３１ｍＰａ・ｓであった。さらに０．４質量％増粘剤水分散液の粘度Ｚ４（３３５０ｍＰａ・ｓ）と、理論粘度α４（１３３１ｍＰａ・ｓ）の関係は、「粘度Ｚ４＞理論粘度α４」となり、この増粘剤は増粘相乗効果を有すると判定した。
[Example 4]
As the thickener, one containing a water-dispersible dry composition C: guar gum in a mass ratio of 6: 4 was selected. A 0.4 mass% thickener aqueous dispersion was prepared and evaluated in the same manner as in Example 1. This 0.4 mass% thickener aqueous dispersion maintained fluidity and was not gelled.
Viscosity X4 (312 mPa · s) of 0.4 mass% guar gum aqueous dispersion obtained in the same manner as in Example 1, and viscosity Y4 of aqueous dispersion of 0.4 mass% aqueous dispersion dry composition C (2010 mPa · s) When the theoretical viscosity was determined from s), the theoretical viscosity α4 was 1331 mPa · s. Further, the relationship between the viscosity Z4 (3350 mPa · s) of the 0.4 mass% thickener aqueous dispersion and the theoretical viscosity α4 (1331 mPa · s) is “viscosity Z4> theoretical viscosity α4”. It was determined to have a viscous synergistic effect.
［実施例５］
増粘剤は、水分散性乾燥組成物Ｃ：グアーガムを４：６の質量比で含有するものを選択した。０．４質量％増粘剤水分散液を、実施例１と同様の方法で調製し、評価した。この０．４質量％増粘剤水分散液は、流動性を維持し、ゲル化していなかった。
実施例１と同様の方法で得た０．４質量％グアーガム水分散液の粘度Ｘ５（３１２ｍＰａ・ｓ）と、０．４質量％水分散乾燥組成物Ｃの水分散液の粘度Ｙ５（２０１０ｍＰａ・ｓ）より、理論粘度を求めたところ、理論粘度α５は９９１ｍＰａ・ｓであった。さらに０．４質量％増粘剤水分散液の粘度Ｚ５（２４８０ｍＰａ・ｓ）と、理論粘度α５（９９１ｍＰａ・ｓ）の関係は、「粘度Ｚ５＞理論粘度α５」となり、この増粘剤は増粘相乗効果を有すると判定した。
[Example 5]
As the thickener, one containing a water-dispersible dry composition C: guar gum in a mass ratio of 4: 6 was selected. A 0.4 mass% thickener aqueous dispersion was prepared and evaluated in the same manner as in Example 1. This 0.4 mass% thickener aqueous dispersion maintained fluidity and was not gelled.
Viscosity X5 (312 mPa · s) of 0.4 mass% guar gum aqueous dispersion obtained in the same manner as in Example 1, and viscosity Y5 (2010 mPa · s) of an aqueous dispersion of 0.4 mass% aqueous dispersion dry composition C. When the theoretical viscosity was determined from s), the theoretical viscosity α5 was 991 mPa · s. Furthermore, the relationship between the viscosity Z5 (2480 mPa · s) of the 0.4 mass% thickener aqueous dispersion and the theoretical viscosity α5 (991 mPa · s) is “viscosity Z5> theoretical viscosity α5”. It was determined to have a viscous synergistic effect.
［実施例６］
増粘剤は、水分散性乾燥組成物Ｃ：グルコマンナンを６：４の質量比で含有するものを選択した。０．４質量％増粘剤水分散液を、実施例１と同様の方法で調製し、評価した。この０．４質量％増粘剤水分散液は、流動性を維持し、ゲル化していなかった。
実施例１と同様の方法で得た０．４質量％グルコマンナン水分散液の粘度Ｘ６（３７２ｍＰａ・ｓ）と、０．４質量％水分散乾燥組成物Ｃの水分散液の粘度Ｙ６（２０１０ｍＰａ・ｓ）より、理論粘度を求めたところ、理論粘度α６は１３５５ｍＰａ・ｓであった。さらに０．４質量％増粘剤水分散液の粘度Ｚ６（３２８０ｍＰａ・ｓ）と、理論粘度α６（１３５５ｍＰａ・ｓ）の関係は、「粘度Ｚ６＞理論粘度α６」となり、この増粘剤は増粘相乗効果を有すると判定した。
[Example 6]
As the thickener, one containing a water-dispersible dry composition C: glucomannan at a mass ratio of 6: 4 was selected. A 0.4 mass% thickener aqueous dispersion was prepared and evaluated in the same manner as in Example 1. This 0.4 mass% thickener aqueous dispersion maintained fluidity and was not gelled.
Viscosity X6 (372 mPa · s) of 0.4 mass% glucomannan aqueous dispersion obtained in the same manner as in Example 1, and viscosity Y6 (2010 mPa) of an aqueous dispersion of 0.4 mass% aqueous dispersion dry composition C When the theoretical viscosity was determined from s), the theoretical viscosity α6 was 1355 mPa · s. Furthermore, the relationship between the viscosity Z6 (3280 mPa · s) of the 0.4 mass% thickener aqueous dispersion and the theoretical viscosity α6 (1355 mPa · s) is “viscosity Z6> theoretical viscosity α6”. It was determined to have a viscous synergistic effect.
〔実施例７〕
水分散性乾燥組成物Ｃとグアーガムを６：４の質量比で粉末混合した増粘剤（以下増粘剤ａと言う）を用いて、以下の手順でフルーツソースＡを調製し、評価を行った。ビーカーに、水１４．３２質量％と果糖ブドウ糖液糖（王子コーンスターチ株式会社製、「Ｆ−５５」）４０質量％を入れて６０℃に加温し、「Ｔ．Ｋ．ホモミクサー」（特殊機化工業株式会社製）で攪拌しながら、０．６８質量％の上記増粘剤ａと、５質量％のグラニュー糖（第一糖業株式会社製）を粉末混合したものを添加し、８０００ｒｐｍで１０分間分散させた。
Example 7
Using a thickener (hereinafter referred to as thickener a) in which water-dispersible dry composition C and guar gum are powder-mixed at a mass ratio of 6: 4, fruit sauce A is prepared by the following procedure and evaluated. It was. In a beaker, 14.32% by mass of water and 40% by mass of fructose-glucose liquid sugar (manufactured by Oji Cornstarch Co., Ltd., “F-55”) were heated to 60 ° C., and “TK homomixer” (special machine) A mixture of 0.68% by mass of the above thickener a and 5% by mass of granulated sugar (manufactured by Daiichi Sugar Industry Co., Ltd.) was added with stirring at 8000 rpm. Dispersed for 10 minutes.
さらに分散装置をプロペラ攪拌翼に交換し、８０℃に暖めて殺菌した４０質量％のイチゴピューレ（冷凍イチゴを解凍し、裏ごししたもの）を加え、４００ｒｐｍで攪拌した。液温が８０℃に達してから２分間経過するまで攪拌を続け、殺菌処理して、これをフルーツソースＡとした。フルーツソースＡを２つのビーカーに充填し、一方のビーカーを２５℃で２４時間静置した後、ビーカーを傾けたところ、流動化してこぼれ落ち、ゲル化していなかった。またもう一方のビーカーに充填されたフルーツソースＡを、２５℃で３時間静置後、粘度を測定したところ、１９８００ｍＰａ・ｓであり、ｐＨは３．４であった。 Further, the dispersion apparatus was replaced with a propeller stirring blade, and 40% by mass of strawberry puree (thawed and thawed frozen strawberry) heated to 80 ° C. and sterilized was added and stirred at 400 rpm. Stirring was continued until 2 minutes had passed after the liquid temperature reached 80 ° C., and sterilization was performed. The fruit sauce A was filled into two beakers, and one beaker was allowed to stand at 25 ° C. for 24 hours, and then the beaker was tilted. Moreover, when the fruit sauce A with which the other beaker was filled was allowed to stand at 25 ° C. for 3 hours and then the viscosity was measured, it was 19800 mPa · s and the pH was 3.4.
〔実施例８〕
実施例７のフルーツソースＡを使用して、以下の手順でソフトヨーグルトＢを調製し、評価した。クリーンベンチ内で、下記の攪拌用ヨーグルト８５質量％と、実施例７で調製したフルーツソースＡ１５質量％を混合した。次にプロペラ攪拌翼を使用して、５℃、４００ｒｐｍで１分間攪拌し、これをソフトヨーグルトＢとした。この時のソフトヨーグルトＢにおける増粘剤ａの含有量は、０．１質量％であった。
Example 8
Using the fruit sauce A of Example 7, soft yogurt B was prepared and evaluated by the following procedure. In a clean bench, 85% by mass of the following yogurt for stirring was mixed with 15% by mass of the fruit sauce A prepared in Example 7. Next, using a propeller stirring blade, the mixture was stirred at 5 ° C. and 400 rpm for 1 minute to obtain soft yogurt B. At this time, the content of the thickener a in the soft yogurt B was 0.1% by mass.
ソフトヨーグルトＢを２つのビーカーに充填した。一方のビーカーを、５℃で２２時間静置して、さらに２５℃で２時間静置した後に、ビーカーを傾けたところ、流動化してこぼれ落ち、ゲル化していなかった。またもう一方のビーカーに充填されたソフトヨーグルトＢを、５℃で１時間静置して、さらに２５℃で２時間静置した後、粘度を測定したところ、２４００ｍＰａ・ｓであり、ｐＨは４．３であった。 Soft yogurt B was filled into two beakers. One beaker was allowed to stand at 5 ° C. for 22 hours, and further allowed to stand at 25 ° C. for 2 hours, and when the beaker was tilted, it fluidized and spilled and did not gel. The soft yogurt B filled in the other beaker was allowed to stand at 5 ° C. for 1 hour, further allowed to stand at 25 ° C. for 2 hours, and then the viscosity was measured to find 2400 mPa · s, and the pH was 4 .3.
ここで使用する攪拌ヨーグルトの製造方法は、以下の通りである。
２１．７質量％の水と、７５質量％の牛乳（南日本酪農協同株式会社製、乳脂肪分３．５％以上、無脂乳固形分８．３％）をステンレスビーカーに注ぎ、プロペラ攪拌翼を使用して、２５℃で２００ｒｐｍで攪拌しながら、３．３質量％の脱脂粉乳（雪印乳業株式会社製）を添加し、１０分間攪拌を続けた。
The manufacturing method of the stirring yogurt used here is as follows.
21.7% by mass of water and 75% by mass of milk (manufactured by Southern Japan Dairy Kyodo Co., Ltd., milk fat content 3.5% or more, non-fat milk solid content 8.3%) are poured into a stainless steel beaker and stirred with a propeller While stirring at 200 rpm at 25 ° C. using a blade, 3.3% by mass of skim milk powder (manufactured by Snow Brand Milk Products Co., Ltd.) was added, and stirring was continued for 10 minutes.
その溶液を、高圧ホモジナイザーを使用し、１５ＭＰａの処理圧力で均質化し、プロペラ攪拌翼を用いて、８０℃、２００ｒｐｍで更に３０分間攪拌し、殺菌処理した。更にクリーンベンチ内で、２００ｒｐｍで攪拌しながら、２０分で３０℃まで冷却した。この溶液に０．０１％質量％水溶液としたスターター（ダニスコ カルター社製、「ＭＳＫ−Ｍｉｘ ＡＢ Ｎ １−４５ Ｖｉｓｂｙｂａｃ ＤＩＰ」）を、外割で０．３２質量％加え、スパチュラで攪拌し、発酵用容器に充填した。これをインキュベーターに移し、４２℃で１２時間発酵させた。発酵後５℃の冷蔵庫に移し、３日間経過したものを攪拌用ヨーグルト（無脂乳固形分９．４％以上）とした。 The solution was homogenized at a processing pressure of 15 MPa using a high-pressure homogenizer, and further stirred for 30 minutes at 80 ° C. and 200 rpm using a propeller stirring blade to sterilize the solution. Furthermore, it cooled to 30 degreeC in 20 minutes, stirring at 200 rpm in a clean bench. A starter (manufactured by Danisco Carter, “MSK-Mix AB N 1-45 Visbybac DIP”) as an aqueous solution of 0.01% by mass was added to this solution in an external ratio of 0.32% by mass, stirred with a spatula, and fermented. The container was filled. This was transferred to an incubator and fermented at 42 ° C. for 12 hours. After fermentation, the mixture was transferred to a refrigerator at 5 ° C. and passed for 3 days to obtain a stirring yogurt (non-fat milk solid content of 9.4% or more).
〔実施例９〕
実施例７のフルーツソースＡと実施例８の攪拌ヨーグルトを使用して、以下の手順では発酵乳飲料Ｃを調製し、評価した。
クリーンベンチ内で、実施例７のフルーツソースＡを３０質量％、実施例８の攪拌ヨーグルト５０質量％、水２０質量％を、プロペラ攪拌翼を使用して４００ｒｐｍで、２分間混合した。この溶液を、高圧ホモジナイザーを使用して、１５ＭＰａの処理圧力で均質化し、耐熱容器に充填し、８５℃の湯浴中で１５分間殺菌処理したものを、はっ酵乳飲料Ｃとした。この時のはっ酵乳Ｃにおける増粘剤ａの含有
量は、０．２質量％であった。はっ酵乳飲料Ｃを２つのビーカーに充填し、一方のビーカーを５℃で２３時間静置して、さらに２５℃で１時間静置した。このビーカーを傾けたところ、はっ酵乳飲料Ｃは流動化してこぼれ落ち、ゲル化していなかった。またもう一方のビーカーを、５℃で２時間静置して、さらに２５℃で１時間静置した後に、はっ酵乳飲料Ｃの粘度を測定したところ、４４６０ｍＰ・ｓの粘度を示し、ｐＨは４．０であった。
Example 9
Using the fruit sauce A of Example 7 and the stirred yogurt of Example 8, fermented milk drink C was prepared and evaluated in the following procedure.
In a clean bench, 30% by mass of fruit source A of Example 7, 50% by mass of stirred yoghurt of Example 8 and 20% by mass of water were mixed at 400 rpm for 2 minutes using a propeller stirring blade. This solution was homogenized at a treatment pressure of 15 MPa using a high-pressure homogenizer, filled into a heat-resistant container, and sterilized for 15 minutes in a 85 ° C. hot water bath to obtain a fermented milk drink C. Content of the thickener a in the fermented milk C at this time was 0.2 mass%. Fermented milk drink C was filled into two beakers, and one beaker was allowed to stand at 5 ° C. for 23 hours and further allowed to stand at 25 ° C. for 1 hour. When this beaker was tilted, the fermented milk drink C was fluidized and spilled and did not gel. The other beaker was allowed to stand at 5 ° C. for 2 hours and further allowed to stand at 25 ° C. for 1 hour, and then the viscosity of the fermented milk beverage C was measured. As a result, it showed a viscosity of 4460 mP · s and a pH of 4 0.0.
〔実施例１０〕
水分散性乾燥組成物Ｃ：グアーガム：キサンタンガム＝５：４：１の質量比で粉末混合した増粘剤（以下増粘剤ｂと言う）を用いて、以下の手順で焼き肉のたれＤを調製し、評価を行った。水４４．６質量％と果糖ブドウ糖液糖（王子コーンスターチ株式会社製、「Ｆ−５５」）１５質量％を入れて６０℃に加温し、「Ｔ．Ｋ．ホモミクサー」（特殊機化工業株式会社製）で攪拌しながら、０．４質量％の上記増粘剤ｂと、グラニュー糖（第一糖業株式会社製）５質量％を粉末混合したものを添加し、８０００ｒｐｍで１０分間分散させた。更に分散装置をプロペラ攪拌翼に交換し、しょうゆ２５質量％（キッコーマン株式会社製、食塩濃度１６％）、食塩５質量％（財団法人塩事業センター製）、旭味１質量％（日本たばこ産業株式会社製）、りんご酢５質量％（株式会社ミツカン製、酸度５．０％）、おろしたまねぎ２質量％、おろしにんにく１質量％、りんご果汁１質量％（アイク株式会社製、果汁１００％）を加え、４００ｒｐｍで攪拌し、液温が８０℃に達してから３分間経過するまで攪拌を続け、殺菌処理したものを、焼き肉のたれＤとした。この焼き肉のたれＤ中に含まれる増粘剤ｂの含有量は０．４質量％であり、焼き肉のたれＤの食塩濃度は９％であった。焼き肉のたれＤを２つのビーカーに充填し、一方のビーカーを２５℃で２４時間静置した後、ビーカーを傾けたところ、流動化してビーカーからこぼれ落ち、ゲル化していなかった。またもう一方のビーカーを、２５℃で３時間静置後、焼き肉のたれＤの粘度を測定したところ、１２００ｍＰａ・ｓであり、ｐＨは４．２であった。
Example 10
A water-dispersible dry composition C: guar gum: xanthan gum = a thick meat sauce D is prepared by the following procedure using a thickener (hereinafter referred to as thickener b) mixed in a mass ratio of 5: 4: 1. And evaluated. 44.6% by mass of water and 15% by mass of fructose glucose liquid sugar (“F-55” manufactured by Oji Cornstarch Co., Ltd.) were added and heated to 60 ° C., and “TK homomixer” (special machine industry stock) While stirring at a company), 0.4% by mass of the above thickener b and 5% by mass of granulated sugar (Daiichi Sugar Co., Ltd.) were added and dispersed at 8000 rpm for 10 minutes. It was. Furthermore, the dispersing device was replaced with a propeller stirring blade, soy sauce 25% by mass (made by Kikkoman Corporation, salt concentration 16%), salt 5% by mass (made by the Salt Business Center), Asahi taste 1% by mass (Japan Tobacco Inc.) Company), apple vinegar 5% by mass (Mitsukan Co., Ltd., acidity 5.0%), grated onion 2% by mass, grated garlic 1% by mass, apple juice 1% by mass (Ike Co., Ltd., fruit juice 100%) In addition, stirring was continued at 400 rpm, and stirring was continued until 3 minutes had elapsed after the liquid temperature reached 80 ° C., and the sterilized product was designated as Sauce D of grilled meat. The content of the thickener b contained in the grilled meat sauce D was 0.4% by mass, and the salt concentration of the grilled meat sauce D was 9%. After the beaker D was filled in two beakers and one beaker was allowed to stand at 25 ° C. for 24 hours, the beaker was tilted and fluidized and spilled from the beaker and did not gel. The other beaker was allowed to stand at 25 ° C. for 3 hours, and then the viscosity of grilled meat sauce D was measured and found to be 1200 mPa · s and pH was 4.2.
〔実施例１１〕
実施例１０で使用した増粘剤ｂを用いて、以下の手順でシロップ薬Ｅを調製し、評価を行った。
果糖ブドウ糖液糖（王子コーンスターチ株式会社製、「Ｆ−５５」）２０質量％と、３７．９５質量％精製水（日本薬局方）をプロペラ攪拌翼で攪拌しながら、以下に示す１質量％増粘剤ｂ水分散液を４０質量％と、以下に示す医薬品混合物ｄを２．０５質量％加え、３００ｒｐｍで３０分間分散させた。
Example 11
Using thickener b used in Example 10, syrup E was prepared and evaluated in the following procedure.
While stirring 20% by mass of fructose-glucose liquid sugar (manufactured by Oji Cornstarch Co., Ltd., “F-55”) and 37.95% by mass purified water (Japanese Pharmacopoeia) with a propeller stirring blade, the following 1% mass increase 40% by mass of the viscous agent b aqueous dispersion and 2.05% by mass of the pharmaceutical mixture d shown below were added and dispersed at 300 rpm for 30 minutes.
この溶液を、高圧ホモジナイザーを使用し、１５ＭＰａの処理圧力で、２回均質化する。これをシロップ薬Ｅとした。このシロップ薬Ｅに含まれる増粘剤ｂの含有量は０．４質量％であった。シロップ薬Ｅを２つのビーカーに充填し、一方のビーカーを２５℃で２４時間静置後、ビーカーを傾けたところ、流動化してビーカーからこぼれ落ち、ゲル化していなかった。またもう一方のビーカーを、２５℃で３時間静置後、シロップ薬Ｅの粘度を測定したところ、２８１０ｍＰａ・ｓであった。１質量％増粘剤ｂ水分散液の調製：「Ｔ．Ｋ．ホモミクサー」（特殊機化工業株式会社製）で攪拌しながら、精製水９９質量％に、増粘剤ｂを１質量％添加し、４０℃、８０００ｒｐｍで１０分間分散させた。界面活性剤ｃの調製：ソルビトールから誘導される脂肪酸エステルである「スパン８０」、およびそのポリオキシエチレン鎖付加誘導体である「ツイン８０」を５：５の質量比で混合した。
医薬品混合物ｄの調製：アセトアミノフェン（日本薬局方）：界面活性剤ｃを、２００：５の質量比で混合した。
This solution is homogenized twice using a high pressure homogenizer at a processing pressure of 15 MPa. This was designated as syrup medicine E. Content of the thickener b contained in this syrup medicine E was 0.4 mass%. Syrup E was filled in two beakers, and one beaker was allowed to stand at 25 ° C. for 24 hours and then the beaker was tilted. As a result, the beaker fluidized and spilled from the beaker and did not gel. The other beaker was allowed to stand at 25 ° C. for 3 hours, and then the viscosity of syrup E was measured and found to be 2810 mPa · s. Preparation of 1% by weight thickener b aqueous dispersion: 1% by weight of thickener b is added to 99% by weight of purified water while stirring with “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.). And dispersed at 40 ° C. and 8000 rpm for 10 minutes. Preparation of surfactant c: “Span 80” which is a fatty acid ester derived from sorbitol and “Twin 80” which is a polyoxyethylene chain addition derivative thereof were mixed at a mass ratio of 5: 5.
Preparation of pharmaceutical mixture d: Acetaminophen (Japanese Pharmacopoeia): Surfactant c was mixed at a mass ratio of 200: 5.
〔実施例１２〕
実施例７で使用した増粘剤ａを配合し、以下の手順でコーンスープＦを調整し、評価を行った。
水８８．６質量％を「Ｔ．Ｋ．ホモミクサー」（特殊機化工業株式会社製）で攪拌しながら、増粘剤ａを０．４質量％添加し、８０℃、７０００ｒｐｍで５分間分散した。さらに１１質量％の多糖類を含有しない市販乾燥スープ（株式会社ポッカ製）を添加して、５分間分散し、コーンスープＦとした。食塩濃度は０．７３質量％となった。
コーンスープＦを２つのビーカーに充填し、一方のビーカーを２５℃で２４時間静置後、ビーカーを傾けたところ、流動化してビーカーからこぼれ落ち、ゲル化していなかった。
またもう一方のビーカーを、２５℃で３時間静置後、コーンスープＦの粘度を測定したところ、１３８４０ｍＰａ・ｓであり、ｐＨは６．８であった。
Example 12
Thickener a used in Example 7 was blended, and corn soup F was prepared and evaluated according to the following procedure.
While stirring 88.6% by mass of water with “TK Homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), 0.4% by mass of thickener a was added and dispersed at 80 ° C. and 7000 rpm for 5 minutes. . Furthermore, a commercial dry soup (manufactured by Pokka Co., Ltd.) containing no 11% by mass of polysaccharide was added and dispersed for 5 minutes to obtain corn soup F. The salt concentration was 0.73% by mass.
Corn soup F was filled into two beakers, and one beaker was allowed to stand at 25 ° C. for 24 hours, and then the beaker was tilted. As a result, it fluidized and spilled from the beaker and did not gel.
The other beaker was allowed to stand at 25 ° C. for 3 hours, and then the viscosity of corn soup F was measured. As a result, it was 13840 mPa · s and pH was 6.8.
〔比較例１〕
実施例７の増粘剤ａの代わりに、グアーガムを配合してフルーツソースＧを調製し、評価を行った。２５℃で３時間静置後、実施例７と同条件でフルーツソースＧの粘度を測定したところ、６９０５ｍＰａ・ｓであり、実施例７と比較すると粘性が顕著に劣っていた。またフルーツソースＧのｐＨは、３．４であった。
[Comparative Example 1]
Instead of the thickener a of Example 7, guar gum was blended to prepare a fruit sauce G and evaluated. After standing at 25 ° C. for 3 hours, the viscosity of the fruit sauce G was measured under the same conditions as in Example 7. As a result, it was 6905 mPa · s, and the viscosity was significantly inferior to Example 7. Moreover, the pH of the fruit sauce G was 3.4.
〔比較例２〕
実施例７の増粘剤ａの代わりに、水分散性乾燥物Ｃを配合してフルーツソースＨを調製し、評価を行った。２５℃で３時間静置後、フルーツソースＨの粘度を測定したところ、１４５００ｍＰａ・ｓであり、実施例７と比較すると粘性が劣っていた。またフルーツソースＨのｐＨは、３．４であった。
[Comparative Example 2]
Instead of the thickener a of Example 7, a water dispersible dried product C was blended to prepare a fruit sauce H, which was evaluated. When the viscosity of the fruit sauce H was measured after standing at 25 ° C. for 3 hours, it was 14500 mPa · s, which was inferior to Example 7. Moreover, the pH of the fruit sauce H was 3.4.
〔比較例３〕
実施例８のフルーツソースＡの代わりに、比較例１のフルーツソースＧを使用して、実施例８と同様の手順でソフトヨーグルトＩを調製し、評価した。
５℃で１時間調温し、更に２５℃で２時間調温した後の、ソフトヨーグルトＩの粘度は、１７００ｍＰａ・ｓであり、実施例８と比較すると粘性が劣っていた。またソフトヨーグルトＩのｐＨは、４．３であった。この時のソフトヨーグルトＩにおけるグアーガムの含有量は、０．１質量％であった。
[Comparative Example 3]
Soft yogurt I was prepared and evaluated in the same procedure as in Example 8, using the fruit source G in Comparative Example 1 instead of the fruit source A in Example 8.
After adjusting the temperature at 5 ° C. for 1 hour and further adjusting the temperature at 25 ° C. for 2 hours, the viscosity of Soft Yogurt I was 1700 mPa · s, which was inferior to that of Example 8. The pH of soft yogurt I was 4.3. At this time, the content of guar gum in the soft yogurt I was 0.1% by mass.
〔比較例４〕
実施例９のフルーツソースＡの代わりに、比較例１のフルーツソースＧを使用して、実施例９と同様の方法で、はっ酵乳飲料Ｊを調製し、評価した。５℃で２時間冷却し、更に２５℃で１時間調温した後、はっ酵乳飲料Ｊの粘度を測定したところ、１８００ｍＰ・ｓの粘度を示し、実施例９と比較すると粘性が劣っていた。またｐＨを測定したところ、４．０であった。
[Comparative Example 4]
A fermented milk drink J was prepared and evaluated in the same manner as in Example 9, using the fruit source G in Comparative Example 1 instead of the fruit source A in Example 9. After cooling at 5 ° C. for 2 hours and further adjusting the temperature at 25 ° C. for 1 hour, the viscosity of the fermented milk beverage J was measured. The viscosity was 1800 mP · s, which was inferior to Example 9. The pH was measured and found to be 4.0.
〔比較例５〕
実施例１０の増粘剤ｂの代わりに、グアーガム：キサンタンガムを４：１の質量比で混合したものを配合し、実施例１０と同様に、焼き肉のたれＫを調製し、評価を行った。
２５℃で３時間静置後、焼き肉のたれＫの粘度を測定したところ、３７０ｍＰａ・ｓと、実施例１０よりも、顕著に低い粘度を示した。また焼き肉のたれＫのｐＨは４．２であった。
[Comparative Example 5]
In place of the thickener b of Example 10, a mixture of guar gum and xanthan gum in a mass ratio of 4: 1 was blended, and a grilled meat sauce K was prepared and evaluated in the same manner as in Example 10.
After standing at 25 ° C. for 3 hours, the viscosity of the grilled meat sauce K was measured to be 370 mPa · s, which was significantly lower than that of Example 10. The pH of the grilled meat sauce K was 4.2.
〔比較例６〕
実施例１０の増粘剤ｂの代わりに、水分散性乾燥組成物Ｃを配合し、実施例１０と同様に、焼き肉のたれＬを調製し、評価を行った。２５℃で３時間静置後、焼き肉のたれＬの粘度を測定したところ、７８５ｍＰａ・ｓと、実施例１０よりも、低い粘度を示した。また焼き肉のたれＬのｐＨは４．２であった。
[Comparative Example 6]
Instead of the thickener b of Example 10, the water dispersible dry composition C was mix | blended, and the sauce L of grilled meat was prepared similarly to Example 10, and evaluation was performed. After standing at 25 ° C. for 3 hours, the viscosity of the grilled meat sauce L was measured, which was 785 mPa · s, which was lower than that of Example 10. The pH of the grilled meat sauce L was 4.2.
〔比較例７〕
実施例１１の増粘剤ｂの代わりに、グアーガム：キサンタンガムを４：１の質量比で混合したものを配合し、実施例１１と同様に、シロップ薬Ｍを調製し、評価を行った。
２５℃で３時間静置後、シロップ薬Ｍの粘度を測定したところ、１１２０ｍＰａ・ｓであり、実施例１１よりも低い粘度を示した。
[Comparative Example 7]
Instead of the thickener b of Example 11, a mixture of guar gum and xanthan gum at a mass ratio of 4: 1 was blended, and the syrup medicine M was prepared and evaluated in the same manner as in Example 11.
When the viscosity of the syrup medicine M was measured after leaving still at 25 degreeC for 3 hours, it was 1120 mPa * s and the viscosity lower than Example 11 was shown.
〔比較例８〕
実施例１１の増粘剤ｂの代わりに、水分散性乾燥組成物Ｃを配合し、実施例１１と同様に、シロップ薬Ｎを調製し、評価を行った。２５℃で３時間静置後、シロップ薬Ｎの粘度を測定したところ、２１１０ｍＰａ・ｓであり、実施例１１よりも低い粘度を示した。
[Comparative Example 8]
Instead of the thickener b of Example 11, a water-dispersible dry composition C was blended, and a syrup N was prepared and evaluated in the same manner as in Example 11. After standing at 25 ° C. for 3 hours, the viscosity of the syrup N was measured, which was 2110 mPa · s, which was lower than that of Example 11.
〔比較例９〕
実施例１２の増粘剤ａの代わりに、グアーガムを配合し、実施例１２と同様に、コーンスープＯを調製し、評価を行った。 ２５℃で３時間静置後、コーンスープＯの粘度を測定したところ、５４６０ｍＰａ・ｓであり、実施例１２よりも顕著に低い粘度を示した。またコーンスープＯのｐＨは６．８であった。
[Comparative Example 9]
Instead of the thickener a in Example 12, guar gum was blended, and corn soup O was prepared and evaluated in the same manner as in Example 12. When the viscosity of corn soup O was measured after standing at 25 ° C. for 3 hours, it was 5460 mPa · s, which was significantly lower than that of Example 12. The pH of corn soup O was 6.8.
〔比較例１０〕
実施例１２の増粘剤ａの代わりに、水分散性乾燥組成物Ｃを配合し、実施例１２と同様に、コーンスープＰを調製し、評価を行った。２５℃で３時間静置後、コーンスープＰの粘度を測定したところ、７６６０ｍＰａ・ｓであり、実施例１２よりも低い粘度を示した。またコーンスープＰのｐＨは６．８であった。
[Comparative Example 10]
Instead of the thickener a in Example 12, a water-dispersible dry composition C was blended, and corn soup P was prepared and evaluated in the same manner as in Example 12. When the viscosity of the corn soup P was measured after standing at 25 ° C. for 3 hours, it was 7660 mPa · s, which was lower than that of Example 12. The pH of corn soup P was 6.8.
本発明の微細な繊維状セルロースである水分散性セルロースと、少なくとも１種類の多糖類を含有する増粘剤は、増粘相乗効果を有し、少量で所望の増粘効果を得ることができる。つまり増粘剤の添加量を低減することが可能である。この性質は、食品分野のみならず、医薬品、化粧品等の用途においても使用が可能である。
The water-dispersible cellulose, which is the fine fibrous cellulose of the present invention, and the thickener containing at least one kind of polysaccharide have a thickening synergistic effect, and a desired thickening effect can be obtained with a small amount. . That is, the amount of thickener added can be reduced. This property can be used not only in the food field but also in applications such as pharmaceuticals and cosmetics.
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| JP2004352169A JP2008048602A (en) | 2004-12-06 | 2004-12-06 | Thickening agent comprising water-dispersible cellulose and at least one kind of polysaccharide |
| TW094143028A TWI306017B (en) | 2004-12-06 | 2005-12-06 | Composition composed of highly dispersible cellulose complex and polysaccharide |
| EP05814199A EP1839499A4 (en) | 2004-12-06 | 2005-12-06 | Composition composed of highly dispersible cellulose complex and polysaccharide |
| PCT/JP2005/022359 WO2006062089A1 (en) | 2004-12-06 | 2005-12-06 | Composition composed of highly dispersible cellulose complex and polysaccharide |
| CNA2005800461628A CN101098632A (en) | 2004-12-06 | 2005-12-06 | Composition composed of highly dispersible cellulose complex and polysaccharide |
| US11/808,115 US20080107789A1 (en) | 2004-12-06 | 2007-06-06 | Composition composed of highly dispersible cellulose complex and polysaccharide |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11253114A (en) * | 1998-01-09 | 1999-09-21 | Asahi Chem Ind Co Ltd | Microcellulose-containing complex |
| JP2000041627A (en) * | 1998-07-30 | 2000-02-15 | Asahi Chem Ind Co Ltd | Food composition containing plural dispersible cellulose composite materials |
| JP2000178377A (en) * | 1998-12-16 | 2000-06-27 | Asahi Chem Ind Co Ltd | Cellulose composite powder |
| JP2000312572A (en) * | 1999-04-30 | 2000-11-14 | Dai Ichi Kogyo Seiyaku Co Ltd | Precipitation-preventing agent for protein beverage |
| JP3247391B2 (en) * | 1996-07-15 | 2002-01-15 | ロディア シミ | Replenishment of essentially amorphous cellulose nanofibrils with high degree of substitution of carboxycellulose |
| JP2003135030A (en) * | 2001-11-02 | 2003-05-13 | Asahi Kasei Corp | Food product composition compounded fine cellulose- containing complex |
| JP2004041119A (en) * | 2002-07-12 | 2004-02-12 | Asahi Kasei Chemicals Corp | Water-dispersible cellulose and method for producing the same |
| JP2004248536A (en) * | 2003-02-18 | 2004-09-09 | Asahi Kasei Chemicals Corp | Heat-resistant gel |
| JP2004283135A (en) * | 2003-03-25 | 2004-10-14 | Asahi Kasei Chemicals Corp | Gel-form composition |
| JP2004313058A (en) * | 2003-04-15 | 2004-11-11 | Asahi Kasei Chemicals Corp | Edible spongy gel |
-
2004
- 2004-12-06 JP JP2004352169A patent/JP2008048602A/en active Pending
-
2005
- 2005-12-06 CN CNA2005800461628A patent/CN101098632A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3247391B2 (en) * | 1996-07-15 | 2002-01-15 | ロディア シミ | Replenishment of essentially amorphous cellulose nanofibrils with high degree of substitution of carboxycellulose |
| JPH11253114A (en) * | 1998-01-09 | 1999-09-21 | Asahi Chem Ind Co Ltd | Microcellulose-containing complex |
| JP2000041627A (en) * | 1998-07-30 | 2000-02-15 | Asahi Chem Ind Co Ltd | Food composition containing plural dispersible cellulose composite materials |
| JP2000178377A (en) * | 1998-12-16 | 2000-06-27 | Asahi Chem Ind Co Ltd | Cellulose composite powder |
| JP2000312572A (en) * | 1999-04-30 | 2000-11-14 | Dai Ichi Kogyo Seiyaku Co Ltd | Precipitation-preventing agent for protein beverage |
| JP2003135030A (en) * | 2001-11-02 | 2003-05-13 | Asahi Kasei Corp | Food product composition compounded fine cellulose- containing complex |
| JP2004041119A (en) * | 2002-07-12 | 2004-02-12 | Asahi Kasei Chemicals Corp | Water-dispersible cellulose and method for producing the same |
| JP2004248536A (en) * | 2003-02-18 | 2004-09-09 | Asahi Kasei Chemicals Corp | Heat-resistant gel |
| JP2004283135A (en) * | 2003-03-25 | 2004-10-14 | Asahi Kasei Chemicals Corp | Gel-form composition |
| JP2004313058A (en) * | 2003-04-15 | 2004-11-11 | Asahi Kasei Chemicals Corp | Edible spongy gel |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010104307A (en) * | 2008-10-31 | 2010-05-13 | House Foods Corp | Viscose fluid food |
| US9181653B2 (en) | 2009-02-13 | 2015-11-10 | Upm-Kymmene Oyj | Method for producing modified cellulose |
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| JP2014018087A (en) * | 2012-07-12 | 2014-02-03 | Lotte Co Ltd | Edible composition having improved flavor persistence |
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