JP2013074852A - Alcoholic suspended beverage - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alcoholic suspended beverage that contains water-insoluble components of a lactic-acid bacterium and fruit or the like and shows a stable dispersed state and suspended state, particularly has a long-term stability and an excellent flavor in an acidic environment.SOLUTION: The alcoholic suspended beverage contains a cellulose composite containing cellulose and hydrophilic gum, wherein a storage modulus (G') in a water dispersion having pH 4 containing 1 mass% of the cellulose composite is 0.06 Pa or more.

Description

  The present invention relates to an alcoholic suspension beverage containing a water-insoluble component such as lactic acid bacteria and fruits and exhibiting a stable dispersed state and suspended state. In particular, the present invention relates to an alcoholic suspension beverage that is acidic and has long-term stability and good flavor.

  In recent years, consumer preferences have diversified, and a wide variety of alcoholic beverages have been developed and distributed in the market. Recently, there is a demand for alcoholic suspension drinks in which citrus fruits or the like are suspended, lactic acid bacteria are suspended like makgeolli, or health ingredients such as turmeric are suspended. In particular, many seasonings have been developed for seasoning, and it is required to achieve suspension stability in acidic alcoholic beverages.

  Conventionally, attempts to increase suspension stability in alcoholic beverages include the following.

  Patent Document 1 discloses a cream liquor composition containing a specific sucrose ester as an alcohol, water, fat, saccharide, and emulsion stabilizer. According to this document, this cream liquor composition is an emulsion that is stable and does not separate even when turbid in coffee or acidic beverages of low pH such as carbonated water (in the examples, pH is disclosed as 4.6). Is described. According to this document, in alcoholic beverages, fats are covered with a specific sucrose ester and emulsified to obtain an alcoholic beverage with high suspension stability even under acidic conditions.

  Patent Document 2 discloses an alcoholic beverage containing fine cellulose having a specific particle size. This document discloses a compound having excellent dispersion, suspension stability, and emulsion stability of fruit components such as tomatoes and oranges, milk components and the like by blending fine cellulose having a specific particle size.

  Patent Document 3 discloses a dry composition having a specific particle size by mixing fine cellulose and sodium carboxymethyl cellulose having a specific substitution degree and viscosity. In this document, the above-mentioned fine cellulose composition is excellent in dispersion stability and emulsion stability in an acidic region in an aqueous beverage not containing alcohol such as orange juice and drink yogurt.

Japanese Patent Laid-Open No. 5-219885 JP-A-8-173135 Japanese Patent Laid-Open No. 9-3243

However, in patent document 1, it is necessary to mix | blend a surfactant with a large amount in a drink, and since surfactant included not only fats but a taste component, there existed a problem of masking a flavor. .
Moreover, in the fine cellulose disclosed in Patent Document 2, as shown in the Examples of the document, although it is excellent in stability for several days after preparing a beverage, in long-term storage for several weeks to several months, There was a problem that separation and aggregation occurred and stability could not be maintained.
Although the fine cellulose composition disclosed in Patent Document 3 is suitable for an aqueous beverage, there is a problem that dispersibility is insufficient in an alcoholic beverage. In addition, when pre-dispersed in an aqueous medium and added to alcohol in a completely dispersed state, suspension stability is achieved for several days, but in long-term storage, separation and aggregation occur, resulting in stability. There was a problem that could not be maintained.

Conventional cellulose composites composed of cellulose and hydrophilic gum (also synonymous with fine cellulose composition), when dispersed in alcoholic beverages, their own dispersion stability is insufficient, fruit components, It was easy to cause aggregation and separation with water-insoluble components such as lactic acid bacteria, and long-term storage stability could not be achieved.
Therefore, as in the present invention, by blending a cellulose composite having specific rheological properties (storage modulus), water-insoluble components such as lactic acid bacteria and fruits can be dispersed and suspended for a long time. Suspension beverages, particularly alcoholic suspension beverages that combine stability and good flavor in acidity have not been known.

  It is an object of the present invention to provide an alcoholic suspension beverage exhibiting a stable dispersed state and a suspended state, in particular, an alcoholic suspension beverage that has long-term stability and good flavor in an acidic state. To do.

  Here, the definitions of dispersion stability and suspension stability in the present specification will be described.

  “Dispersion stability” means the dispersion stability of the cellulose composite itself when the cellulose composite is dispersed in an aqueous medium. Specifically, there is no occurrence of separation, aggregation, sedimentation, or the like of cellulose particles, and a uniform appearance is exhibited.

  “Suspension stability” means that when an aqueous medium contains components other than cellulose composites such as fruit ingredients, functional food materials such as lactic acid bacteria and turmeric, the components are It means that the suspension is stabilized. Specifically, not only cellulose but also other particles are not separated, aggregated, settled, etc., and a uniform appearance is exhibited.

  The inventors of the present invention have developed a cellulose complex in which cellulose and a hydrophilic gum are highly complexed to increase the storage elastic modulus (G ′). The inventors found that the suspension stability was excellent, and reached the present invention.

  Furthermore, when kneading cellulose and a hydrophilic gum, the present inventors kneaded with a high kneading energy in a semi-solid state where the viscosity of the kneaded material is high as a solid content of a specific concentration or higher, thereby kneading energy. Is easily transmitted to the kneaded product, and as a result, the composite of cellulose and hydrophilic gum proceeds, and the storage elastic modulus (G ′) of the obtained cellulose composite can be increased. The cellulose composite is an acidic alcohol. It has been found for the first time that it exhibits high stability even in a sexual suspension beverage.

That is, the present invention is as follows.
(1) A cellulose composite containing cellulose and a hydrophilic gum, wherein the storage elastic modulus (G ′) is 0.06 Pa or more in a pH 4 aqueous dispersion containing 1% by mass of the cellulose composite. An alcoholic suspension beverage containing
(2) The alcoholic suspension beverage according to (1), wherein the cellulose composite contains 50 to 99% by mass of cellulose and 1 to 50% by mass of hydrophilic gum.
(3) The alcoholic suspension beverage according to (1) or (2), wherein the hydrophilic gum is psyllium seed gum.
(4) The cellulose composite further includes a water-soluble gum different from the hydrophilic gum, and the mass ratio of the hydrophilic gum to the water-soluble gum is 30/70 to 99/1. (1) The alcoholic suspension beverage according to any one of to (3).
(5) The alcoholic suspension beverage according to (4), wherein the water-soluble gum is at least one selected from the group consisting of sodium carboxymethylcellulose, LM pectin, sodium alginate, and gellan gum.
(6) Alcoholic suspension drink as described in any one of (1)-(5) whose pH is 6 or less.

  The present invention blends a low-viscosity cellulose composite with excellent dispersion stability and suspension stability into an alcoholic beverage, so that the alcoholic suspension has excellent suspension stability and good flavor over a long period of time. Beverages can be provided. Furthermore, when water-insoluble components such as functional food materials such as turmeric are added to these foods and drinks, their separation, aggregation, sedimentation, etc. are suppressed, exhibiting a uniform appearance, and excellent suspension stability. Alcoholic suspension beverages can be provided.

It is a distortion-stress curve obtained by the measurement of viscoelasticity about the water dispersion in 1 mass% of the cellulose composite A (refer Example 1). It is a distortion-stress curve obtained by the measurement of viscoelasticity about the water dispersion in 1 mass% of the cellulose composite L (refer the comparative example 3). It is the image observed with the atomic force microscope (AFM) about the water dispersion (ion-exchange water, neutrality) of the cellulose composite A (refer Example 1). It is the image observed with the atomic force microscope (AFM) about the aqueous dispersion (pH 4) of the cellulose composite A (refer Example 1).

  The present invention will be specifically described below.

The cellulose composite used in the present invention is a cellulose composite containing cellulose and a hydrophilic gum, and a storage elastic modulus (G ′) is 0.06 Pa in an aqueous dispersion of pH 4 containing 1% by mass of the cellulose composite. That's what it is. The term “complexing” as used in the present invention means that the surface of cellulose is coated with a hydrophilic gum by chemical bonds such as hydrogen bonds.
<Cellulose>
In the present invention, “cellulose” is a naturally derived water-insoluble fibrous material containing cellulose. Examples of raw materials include wood, bamboo, wheat straw, rice straw, cotton, ramie, bagasse, kenaf, beet, squirts, and bacterial cellulose. Even if one kind of natural cellulosic material is used as a raw material, a mixture of two or more kinds can be used.

  The average degree of polymerization of crystalline cellulose (MCC) used in the present invention is preferably crystalline cellulose of 500 or less. The average degree of polymerization can be measured by a reduced specific viscosity method using a copper ethylenediamine solution specified in the crystalline cellulose confirmation test (3) of “14th revised Japanese pharmacopoeia” (published by Yodogawa Shoten). If the average degree of polymerization is 500 or less, the cellulosic substance is preferably subjected to physical treatment such as stirring, pulverization, and grinding in the step of compounding with the hydrophilic gum, and the compounding is facilitated, which is preferable. More preferably, the average degree of polymerization is 300 or less, and still more preferably, the average degree of polymerization is 250 or less. The lower the average degree of polymerization, the easier the control of complexing. Therefore, the lower limit is not particularly limited, but a preferred range is 10 or more.

  Examples of a method for controlling the average degree of polymerization include hydrolysis treatment. By the hydrolysis treatment, the depolymerization of the amorphous cellulose inside the cellulose fiber proceeds, and the average degree of polymerization decreases. At the same time, in addition to the above-mentioned amorphous cellulose, impurities such as hemicellulose and lignin are removed by the hydrolysis treatment, so that the inside of the fiber becomes porous. Thereby, in the step of imparting mechanical shearing force to cellulose and the hydrophilic gum in the kneading step or the like, the cellulose is easily subjected to mechanical treatment, and the cellulose is easily refined. As a result, the surface area of the cellulose is increased, and the control of complexing with the hydrophilic gum is facilitated.

  The method for hydrolysis is not particularly limited, and examples thereof include acid hydrolysis, hydrothermal decomposition, steam explosion, and microwave decomposition. These methods may be used alone or in combination of two or more. In the acid hydrolysis method, an average polymerization is easily carried out by adding an appropriate amount of a protonic acid, a carboxylic acid, a Lewis acid, a heteropolyacid, and the like while stirring the cellulose-based substance in an aqueous medium, and heating while stirring. You can control the degree. The reaction conditions such as temperature, pressure, and time at this time vary depending on the cellulose species, cellulose concentration, acid species, and acid concentration, but are appropriately adjusted so as to achieve the desired average degree of polymerization. For example, the conditions of processing a cellulose for 10 minutes or more under 100 degreeC or more and pressurization using the mineral acid aqueous solution of 2 mass% or less are mentioned. Under these conditions, a catalyst component such as an acid penetrates into the inside of the cellulose fiber, the hydrolysis is accelerated, the amount of the catalyst component to be used is reduced, and subsequent purification is facilitated.

  The cellulose in the cellulose composite in the present invention preferably has a fine particle shape. As for the particle shape of cellulose, the cellulose composite in the present invention is made into a pure water suspension at a concentration of 1% by mass and treated with a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”): A water dispersion dispersed at a rotational speed of 15,000 rpm × 5 minutes) is diluted with pure water to 0.1 to 0.5% by mass, cast on mica, and air-dried. 100 particles represented by the ratio (L / D) of the major axis (L) and minor axis (D) of the particle image obtained when measured with a microscope (SEM) or atomic force microscope (AFM) Calculated as an average of ~ 150 particles.

L / D is preferably less than 20, more preferably 15 or less, further preferably 10 or less, particularly preferably 5 or less, particularly preferably less than 5, and most preferably 4 or less.
<Hydrophilic gum>
The hydrophilic gum is a hydrophilic polymer substance containing sugar or polysaccharide as part of its chemical structure. Here, the hydrophilic property means that a part of the material is dissolved in pure water at room temperature. When the hydrophilicity is quantitatively defined, 0.05 g of this new aqueous gum is dissolved in 50 mL of pure water under stirring (stirrer chip) until equilibrium and processed with a membrane filter having an opening of 1 μm. The component to be contained is contained in the hydrophilic gum in an amount of 1% by mass or more. In the case where a polysaccharide is used as the hydrophilic gum, the following are suitable.

For example, psyllium seed gum (PSG), locust bean gum, guar gum, tamarind seed gum, karaya gum, chitosan, gum arabic, gati gum, tragacanth gum, agar, carrageenan, alginic acid, sodium alginate, calcium alginate, HM pectin, LM pectin, azotobacter Examples include cellulose derivatives such as vinelansy gum, xanthan gum, curdlan, pullulan, dextran, gellan gum, gelatin, sodium carboxymethylcellulose, carboxymethylcellulose calcium, methylcellulose, hydroxypropylcellulose, and hydroxyethylcellulose. Two or more of these hydrophilic gums may be combined.
<Anionic polysaccharide>
Among the above-mentioned hydrophilic gums, those that release cations in water and become anions themselves are called anionic polysaccharides. It is preferable to use an anionic polysaccharide as the hydrophilic gum, since the complexing with cellulose is further promoted, and the acid resistance and salt resistance of the cellulose composite are increased.

  The following are preferable as the anionic polysaccharide.

Examples thereof include cellulose derivatives such as psyllium seed gum (PSG), karaya gum, carrageenan, alginic acid, sodium alginate, calcium alginate, HM pectin, LM pectin, azotobacter vinelandie gum, xanthan gum, gellan gum, sodium carboxymethylcellulose, carboxymethylcellulose calcium and the like. These anionic polysaccharides may be used in combination of two or more.
<Branched anionic polysaccharide>
Among the above-mentioned anionic polysaccharides, those having a branched structure in the chemical structure are called branched anionic polysaccharides. It is preferable to use a branched anionic polysaccharide as the hydrophilic gum in the cellulose composite in the present invention because the acid resistance of the cellulose composite is further increased. The branched structure here means that one or more of the three hydroxyl groups (C6-position is a primary alcohol) in the hexasaccharide contained in the polysaccharide is substituted with a higher molecular weight substituent than methylol through a chemical bond. It is the structure that is done. The substituent is preferably a sugar or polysaccharide structure via an ether bond. The following are preferred as the branched anionic polysaccharide.

  Examples thereof include psyllium seed gum (PSG), karaya gum, xanthan gum, and gellan gum. These anionic polysaccharides may be used in combination of two or more.

Among these branched anionic polysaccharides, psyllium seed gum (PSG) is particularly preferable because it improves the dispersion stability and suspension stability of the cellulose composite when it is combined with cellulose.
<Psyllium seed gum>
Psyllium seed gum (PSG) is a polysaccharide (gum) obtained from the seed coat of a plant of the plantain family (Plantago ovata Forskal). Specific examples include polysaccharides obtained from Isagor and plantago / Obata seed coats.

  The psyllium seed gum (PSG) of the present invention contains a contaminant as long as it contains a polysaccharide (gum) obtained from the seed coat of the plant of the above plant family (Plantago ovata Forskal). Also applies. For example, a gum obtained by extracting the polysaccharide with a solvent such as water, a husk whose outer skin has been pulverized, a combination of them, and any of them are included. In addition, they may be in any state of powder, lump, cake, or liquid.

  The chemical structure of PSG is a structure in which the main chain is highly branched as xylan in the non-cellulose polysaccharide and the side chain is composed of arabinose, xylose, galacturonic acid, and rhamnose. The sugar composition ratio in the side chain is about 60% by mass of D-xylose, about 20% by mass of L-arabinose, about 10% by mass of L-rhamnose, and about 10% by mass of D-galacturonic acid. These mass ratios are about 5% by mass depending on the PSG raw material and the manufacturing process of PSG.

  Moreover, if it has the above-mentioned structure, in order to adjust a viscosity, you may hydrolyze PSG with an acid, an enzyme like a xylanase, etc.

PSG preferably has a viscosity of 200 mPa · s or less measured with a 1% by mass pure aqueous solution. Here, the viscosity refers to a viscometer (TVB-10 type viscometer manufactured by Toki Sangyo Co., Ltd.) after filling a 200 ml beaker with an aqueous solution prepared to 1% by mass in pure water and adjusting the temperature to 25 ° C. The measured value immediately after rotating the rotor at 60 rpm for 30 seconds is used (however, the rotor can be appropriately changed depending on the viscosity. The rotor used is as follows. 1 to 20 mPa · s: BL type) 21-100 mPa · s: No1, 101-300 mPa · s: No2, 301 mPa · s: No3). The lower the viscosity, the more easily the complexing with cellulose is facilitated. Moreover, since it becomes easy to express a refreshing throat when used for a drink, it is preferable. More preferably, it is 100 mPa * s or less, More preferably, it is 50 mPa * s or less. The lower limit is not particularly set, but the range obtained as an industrial raw material is preferably 5 mPa · s or more.
<Storage modulus>
Next, the storage elastic modulus (G ′) of the cellulose composite in the present invention will be described.

  In the cellulose composite of the present invention, the storage elastic modulus (G ′) of an aqueous dispersion having a pH of 4 and containing 1% by mass of the cellulose composite is 0.06 Pa or more. The storage elastic modulus represents the rheological elasticity of the aqueous dispersion, and represents the degree of complexation of cellulose and hydrophilic gum, or of cellulose, hydrophilic gum and other water-soluble gums. Is. The higher the storage elastic modulus, the more complex the cellulose and hydrophilic gum, or the cellulose and the hydrophilic gum and other water-soluble gums, and the more rigid the network structure in the aqueous dispersion of the cellulose complex. It means that there is. The more rigid the network structure, the better the dispersion stability and suspension stability of the cellulose composite.

  Conventional cellulose has low storage elastic modulus in acidity, and extremely low dispersion stability and suspension stability. However, the cellulose composite in the present invention exhibits a high storage elastic modulus even in acidity, and is excellent in dispersion stability and suspension stability.

  In the present invention, the storage elastic modulus is a value obtained by dynamic viscoelasticity measurement of an aqueous dispersion in which a cellulose composite is dispersed in an aqueous medium having a pH of 4. An elastic component that holds the stress stored in the cellulose composite network structure when the aqueous dispersion is distorted appears as a storage elastic modulus.

  As a method for measuring the storage elastic modulus, first, a cellulose composite is subjected to a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7” treatment condition: 15,000 rpm × 5 minutes). And dispersed in pure water to prepare a 1.8% by mass pure water dispersion. The aqueous dispersion was mixed with 0.2 M Mclvaine buffer (0.2 M disodium hydrogen phosphate and 0.1 M citric acid aqueous solution) at a pH of 4 to adjust the concentration of the cellulose complex to 1 mass. % (Total amount 300 g, ion concentration 0.06 mol / l, pH 4), and the resulting aqueous dispersion is allowed to stand at room temperature for 3 days. The strain dependence of the stress of this water dispersion was measured using a viscoelasticity measuring device (Rheometric Scientific, Inc., ARES100FRTN1 type, geometry: Double Wall Couette type, temperature: constant 25.0 ° C., angular velocity: 20 rad / sec, strain: Sweeping within the range of 1 → 794%, the aqueous dispersion is slowly charged using a dropper so as not to break the fine structure, and after standing for 5 minutes, measurement is started in the Dynamic Strain mode). The storage elastic modulus in the present invention is a value of 20% strain on the strain-stress curve obtained by the above measurement. The larger the value of the storage elastic modulus, the more elastic the structure of the aqueous dispersion formed by the cellulose composite, indicating that cellulose, hydrophilic gum, and other water-soluble gum are highly complexed. Yes.

  The storage elastic modulus of the cellulose composite is preferably 0.15 or more, more preferably 0.2 Pa or more, and further preferably 0.5 Pa or more.

The upper limit is not particularly set, but it is 6.0 Pa or less in consideration of ease of drinking when it is used as a beverage. When it is 6.0 Pa or less, the amount of the mouthpiece is light at the addition amount of the cellulose composite that can sufficiently obtain the suspension stability (depending on the beverage, for example, 0.1 to 1.0% by mass for the fruit juice beverage). Therefore, it is preferable. Moreover, even if the addition amount of the cellulose composite is low (for example, 0.5% by mass or less) in order to adjust the texture, it is difficult to cause aggregation or the like with water-insoluble components other than cellulose.
<Structure of cellulose composite>
The cellulose composite in the present invention is characterized in that the spread of the hydrophilic gum extending radially from the cellulose surface is sufficiently large even under acidic conditions. The larger the spread of the hydrophilic gum extending from the cellulose surface, the easier it becomes to entangle with the hydrophilic gum of the adjacent cellulose composite. As a result, the entanglement between the cellulose composites occurs densely, the network structure becomes rigid, the storage elastic modulus (G ′) is improved, and the dispersion stability and suspension stability are increased. The spread of the hydrophilic gum can be measured by the following method.

  First, the cellulose composite was put into pure water using a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7” treatment condition: 15,000 rpm × 5 minutes, total amount 300 g). Disperse to prepare a 1.0% by mass pure water dispersion. The aqueous dispersion is mixed with McClvaine buffer (0.2 M disodium hydrogen phosphate and 0.1 M citric acid aqueous solution) at 0.2 M and pH 3.5 to adjust the concentration of the cellulose complex. After adjusting to 0.5 mass% (ion concentration 0.06 mol / l, pH 4.0), the concentration of the cellulose composite is diluted to 0.1 mass% with pure water. The obtained aqueous dispersion is allowed to stand at room temperature for 3 days or more. Slowly suck out 5 μl using a dropper so as not to break the fine structure of the water dispersion, slowly drop it onto the 1 cm × 1 cm wall-opened mica, and blow off excess water with an air duster. The sample fixed on the surface is observed with an AFM (using a scanning probe microscope SPM-9700, manufactured by Shimadzu Corporation, phase mode, Olympus probe OMCL-AC240TS). In this observed image, the cellulose particles are observed as rod-like particles having a height of 2 nm or more, and a hydrophilic gum having a height of less than 2 nm extending radially from the cellulose particles to the periphery can be observed.

It is preferable to use a branched anionic polysaccharide as the hydrophilic gum because this spread becomes larger and a dense (web-like) network structure is formed with that of adjacent particles. Moreover, it is preferable to use psyllium seed gum as the hydrophilic gum because this spread becomes larger and the network structure becomes dense.
<Combination ratio of cellulose and hydrophilic gum>
The cellulose composite in the present invention preferably contains 50 to 99% by mass of cellulose and 1 to 50% by mass of hydrophilic gum.

  As a result of the complexing, the hydrophilic gum coats the surface of the cellulose particles with chemical bonds such as hydrogen bonds, so that when dispersed in an acidic aqueous solution, the dispersion stability and suspension stability of the cellulose composite are improved. .

In addition, by making cellulose and hydrophilic gum into the above composition, compounding is promoted, suspension stability and dispersion stability in an acidic water dispersion are improved, and water-insoluble components such as functional food materials The effect of preventing sedimentation can be achieved.
<Water-soluble gum>
The cellulose composite in the present invention preferably further contains a water-soluble gum other than the hydrophilic gum. The water-soluble gum is preferably a gum that has high water swellability and is easily complexed with cellulose.

  For example, locust bean gum, guar gum, tamarind seed gum, caraya gum, chitosan, gum arabic, agar, carrageenan, alginic acid, sodium alginate (hereinafter referred to as “ARG-Na”), HM pectin, LM pectin (hereinafter referred to as “LMP”). ), Azotobacter vinelanzie gum, xanthan gum, curdlan, pullulan, dextran, gellan gum (hereinafter referred to as “GLG”), gelatin, sodium carboxymethylcellulose (hereinafter referred to as “CMC-Na”), carboxymethylcellulose calcium, methylcellulose, hydroxypropylcellulose And cellulose derivatives such as hydroxyethyl cellulose. Two or more of these water-soluble gums may be combined.

  Among the above-mentioned water-soluble gums, one or more selected from CMC-Na, LMP, ARG-Na, and GLG are preferable. These gums are preferable because they are easily combined with cellulose and hydrophilic gum.

  “CMC-Na” is one in which the hydroxyl group of cellulose is substituted with monochloroacetic acid and has a linear chemical structure in which D-glucose is linked by β-1,4. CMC-Na is obtained by dissolving pulp (cellulose) with a sodium hydroxide solution and etherifying with monochloro acid (or its sodium salt).

  In particular, it is preferable from the viewpoint of complexing to use CMC-Na having a substitution degree and a viscosity adjusted within a specific range. The degree of substitution is the degree to which a carboxymethyl group is ether-bonded to a hydroxyl group in cellulose, and is preferably 0.6 to 2.0. If the degree of substitution is in the above range, it is preferable because the dispersibility of CMC-Na is sufficient and the production is easy. More preferably, the substitution degree is 0.6 to 1.3. The viscosity of CMC-Na is preferably 500 mPa · s or less, more preferably 200 mPa · s or less, and further preferably 50 mPa · s or less in a 1% by mass pure aqueous solution. Particularly preferably, it is 20 mPa · s or less. The lower the viscosity of CMC-Na, the easier the complexing with cellulose and hydrophilic gum is promoted, and the lower limit is not particularly set, but the preferred range is 1 mPa · s or more.

  “LMP” refers to a structure having an acidic polysaccharide (gum) mainly composed of galacturonic acid and several neutral sugars. What has this chemical structure corresponds to LMP in this invention irrespective of a raw material and a manufacturing method. Pectin binds to cellulose and the like in plant tissues and exists as an insoluble component in water, and thus can be obtained by separating it from protopectin together with other soluble components under high temperature acidity. LMP exists in the above-mentioned galacturonic acid in two forms, a methyl ester form and an acid, but the degree of esterification (the ratio of galacturonic acid present in the ester form) is less than 50%. From the viewpoint of complexing with a hydrophilic gum.

  “ARG-Na” is a structure in which α-L-glucuronic acid and β-D-mannuronic acid have a pyranose-type 1,4-glycosidically bonded structure. Regardless of the production method, it corresponds to ARG-Na in the present invention. ARG-Na is a kind of polysaccharide mainly contained in brown algae represented by seaweed, kombu, and hijiki.

  Industrially, alginic acid is obtained from raw algae such as Lessonia, Macrocystis, Kajime, Davilia, Ascophilum, etc., which have a high alginate content. Algaic acid is obtained by acid-treating the pulverized raw algae and extracting the pulverized one by acid treatment and filtering the resulting precipitate. This alginic acid is sodiumated with sodium carbonate or the like, dried and pulverized to obtain powdered sodium alginate.

  The ARG-Na aqueous solution is neutral and exhibits a smooth viscosity. The viscosity of ARG-Na is preferably 300 mPa · s or less in a 1% by mass pure aqueous solution. More preferably, the viscosity is 100 mPa · s or less. More preferably, the viscosity is 30 mPa · s or less. The lower the viscosity, the more easily the complexing with cellulose and hydrophilic gum is facilitated.

  “GLG” is a product obtained by deacetylating a microbial polysaccharide produced outside the cell by a microorganism called Sphingomo elodea. GLG is a linear heteropolysaccharide, is composed of glucose, glucuronic acid, four sugar repeating units of glucose and L-rhamnose, and has a glucuronic acid-derived carboxyl group. There are two types of GLG, deacylated type and native type, and the difference is the presence or absence of acetyl group and glyceryl group present in 1-3 linked glucose. The deacyl type is obtained by removing the acetyl group and glyceryl group. In the native type, 1 residue of glyceryl group and an average of 1/2 residue of acetyl group are bonded to a glucose residue. In the present invention, both the deacylated type and the native type can be used. However, the deacylated type is preferable because it has the above-described structure, so that complexation with cellulose and hydrophilic gum is facilitated.

Among the above, it is more preferable to use CMC-Na or LMP. From the viewpoint of complexing, CMC-Na is most preferable.
<Mass ratio of hydrophilic gum and water-soluble gum>
The mass ratio between the hydrophilic gum and the water-soluble gum is preferably 30/70 to 99/1. The cellulose composite in the present invention includes the cellulose composite in the present invention in a wide pH range from weakly alkaline (pH 8) to acidic (pH 3) because the hydrophilic gum and the water-soluble gum are in the above range. In the aqueous dispersion, the cellulose composite in the present invention exhibits dispersion stability and suspension stability. In addition, by adding a water-soluble gum to the cellulose composite in the present invention, the suspension stability of the cellulose composite in the present invention in the acidic region (pH 5 or less) of the aqueous dispersion is particularly excellent. . As a compounding quantity ratio of these hydrophilic gums and water-soluble gums, More preferably, it is 40 / 60-90 / 10, More preferably, it is 40 / 60-80 / 20.
<Volume average particle diameter of cellulose composite>
The volume average particle size of the cellulose composite is preferably 20 μm or less. Here, the volume average particle size was determined by treating the cellulose composite with a pure water suspension at a concentration of 1% by mass, and treating with a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”). : Volume obtained by dispersion at a rotational speed of 15,000 rpm × 5 minutes) and laser diffraction (manufactured by Horiba, Ltd., trade name “LA-910”, ultrasonic treatment for 1 minute, refractive index 1.20) It is the cumulative 50% particle size in the frequency particle size distribution.

  Moreover, it is preferable that a cellulose composite consists of cellulose composite fine particles with a volume average particle diameter of 0.01-200 micrometers. What was manufactured as a dry powder has aggregated these microparticles | fine-particles and formed the secondary aggregate with an apparent weight average particle diameter of 10-250 micrometers. This secondary aggregate is disintegrated when stirred in water and dispersed in the above-mentioned cellulose composite fine particles. This apparent weight average particle diameter was obtained by sieving 10 g of a sample for 10 minutes using a low-tap type sieve shaker (Sieve Shaker A type manufactured by Hira Kogakusho) or a JIS standard sieve (Z8801-1987). The cumulative weight is 50% particle size in the particle size distribution. The weight-average particle diameter of the secondary aggregate of the cellulose composite after drying and the volume-average particle diameter of the cellulose composite in the dispersion by laser diffraction were completely different in measurement principle, and thus were obtained respectively. The values are not necessarily correlated.

When the volume average particle size of the cellulose composite is 20 μm or less, the dispersion stability and suspension stability of the cellulose composite are more easily improved. In addition, when a food containing a cellulose composite is eaten, a smooth texture with no roughness can be provided. More preferably, the volume average particle diameter is 15 μm or less, particularly preferably 10 μm or less, and further preferably 8 μm or less. Since the dispersion stability and suspension stability of the cellulose composite are more easily improved as the volume average particle size is smaller, the lower limit is not particularly limited, but a preferable range is 0.1 μm or more.
<Amount of colloidal component of cellulose composite>
Furthermore, the cellulose composite preferably contains 30% by mass or more of the colloidal cellulose component. The content of the colloidal cellulose component as used herein means that the cellulose composite is made into a pure water suspension at a concentration of 1% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”). “Processing conditions: Dispersed at 15,000 rpm × 5 minutes) and centrifuged (trade name“ 6800 type centrifuge ”, rotor type RA-400, manufactured by Kubota Corporation), processing conditions: centrifugal force 2, 000 rpm (5600 G * G is gravitational acceleration) × 15 minutes) and is a mass percentage of solid content (including cellulose, hydrophilic gum, and water-soluble gum) remaining in the supernatant after centrifugation. The size of the colloidal cellulose component is 10 μm or less, more preferably 5.0 μm or less, and particularly preferably 1.0 μm or less. The size here refers to a cellulose composite made into a pure water suspension at a concentration of 1% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”). 15,000 rpm × 5 minutes), volume frequency particle size distribution obtained by laser diffraction method (manufactured by Horiba, Ltd., trade name “LA-910”, ultrasonic treatment 1 minute, refractive index 1.20) This is the 50% cumulative particle diameter (volume average particle diameter). When the content of the colloidal cellulose component is 30% by mass or more, the dispersion stability and the suspension stability are more easily improved. More preferably, it is 40 mass% or more, Most preferably, it is 50 mass% or more. The greater the colloidal cellulose component content, the higher the dispersion stability. Therefore, the upper limit is not particularly limited, but a preferred range is 100% by mass or less.
<Hydrophilic substance>
In addition to the hydrophilic gum and the water-soluble gum, a hydrophilic substance may be further added to the cellulose composite in the present invention for the purpose of enhancing the dispersibility in water. A hydrophilic substance is an organic substance that is highly soluble in cold water and hardly causes viscosity. Hydrophilic polysaccharides such as starch hydrolysates, dextrins, indigestible dextrin, polydextrose, fructooligosaccharides, galactooligosaccharides , Maltooligosaccharides, isomaltooligosaccharides, lactose, maltose, sucrose, oligosaccharides such as α-, β-, γ-cyclodextrin, monosaccharides such as glucose, fructose, sorbose, sugar alcohols such as maltitol, sorbit, erythritol Kinds etc. are suitable. Two or more kinds of these hydrophilic substances may be combined. Among the above, hydrophilic polysaccharides such as starch hydrolysates, dextrins, indigestible dextrins, and polydextrose are preferable from the viewpoint of dispersibility.

Regarding the blending of the other components, it is free to blend to such an extent that the dispersion and stability of the composition in water are not impaired.
<Method for producing cellulose composite>
Next, the manufacturing method of the cellulose composite in this invention is demonstrated.

  The cellulose composite satisfying the specific storage elastic modulus of the present invention is obtained by imparting mechanical shearing force to cellulose and hydrophilic gum in the kneading step to make the cellulose finer and to make the hydrophilic gum complex on the cellulose surface. can get. Moreover, you may add water-soluble gums other than hydrophilic gum, another additive, etc. What passed through the above-mentioned process is dried as needed. The cellulose composite in the present invention may be in any form such as an undried one and a dried one after the mechanical shear described above.

  In order to give mechanical shearing force, a kneading method using a kneader or the like can be applied. As the kneading machine, a kneader, an extruder, a planetary mixer, a reiki machine or the like can be used, and it may be a continuous type or a batch type. The temperature at the time of kneading may be a result, but when heat is generated due to a compounding reaction, friction, or the like at the time of kneading, the kneading may be performed while removing the heat. These models can be used alone, but two or more models can be used in combination. These models may be appropriately selected depending on the viscosity requirements in various applications.

  Further, the lower the kneading temperature, the better the deterioration of the hydrophilic gum is suppressed, and the resulting cellulose composite has a higher storage elastic modulus (G ′), which is preferable. The kneading temperature is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, particularly preferably 20 to 70 ° C, further preferably 20 to 60 ° C, and most preferably 20 to 50 ° C. In order to maintain the above kneading temperature under high energy, it is also free to devise slow heating such as jacket cooling and heat dissipation.

  The solid content during kneading is preferably 20% by mass or more. It is preferable to knead the kneaded material in a semi-solid state where the viscosity of the kneaded material is high, because the kneaded material does not become a shab-subber state, and the kneading energy described below is easily transmitted to the kneaded material, and the compounding is promoted. The solid content at the time of kneading is more preferably 30% by mass or more, and further preferably 40% by mass or more. The upper limit is not particularly limited, but the practical range is preferably 90% by mass or less, considering that the kneaded product does not become a crumbly state with a small amount of water and a sufficient kneading effect and a uniform kneading state can be obtained. More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less. Moreover, in order to make solid content into the said range, as a timing to add water, a required amount may be added before a kneading | mixing process, may be added in the middle of a kneading | mixing process, or both may be implemented. good.

  Here, the kneading energy will be described. The kneading energy is defined by the amount of electric power (Wh / kg) per unit mass of the kneaded product. The kneading energy is preferably 50 Wh / kg or more. If the kneading energy is 50 Wh / kg or more, the grindability imparted to the kneaded product is high, the complexing of cellulose with hydrophilic gums and other water-soluble gums is promoted, and the dispersion stability of acidic cellulose composites Suspension stability is improved. More preferably, it is 80 Wh / kg or more, More preferably, it is 100 Wh / kg or more.

  The higher the kneading energy, the more complex is considered to be promoted. However, if the kneading energy is too high, the equipment becomes industrially excessive and the equipment is overloaded. Is preferably 1000 Wh / kg.

  The degree of complexation is considered to be the proportion of hydrogen bonds between cellulose and other components. As the compounding progresses, the proportion of hydrogen bonds increases and the effect of the present invention improves. Moreover, the storage elastic modulus (G ′) of the cellulose composite increases as the composite progresses.

  In obtaining the cellulose composite in the present invention, when drying the kneaded product obtained from the above-mentioned kneading step, known methods such as shelf-type drying, spray drying, belt drying, fluidized bed drying, freeze drying, microwave drying, etc. The drying method can be used. When the kneaded product is subjected to a drying step, it is preferable that water is not added to the kneaded product, and the solid content concentration in the kneading step is maintained and the dried step is used. The moisture content of the dried cellulose composite is preferably 1 to 20% by mass. By setting the moisture content to 20% or less, problems such as stickiness and rot, and cost problems in transportation and transportation are less likely to occur. More preferably, it is 15% or less, and particularly preferably 10% or less. Moreover, by setting it as 1% or more, dispersibility does not deteriorate because of excessive drying. More preferably, it is 1.5% or more.

  When the cellulose composite is distributed in the market, it is preferable to pulverize the cellulose composite obtained by drying into a powder form because the powder is easier to handle. However, when spray drying is used as a drying method, drying and pulverization can be performed at the same time, so pulverization is not necessary. When the dried cellulose composite is pulverized, a known method such as a cutter mill, a hammer mill, a pin mill, or a jet mill can be used. The degree of pulverization is such that the pulverized product passes through a sieve having an opening of 1 mm. More preferably, it is preferable to pulverize the sieve having a mesh opening of 425 μm so that the average particle size (weight average particle size) is 10 to 250 μm.

When the dried cellulose composite is stirred in water, a stable colloidal dispersion having a smooth structure and a smooth texture in which cellulose is easily dispersed and is uniformly dispersed is formed. In particular, in an acidic state, cellulose does not cause aggregation or separation, and forms a stable colloidal dispersion, so that it exhibits an excellent function as a stabilizer or the like.
<Alcoholic suspension drink>
The alcoholic suspension beverage containing the cellulose composite of the present invention preferably contains 0.5 to 30% by mass as the ethanol concentration. Furthermore, it is preferable that it is an acidic alcoholic suspension drink whose pH is 3-6. For example, vodka, gin, rum, liqueur, tequila, whiskey, brandy, shochu, wine, beer, sake, various cocktails that contain drinking ethanol, fruit liquor obtained by brewing fruit juice, muddy liquor leaving liquor Is included in the alcoholic suspension beverage of the present invention.

  In particular, based on the above-mentioned distilled liquor and brewed liquor, fruit or vegetable components such as pulp and fiber are suspended, and further, an acidic suspension drink such as acidic chuhai with added acidity, carbonated water, etc. Alcoholic suspension drinks such as makgeolli and dobrot in which microorganisms such as lactic acid bacteria and yeast as fermentation components are suspended are preferable because the suspension function of the cellulose composite in the present invention is exhibited.

  Although the ethanol concentration depends on the type of the suspended component, it is closely related to the suspension stability, and high stability can be achieved within an appropriate range. As a more preferable ethanol concentration, it is 2-15 mass%, More preferably, it is 6-12 mass%.

The pH is also closely related to the suspension stability, although depending on the type of the suspended component, and high stability can be achieved within an appropriate range. A more preferred pH is 4-5.
As used herein, the definition of ethanol concentration and pH is defined as the ethanol concentration and pH when the food and drink of the above-described form subjected to various processes is stored for one day or more in the distribution stage, or when the food and drink are provided. Refers to that. As a measuring method of ethanol concentration and pH, after removing solid content in the above-mentioned food and drink by centrifugation and / or filtration, when containing carbon dioxide gas, after volatilizing the gas component, the alcohol meter ( It can be measured using a wine accessory creation) and a pH meter (pH meter D-50, manufactured by HORIBA).
<Addition amount of cellulose composite>
Although there is no restriction | limiting in particular as addition amount of a cellulose composite, For example, 0.01 mass% or more is preferable with respect to alcoholic suspension drink. By making the addition amount of the cellulose composite 0.01% by mass or more, dispersion and suspension stability increase, and the effect of emulsion stability and water separation prevention is excellent. More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, Especially preferably, it is 0.3 mass% or more, Most preferably, it is 0.5 mass% or more. By adding the cellulose composite in an amount of 5% by mass or less, it is preferable that the amount is 5% by mass or less from the viewpoint of ease of drinking (grooves in the throat and tongue) without causing aggregation and separation. .
<Insoluble component>
In particular, the alcoholic suspension beverage of the present invention preferably contains a water-insoluble component. The water-insoluble component is a component that does not dissolve in water, and in the present invention, means a component that passes through a 10-mm aperture sieve. More preferably, it passes through a 5 mm sieve, and more preferably passes through a 2 mm sieve. The water-insoluble component is unstable when the ethanol concentration of the alcoholic suspension beverage is high and becomes acidic, but excellent suspension stability can be obtained by adding the cellulose composite in the present invention.

  Water-insoluble components include fruits, vegetable-derived pulp, fruit scraps, vegetable juice pulp, lactic acid bacteria, yeast and other microorganisms, milk calcium, calcium carbonate, beta glucan, protein (soy protein, milk protein, collagen), Functional food materials with a higher specific gravity than water such as turmeric, litchi, etc., ubidecalenone compounds such as coenzyme Q10, omega-3 compounds such as docosahexaenoic acid, eicosapentaenoic acid, or esters thereof, and functionalities that have a lower specific gravity than water such as ceramide compounds Examples include food materials.

The insoluble component described above is preferably added in an amount of 0.01% by mass or more based on the beverage, depending on the daily intake of the beverage and the effectiveness of the material. More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more.
<Chew high with vegetable juice and / or fruit juice>
Vegetable juice and / or fruit juice chu-hi contains 10% by mass or more and 100% by mass or less of vegetable juice and / or fruit juice as components other than the cellulose complex. In the present invention, “containing 10% by mass or more of vegetable juice and fruit juice” means that the ratio of vegetable juice to the whole beverage is 10% by mass or more in straight conversion.

  Vegetable juice means vegetable juice, vegetable puree, powder obtained by drying a crushed vegetable product, or a mixture thereof. Vegetables that are generally bluish and difficult to drink are used as raw materials. For example, fruits and vegetables such as tomatoes, peppers, pumpkins, leafy vegetables such as cabbage, spinach, lettuce, parsley, watercress, kale, komatsuna, etc., root vegetables such as carrots, radish, beef bowl, asparagus as stem vegetables, Broccoli, cauliflower, etc. are mentioned as flower vegetables such as celery. Green vegetables include young barley leaves, kale, tomorrow leaves, alfalfa, morroheiya, young wheat leaves, young wheat leaves, broccoli, broccoli sprout, cabbage, komatsuna, radish leaves, radish, mizuna, mustard, watercress, cress sprout, wasabi Examples include leaves and spinach. Two or more kinds of vegetables may be used in combination. The production method and production conditions of vegetable juice are not particularly limited, and may be performed by a known method. Examples of the method for producing the juice include a method of crushing and squeezing the vegetable after blanching the vegetable, a method of squeezing the juice at a low temperature, and the like. In addition, as a puree production method, after blanching vegetables, they are lined with a pulper or finisher or crushed with a stone mortar. Moreover, the method of crushing and manufacturing finely with a mixer is mentioned.

  Fruit juice is a liquid squeezed from fruit. Fruits include citrus fruits, apples, grapes, peaches, pineapples, guava, bananas, mangoes, cassis, blueberries, acerola, prunes, papayas, passion fruits, plums, pears, apricots, litchis, melons, pears, plums, etc. Is mentioned. You may use a fruit individually or in mixture of 2 or more types.

  Citrus fruit refers to the fruit of a plant belonging to the citrus fruit family. Specifically, mandarin oranges such as Wenzhou mandarin oranges, Kishu mandarin oranges, Ponkan, Angkor, Mandarin, Danzerin, Koji, Sikhwasha, Tachibana, Shiranui, etc. Oranges such as Valencia Orange, Navel Orange and Blood Orange, Tancan, Iyo, Marcot, Kiyomi, Orlando, Mineola, Seminole and other Tangor Tan Zero, Mexican Lime, Tahitian Lime and other limes, Lisbon Lemon, Eureka Lemon, Diamante, Lemon citrons such as etrog, Bunpeille, Buntan such as Tosa Bungtan, Grapefruit such as Duncan, Marsh, Thomson, and Ruby Red, Yuzus such as Yuzu, Kabos, Sudachi, Hanayu, Scratches, Kin Down, the trifoliate orange can be exemplified.

  Among the above, citrus fruits such as lemon, orange, lime and cassis, apples such as apple and green apple, acerolas, plums, grapes, peaches, melons, watermelons and other fruit juices are mixed with vegetable drinks It is important to maintain a flavor balance such as acidity and bitterness, and these are suitable for the alcoholic suspension beverage of the present invention.

The method and conditions for producing the fruit juice are not particularly limited, and may be performed according to a known method, and the concentration rate and concentration method of the fruit juice are not limited at all.
<Alcoholic suspension drink with acidic milk>
The alcoholic suspension beverage containing acidic milk is an alcoholic suspension beverage containing 1% by mass or more of acidic milk, and is sometimes called calpis high. As used herein, acidic milk refers to milk or dairy products that are used regardless of the amount of milk or dairy products, as defined by ministerial ordinances regarding milk and dairy product component standards. Here, milk and dairy products include liquid milk such as cow milk and processed milk, cream, skim milk powder, whole milk powder, fermented milk, and the like. Moreover, fermented milk drink and non-fermented milk drink are contained in the alcoholic suspension drink containing acidic milk of this invention. 3-5 are preferable, as for the pH of the acidic milk drink of this invention, 3.3-4.5 are more preferable, and 3.6-4.4 are especially preferable. When the pH is within this range, it is preferable in terms of the taste of the beverage. Organic as well as inorganic edible acids may be used to adjust the pH. Organic and inorganic edible acids may be those generally used in foods. For example, lactic acid, citric acid, tartaric acid, malic acid, ascorbic acid, acetic acid, fumaric acid, phosphoric acid, adipic acid, gluconic acid Succinic acid, potassium hydrogen phosphate or sodium, potassium dihydrogen phosphate or sodium, fruit juice, or the like can be used. In particular, lactic acid, citric acid, tartaric acid, malic acid, ascorbic acid, and acetic acid are preferable in terms of sourness.
<Alcoholic suspension drink containing lactic acid bacteria and yeast>
Lactic acid bacteria and yeast-containing alcoholic suspension beverages are beverages containing 0.01% by mass or more of live or dead lactic acid bacteria and yeast, and are sometimes called makgeolli or dobloc. The alcoholic beverage may be a raw fermented liquor containing microorganisms as it is, may be concentrated using ordinary means, or may be a product obtained by reducing the concentrate with water or the like. Moreover, what added microorganisms to the alcoholic beverage prepared based on the distilled liquor and brewing liquor which do not contain microorganisms may be used. Since the effect of the present invention increases as the blending amount of lactic acid bacteria and yeast increases, it is more preferably 0.05% by mass, and still more preferably 0.1% by mass or more.
<Method for adding cellulose composite>
The following method is mentioned as a method of adding the cellulose composite in the present invention to an acidic food or drink. It can be added by dispersing the cellulose composite of the present invention in water simultaneously with the main raw material or components such as a coloring agent, a flavoring agent, a sour agent, and a thickener.

  When the dry powder of the cellulose composite is dispersed in an acidic aqueous medium, the dispersion stability of the cellulose composite is better when the cellulose composite is once dispersed in water and then added to the target food form. Is preferable. When the cellulose composite is a dry powder, it can be dispersed using various kneaders such as various dispersers, emulsifiers, and grinders that are usually used in the production process of foods and the like as a dispersion method in water. . Specific examples of the kneader include various types of mixers such as a propeller stirrer, high-speed mixer, homomixer, and cutter, mills such as a ball mill, colloid mill, bead mill, and laika machine, and dispersions represented by high-pressure homogenizers such as a high-pressure homogenizer and nanomizer. A kneader represented by a machine / emulsifier, a planetary mixer, a kneader, an eccluder, a turbulizer, or the like can be used. Two or more kneaders may be used in combination. Dispersion is easier when performed while heating.

  For example, a method in which a cellulose composite is mixed in an alcoholic suspension beverage and then dispersed with a homomixer, or a method in which the cellulose composite is previously dispersed in water with a homomixer and then mixed with an alcoholic beverage. Insoluble components such as vegetable fruit juice, milk components, microorganisms such as lactic acid bacteria, and cellulose composites can be mixed with water in advance before adding alcohol, thereby being excellent in suppressing sedimentation of insoluble components. .

  When the alcoholic suspension beverage of the present invention contains 0.01% by mass or more of particles having a size of 20 μm or more as a water-insoluble component, it is 10 MPa or more with a high-pressure homogenizer (for example, Manton Gorin homogenizer manufactured by APV) in the production process. Applying pressure to homogenize is preferable from the viewpoint of long-term storage stability.

The invention is illustrated by the following examples. However, these do not limit the scope of the present invention.
<Method for measuring storage elastic modulus of cellulose composite>
(1) Disperse the cellulose composite in pure water using a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7” treatment condition: 15,000 rpm × 5 minutes). A pure water dispersion having a concentration of 1.8% by mass was prepared.
(2) Mixing the aqueous dispersion with a 0.2 M Mclvaine buffer solution at pH 4 (0.2 M disodium hydrogen phosphate and 0.1 M citric acid aqueous solution) to obtain a concentration of the cellulose complex Was adjusted to 1% by mass (total amount 300 g, ion concentration 0.06 mol / L, pH 4), and the obtained aqueous dispersion was allowed to stand at room temperature for 3 days.
(3) The strain dependence of the stress of this aqueous dispersion is measured by a viscoelasticity measuring device (Rheometric Scientific, Inc., ARES100FRTN1 type), geometry: Double Wall Couette type, strain is swept within a range of 1 → 794%) It was measured. In the present invention, the storage elastic modulus (G ′) uses a value of 20% strain on the strain-stress curve obtained by the above measurement.
<Volume average particle diameter of cellulose composite>
(1) A cellulose composite is made into a pure water suspension at a concentration of 1% by mass, and a high-shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”) Processing conditions: 15,000 rpm × For 5 minutes).
(2) The particle size distribution of the obtained aqueous dispersion was measured by a laser diffraction method (manufactured by Horiba, Ltd., trade name “LA-910”, ultrasonic treatment for 1 minute, refractive index 1.20). The 50% cumulative particle size in the volume frequency particle size distribution obtained here was taken as the volume average particle size.
<Colloidal cellulose component content of cellulose composite>
(1) A cellulose composite is made into a pure water suspension at a concentration of 1% by mass, and a high-shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”) Processing conditions: 15,000 rpm × For 5 minutes).
(2) Next, it was centrifuged. (Made by Kubota Corporation, trade name "6800 type centrifuge" rotor type RA-400 type, processing conditions: centrifugal force 2,000 rpm (5600G * G is gravitational acceleration) x 15 minutes, total amount of centrifuge tube 50g Was charged.)
(3) The supernatant after centrifugation was introduced into a glass weighing bottle, dried at 60 ° C. for 15 hours, then dried at 105 ° C. for 2 hours, weighed in a desiccator, and then weighed. Separately, the non-centrifugated aqueous dispersion was similarly dried and weighed. From these results, the mass percentage of the solid content of cellulose remaining in the supernatant was determined from the following formula.
Calculation formula: (solid content of supernatant 50 g) / (solid content in non-centrifugated 50 g) × 100
<Dispersion stability: Appearance observation of aqueous dispersion of dispersed cellulose composite>
With respect to the aqueous dispersion obtained by the above-described storage modulus measurement method (2), the following four items were determined and visually judged.
(Separation) The volume at the top of the sedimentation tube was evaluated by the volume of the thin layer.
◎ (excellent): no separation, ○ (good): separation is less than 10%, △ (possible): separation is less than 30%, x (impossible): separation is 30% or more (sedimentation). did.
◎ (excellent): No sedimentation, ○ (good): Partially thin sedimentation, △ (possible): Thin sedimentation on one side, x (impossible): Overall dark sedimentation (aggregation) Uneven in the entire sedimentation tube The amount of the part was evaluated.
◎ (excellent): Uniform, ○ (good): Slightly non-uniform, Δ (possible): partially non-uniform, x (impossible): overall non-uniform <viscosity of cellulose composite aqueous dispersion>
The water dispersion obtained by the above-mentioned storage elastic modulus measurement method (2) was subjected to a B-type viscometer (rotor rotation speed 60 rpm. After setting for 3 hours (stored at 25 ° C.), and left standing for 30 seconds after setting. , Measured by rotating for 30 seconds, but the rotor can be appropriately changed depending on the viscosity.The rotor used is as follows: 1 to 20 mPa · s: BL type, 21 to 100 mPa · s: No1, 101 ˜300 mPa · s: No2, 301 mPa · s: No3). The measurement results were classified according to the following criteria.
(Viscosity) ◎ (excellent): 1 to 50, ○ (good): 51 to 75, Δ (possible): 76 to 100, x (impossible): 101 to [mPa · s]
<Particle shape of cellulose 1: applicable to cellulose composites A to M>
The cellulose composite was made into a pure water suspension at a concentration of 1% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7” treatment condition: 15,000 rpm × 5 minutes) The aqueous dispersion dispersed in was diluted to 0.1% by mass with pure water, and one drop was cast on mica using a dropper. Excess water was blown off with an air duster and air-dried to prepare a sample. From the shape of particles with a major axis (L) of 2 μm or less based on images measured with an atomic force microscope (Nano Scope IV MM manufactured by Digital Instruments, scanner EV, measurement mode Tapping, probe NCH type silicon single crystal probe) The major axis (L) and the minor axis (D) were obtained, and the ratio (L / D) was the shape of the cellulose particles, and was calculated as the average value of 100 to 150 particles.
<Particle shape of cellulose 2: applicable to cellulose composites N and O>
The cellulose composite was made into a pure water suspension at a concentration of 0.25% by mass, and a high-shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”) Treatment conditions: 15,000 rpm × 5 The aqueous dispersion dispersed in 1 minute) was diluted with pure water to 0.01 to 0.05% by mass, and one drop was cast on mica using a dropper. Excess water was blown off with an air duster, air-dried, a sample was prepared, and platinum palladium was deposited in a thickness of 3 nm. Based on an image measured with a scanning electron microscope (device JSM-5510LV type manufactured by JEOL Ltd.), a major axis (L) and a minor axis (D) are obtained, and the ratio (L / D) is the particle shape of cellulose. It calculated as an average value of 100 to 150 particles.
<Structure of cellulose composite: Observation of spreading of hydrophilic gum from cellulose>
(1) The cellulose composite is purified using pure water using a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7” treatment condition: 15,000 rpm × 5 minutes, total amount 300 g). To prepare a 1.0% by mass pure water dispersion.
(2) The above-mentioned aqueous dispersion is mixed with 0.2 M Mclvaine buffer solution (pH 3.5) (0.2 M disodium hydrogen phosphate and 0.1 M citric acid aqueous solution) to obtain a cellulose composite. Was adjusted to 0.5 mass% (ion concentration 0.06 mol / l, pH 4.0), and then the concentration of the cellulose composite was diluted to 0.1 mass% with pure water.
(3) The aqueous dispersion obtained in (1) and (2) was allowed to stand at room temperature for 3 days or more. Slowly suck out 5 μl using a dropper so as not to break the fine structure of the water dispersion, slowly drop it onto the 1 cm × 1 cm wall-opened mica, and blow off excess water with an air duster. The sample fixed on the surface was observed with an AFM (scanning probe microscope SPM-9700, manufactured by Shimadzu Corporation, phase mode, using Olympus probe OMCL-AC240TS).
<Suspension stability: Appearance observation of alcoholic suspension beverage>
In various beverages (refer to the following examples and comparative examples for the production method), standards were determined for the following items and judged visually.
(Separation) The volume at the top of the sedimentation tube was evaluated by the volume of the thin layer.
◎ (excellent): no separation, ○ (good): separation is less than 10%, △ (possible): separation is less than 30%, x (impossible): separation is 30% or more (sedimentation). did.
◎ (excellent): No sedimentation, ○ (good): Partially thin sedimentation, △ (possible): Thin sedimentation on one side, x (impossible): Overall dark sedimentation (aggregation) Uneven in the entire sedimentation tube The amount of the part was evaluated.
(Excellent): Uniform, ○ (good): Slightly non-uniform, △ (possible): partially non-uniform, x (impossible): overall non-uniform (redispersibility) Slowly rotate the sedimentation tube up and down (As a guideline, rotate once for about 5 to 6 seconds and restore it. This is defined as the number of redispersion times) and rotate the settling tube until there is no water-insoluble component settled at the bottom. , Count the number of times. The smaller the number of redispersions, the higher the dispersibility and suspension stability.
<Viscosity of beverages * For foods other than beverages, this evaluation standard does not apply. >
Various beverages (for the production method, refer to the following Examples and Comparative Examples), 1 hour after production (stored at 25 ° C.), B type viscometer (rotor rotation speed 60 rpm. Measured by rotating for 2 seconds, but the rotor can be appropriately changed depending on the viscosity.The rotor to be used is as follows: 1-20 mPa · s: BL type, 21-100 mPa · s: No1, 101-300 mPa · s: No2, 301 mPa · s: No 3) The measurement results were classified according to the following criteria.
(Viscosity) ◎ (excellent): 1 to 10, ○ (good): 10 to 20, Δ (possible): 20 to 50, x (impossible): 50 to (mPa · s)
Hereinafter, cellulose is abbreviated as MCC, psyllium seed gum as PSG, sodium carboxymethylcellulose as CMC-Na, gellan gum as GLG, sodium alginate as ARG-Na, and LM pectin as LMP.
Example 1
After cutting commercially available DP pulp, it was hydrolyzed in 2.5 mol / L hydrochloric acid at 105 ° C. for 15 minutes, then washed with water and filtered to produce wet cake-like crystalline cellulose (MCC) with a solid content of 50 mass%. (Average polymerization degree was 220).

  Next, wet cake-like MCC, PSG (manufactured by MRC polysaccharides, PG020, viscosity of 1% by mass solution 40 mPa · s), CMC-Na (Daiichi Kogyo Seiyaku Co., Ltd., F-7A, 1 % Dissolved solution viscosity 11 mPa · s), and a mass ratio of MCC / PSG / CMC-Na is 90 to a planetary mixer (manufactured by Shinagawa Kogyo Co., Ltd., 5DM-03-R, stirring blade is hook type). / 5/5 was added, and water was added so that the solid content was 45% by mass.

  Thereafter, the mixture was kneaded at 126 rpm to obtain a cellulose composite. The kneading energy was controlled by the kneading time of the planetary mixer, and the actually measured value was 0.6 kWh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured by using a thermocouple. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. This was granulated in a diameter of 3 to 5 mm, and in a wet state, 100 g was dried at 100 ° C. for 1 hour in a ventilation dryer (Perfect oven manufactured by Tabai Espec). The dried product was pulverized with an ultracentrifugal crusher (ZTN100 type manufactured by RETSCHE) at a rotor rotation speed of 18000 rpm using a screen with an aperture of φ1.0 mm, and further pulverized using a screen with φ0.25 mm, Cellulose composite A was obtained.

The obtained cellulose composite A had a storage elastic modulus (G ′) of 0.48 Pa. Moreover, the volume average particle diameter of the cellulose composite A was 6.2 micrometers, the colloidal cellulose component was 55 mass%, and particle | grains L / D was 1.6. The dispersion stability (separation, sedimentation, aggregation, viscosity) of the cellulose composite A was evaluated, and the results are shown in Table-1.
Moreover, in the observed image of AFM, the cellulose particles are observed as rod-shaped particles having a height of 2 nm or more, and an aqueous dispersion prepared with ion-exchanged water (neutral) (FIG. 3) and an aqueous dispersion prepared at pH 4 (FIG. 4). ), A hydrophilic gum having a height of less than 2 nm extending radially from the cellulose particles was observed.
(Example 2)
After cutting the commercially available DP pulp, a wet cake-like cellulose was prepared in the same manner as in Example 1 (average polymerization degree was 220), and the mass ratio with MCC / PSG / CMC-Na was 90/3/7, solid content A cellulose aqueous dispersion was prepared under the condition of 40% by mass. This cellulose aqueous dispersion was kneaded with the same apparatus as in Example 1 to obtain a cellulose composite. The kneading energy was 0.1 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Moreover, this kneaded material was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite B.

The storage elastic modulus (G ′) was 0.2 Pa, the volume average particle size was 6.8 μm, the colloidal cellulose component was 45% by mass, and the particle L / D was 2.0. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite B.
(Example 3)
After cutting the commercially available DP pulp, a wet cake-like cellulose was prepared in the same manner as in Example 1 (average polymerization degree was 220), and MCC / PSG / GLG (manufactured by CP Kelco, Kelco Gel, Lot070628, 1% by mass of the solution) Weighing so that the mass ratio with respect to the viscosity of 1222 mPa · s is 90/9/1, adding water so that the solid content is 49.5% by mass, and then kneading with a planetary mixer to obtain a cellulose composite. It was. The kneading energy was 0.5 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Further, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite C.

The obtained cellulose composite C had a storage elastic modulus (G ′) of 0.18 Pa, a volume average particle diameter of 7.5 μm, a colloidal cellulose component of 53 mass%, and a particle L / D of 1.6. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite C.
Example 4
After cutting the commercially available DP pulp, wet cake-like cellulose is prepared in the same manner as in Example 1 (average polymerization degree is 220), and the mass ratio with MCC / PSG / CMC-Na is 50/25/25. Weighing, adding water to a solid content of 49% by mass, and kneading with a planetary mixer to obtain a cellulose composite. The kneading energy was 0.6 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Moreover, this kneaded material was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite D.

The storage elastic modulus (G ′) was 0.2 Pa, the volume average particle size was 5.8 μm, the colloidal cellulose component was 36% by mass, and the particle L / D was 1.6. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite D.
(Example 5)
After cutting the commercially available DP pulp, wet cake-like cellulose was prepared in the same manner as in Example 1 (average polymerization degree was 220), and MCC / PSG / ARG-Na (manufactured by Kimika Co., Ltd., Kimika Argin SKAT-UVL, 1 % Dissolved solution with a viscosity of 4.1 mPa · s) is weighed so that the mass ratio is 95 / 2.5 / 2.5, added to a solid content of 45% by mass, and kneaded with a planetary mixer. Thus, a cellulose composite was obtained. The kneading energy was 0.6 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Further, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite E.

The storage elastic modulus (G ′) was 0.5 Pa, the volume average particle diameter was 7.8 μm, the colloidal cellulose component was 43% by mass, and the particle L / D was 1.6. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite E.
(Example 6)
After cutting the commercially available DP pulp, a wet cake-like cellulose was prepared in the same manner as in Example 1 (average polymerization degree was 220), and weighed so that the mass ratio with MCC / PSG was 90/10. Water was added to 45 mass%, and the mixture was kneaded with a planetary mixer to obtain a cellulose composite. The kneading energy was 0.5 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. In addition, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite F.

The storage elastic modulus (G ′) was 0.15 Pa, the volume average particle diameter was 7.4 μm, the colloidal cellulose component was 56 mass%, and the particle L / D was 1.6. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite F.
(Example 7)
After cutting the commercially available DP pulp, a wet cake-like cellulose is prepared in the same manner as in Example 1 (average polymerization degree is 220), and the mass ratio with MCC / PSG / LMP (manufactured by Unitech Foods, Inc., LNSN 325) is Weighed to 90/5/5, added water to a solid content of 45% by mass, and kneaded with a planetary mixer to obtain a cellulose composite. The kneading energy was 0.5 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Further, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite G.

The storage elastic modulus (G ′) was 0.17 Pa, the volume average particle diameter was 7.2 μm, the colloidal cellulose component was 54 mass%, and the particle L / D was 1.6. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite G.
(Example 8)
After cutting the commercially available DP pulp, a wet cake-like cellulose is prepared in the same manner as in Example 1 (average polymerization degree is 220). Gellan gum (GLG) is used instead of PSG as the hydrophilic gum, and the cellulose composite is prepared. Prepared. The preparation method is as follows. The mass ratio of MCC / GLG (Deacyl Gellan Gum, CP Kelco manufactured by CP Kelco, trade name Kelco Gel) / CMC-Na (Daiichi Kogyo Seiyaku Co., Ltd., F-7A, 1% viscosity of dissolved solution 11 mPa · s) is 90. / 5/5, watered to a solid content of 50% by mass, and kneaded with a planetary mixer to obtain a cellulose composite N. The kneading energy was 0.6 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Further, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite H.

The storage elastic modulus (G ′) was 0.32 Pa, the volume average particle diameter was 6.5 μm, the colloidal cellulose component was 45 mass%, and the particle L / D was 1.6. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite H.
Example 9
After cutting the commercially available DP pulp, wet cake-like cellulose was prepared in the same manner as in Example 1 (average polymerization degree was 220), and xanthan gum was used in place of PSG as a hydrophilic gum to prepare a cellulose composite. The prototype method is as follows. Mass with MCC / xanthan gum (Bistop NSD-X, manufactured by San-Ei Gen FFI Co., Ltd.) / CMC-Na (Daiichi Kogyo Seiyaku Co., Ltd., F-7A, 1% dissolved solution viscosity 11 mPa · s) A cellulose composite O was obtained by weighing to a ratio of 90/2/8, adding water so that the solid content was 48% by mass, and kneading with a planetary mixer. The kneading energy was 0.6 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Further, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite I.

The storage elastic modulus (G ′) was 0.35 Pa, the volume average particle size was 6.3 μm, the colloidal cellulose component was 49% by mass, and the particle L / D was 1.6. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite I.
(Comparative Example 1)
After cutting the commercially available DP pulp, wet cake-like cellulose is prepared in the same manner as in Example 1 (average polymerization degree is 220), and the mass ratio with MCC / PSG / CMC-Na is 80/0/20. A cellulose composite J was obtained by weighing, adding water to a solid content of 45% by mass, and kneading with a planetary mixer. The kneading energy was 0.5 kWh / kg, and the kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Further, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite J.

The storage elastic modulus (G ′) was 0.02 Pa, the volume average particle size was 8.8 μm, the colloidal cellulose component was 35% by mass, and the particle L / D was 1.6. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite J.
(Comparative Example 2)
After cutting the commercially available DP pulp, wet cake-like cellulose is prepared in the same manner as in Comparative Example 1 (average polymerization degree is 220), and the mass ratio with MCC / PSG / CMC-Na is 90/5/5. A cellulose composite K was obtained by weighing, adding water to a solid content of 28% by mass, and kneading with a planetary mixer. The kneading energy was 0.04 kWh / kg, and the kneading temperature was measured in the same manner as in Example 1. Through kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. In addition, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite K.

The storage elastic modulus (G ′) was 0.01 Pa, the volume average particle diameter was 13.5 μm, the colloidal cellulose component was 28% by mass, and the particle L / D was 2.4. Dispersion stability was evaluated in the same manner as in Comparative Example 1 using the cellulose composite K.
(Comparative Example 3)
After cutting the commercially available DP pulp, the acid-insoluble residue obtained by hydrolysis at 105 ° C. for 20 minutes in 10% by mass hydrochloric acid was filtered and washed, and then a cellulose aqueous dispersion having a solid content of 10% by mass was prepared (average) The degree of polymerization was 200). The average particle size of the hydrolyzed cellulose was 17 μm. The cellulose aqueous dispersion was mixed with a medium stirring wet pulverizer (Apex Mill manufactured by Kotobuki Giken Kogyo Co., Ltd., AM-1 type), using zirconia beads having a diameter of 1 mmφ as a medium, the rotation speed of the stirring blade being 1800 rpm, Grinding was performed by passing twice under the condition of a supply amount of 0.4 L / min to obtain a fine cellulose paste.

  Weigh so that the mass ratio of paste-like fine cellulose / PSG / CMC-Na (substitution degree 0.90, viscosity 7 mPa · s) is 80/0/20, so that the total solid content concentration becomes 11% by mass. Prepared with pure water and dispersed for 20 minutes at 8,000 rpm using a TK homomixer (MARKKII manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a pasty water dispersion (consumption of apex mill and TK homogenizer) The kneading energy calculated from the electric power and the processing amount was 0.03 kWh / kg The kneading temperature was measured in the same manner as in Example 1. The kneading temperature was 20 to 60 ° C. and the final temperature was 50 to 60 ° C. )

The aqueous dispersion was dried with a drum dryer (KDD-1 type, manufactured by Kashiwagi Machine Mfg. Co., Ltd.) at a water vapor pressure of 2 kg / cm 2 and a rotation speed of 0.6 rpm, scraped off with a scraper, and flash mill (Fuji Powder) The product was roughly crushed to obtain a flaky and scaly cellulose composite L. The kneading energy is 0.03 kWh / kg, the storage elastic modulus (G ′) of the cellulose composite L is 0.01 Pa, the volume average particle diameter is 3.4 μm, the colloidal cellulose component is 40% by mass, and the particle L / D. Was 2.4. Dispersion stability was evaluated in the same manner as in Comparative Example 1 using the cellulose composite L.
(Comparative Example 4)
After cutting a commercially available DP pulp, the acid-insoluble residue obtained by hydrolysis in 10% by mass hydrochloric acid at 105 ° C. for 20 minutes is filtered and washed to give wet cake-like cellulose having a moisture content of 60% by mass (average polymerization) The degree was 200). Water was added to a solid content of 45% by mass, and this was treated for 2 hours with a planetary mixer under the same conditions as in Example 1. Water was added to the milled product to adjust the solid content to 7% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”) Processing conditions: 15,000 rpm × 5 Minutes). Then, it centrifuged for 10 minutes with the centrifugal force of 2500G, and obtained the MCC water dispersion of solid content 4 mass% as an upper layer part.

  Next, PSG and CMC-Na were charged into the MCC aqueous dispersion so as to have the composition of Example 1, and uniformly mixed using a propeller-type stirrer to prepare an aqueous dispersion (in this case, the solid content) Is 4-5 mass%). The aqueous dispersion was treated with a silicone release agent with a drum dryer (KDD-1 type manufactured by Kashiwagi Machinery Co., Ltd.), and then dried at a water vapor pressure of 0.12 MPa and a rotation speed of 1.0 rpm. A film-like cellulose composite M was obtained.

  The kneading energy was 0.08 kWh / kg as the total amount (the planetary mixer was 0.08 kWh / kg, and the others were less than 0.005 kWh / kg as the total amount). The kneading temperature (propeller stirring) in the coexistence with the hydrophilic gum was measured in the same manner as in Example 1, and was 20 to 60 ° C. and the final temperature was 50 to 60 ° C. throughout the kneading.

  The volume average particle size was 3.5 μm, and the colloidal cellulose component was 72% by mass. The particle L / D was 1.6 (the proportion of particles of 10 μm or more in the particle size distribution obtained by measuring the volume average particle size was 2). .5%). As a result of measuring the storage elastic modulus by the same operation as in Example 1, it was 0.01 Pa.

In Comparative Example 4, the kneading energy applied to the cellulose falls within the preferred range of the present invention, but PSG and CMC-Na were not present in the processing of the planetary mixer that occupies most of the kneading energy. The compounding of MCC with PSG and CMC-Na naturally does not proceed, and the storage elastic modulus is considered to be out of the scope of the present invention.
(Comparative Example 5)
Commercially available wood pulp (average polymerization degree = 1720, α-cellulose content = 78% by mass) was cut into a 6 × 16 mm square and water was added so that the solid content concentration was 80% by 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. 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. Subsequently, the obtained aqueous dispersion was directly subjected to 18 passes with a high-pressure homogenizer (treatment pressure: 55 MPa) to obtain a cellulose slurry. When observed with a scanning electron microscope, very fine fibrous cellulose having a major axis / minor axis ratio of 30 to 300 was observed.

  To the fine fibrous cellulose slurry obtained above, carboxymethylcellulose.sodium so as to be cellulose: carboxymethylcellulose.sodium (water-soluble gum): dextrin (hydrophilic substance) = 70: 18: 12 (parts by mass). Sodium (1% by weight aqueous solution viscosity: about 3400 mPa · s) and dextrin (DE: about 23) were added, and 15 kg was stirred with a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd., “TK AUTO HOMO MIXER”). The mixture was stirred and mixed at 8000 rpm for 30 minutes to obtain a cellulose mixed solution. Next, this mixed solution was cast into an aluminum plate 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 Paudal Co., Ltd.) so that the sieve having an opening of 1 mm was almost completely passed through to obtain a dried cellulose composition.

  Next, a stabilizer containing a dry cellulose composition: psyllium seed gum (same as Example 1, hydrophilic gum) at a mass ratio of 9: 1 is prepared. The stabilizer and water are weighed out so that the solid content becomes a 1% by mass aqueous dispersion, and dispersed using TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 8000 rpm for 10 minutes. Cellulose composition N (only mixed, not composite) was obtained. The kneading energy (stirring energy by TK homo) was less than 0.005 kWh / kg as a total amount. The kneading (stirring with TK homo) temperature in the presence of the hydrophilic gum was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C, and the ultimate temperature was 50 to 60 ° C.

The volume average particle diameter was 37.9 μm, and the colloidal cellulose component was 75% by mass. The storage elastic modulus was measured by the same operation as in Example 1, and as a result, it was 22 Pa. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composition N.
(Example 10)
A wet cake cellulose was prepared in the same manner as in Example 1, and PSG was used as a hydrophilic gum and CMC-Na was used as a water-soluble gum to prepare a cellulose composite. The prototype method is as follows. MCC / PSG (Psylum seed husk made by Shikibo Co., Ltd. Food made 1% solution viscosity is 198 mPa · s) / CMC-Na (Daiichi Kogyo Seiyaku Co., Ltd., F-7A, 1% solution viscosity 11 mPa · s) ) And a water content such that the solid content is 37% by mass and kneaded with a planetary mixer to obtain a cellulose composite. The kneading energy was 0.05 kWh / kg (the operating conditions of the planetary mixer were the same as in Example 1, and the kneading energy was adjusted according to the operating time). The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 60 ° C., and the ultimate temperature was 50 to 60 ° C. Further, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite O.

The storage elastic modulus (G ′) was 0.06 Pa, the volume average particle size was 8.2 μm, the colloidal cellulose component was 38% by mass, and the particle L / D was 2.2. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite O.
(Example 11)
A wet cake-like cellulose was prepared in the same manner as in Example 1, and a cellulose aqueous dispersion was prepared under the conditions of a mass ratio of 90/5/5 to MCC / PSG / CMC-Na and a solid content of 40% by mass. The cellulose aqueous dispersion was kneaded by the same apparatus as in Example 1, and warm water (50 ° C.) was passed through the jacket in the kneading container to control the kneading temperature to obtain a cellulose composite. The kneading time was extended from that of Example 1, and the total kneading energy was 0.50 kWh / kg. The kneading temperature was measured in the same manner as in Example 1. Through the kneading, the temperature was 20 to 80 ° C., and the ultimate temperature was 70 to 80 ° C. Further, this kneaded product was dried and pulverized in the same manner as in Example 1 to obtain a cellulose composite P.

The storage elastic modulus (G ′) was 0.13 Pa, the volume average particle size was 6.3 μm, the colloidal cellulose component was 55% by mass, and the particle L / D was 2.0. Dispersion stability was evaluated in the same manner as in Example 1 using the cellulose composite P.
[Dispersion stability of cellulose composite in ethanol water]
Using the cellulose composites A to P obtained in Examples 1 to 11 and Comparative Examples 1 to 5, the dispersion stability in ethanol water was verified by the following method.

  First, cellulose composite Examples 1 to 11 were made into a pure water suspension at a concentration of 1% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”) Processing conditions: rotational speed (15,000 rpm × 5 minutes) to obtain a cellulose composite dispersion. 50 mL of aqueous solutions having various ethanol concentrations were added to 50 mL of the dispersion, and charged into a 100 mL glass settling tube. Finally, two levels of ethanol concentration of 10% by mass and 20% by mass were prepared. Thereafter, the mixture was allowed to stand at room temperature for 2 weeks, and the dispersion stability was evaluated every week.

At an ethanol concentration of 10% by mass, in all of the Examples, there was no abnormality in separation, aggregation, sedimentation, and viscosity during storage after 2 weeks (all were ◯ to ◎). When the ethanol concentration was 20% by mass, the cellulose composites F, O, and P of Examples 6, 10, and 11 caused sedimentation after storage for 1 week (sedimentation = Δ, other items were ◯). In Examples 1 to 5 and 7 to 9 other than those described above, there was no problem in separation, aggregation, and sedimentation viscosity (all ◯ to ◎).
[Alcoholic suspension drink with lactic acid bacteria (makgeolli)]
Using the cellulose composites A to P and the cellulose composition N obtained in Examples 1 to 11 and Comparative Examples 1 to 5, alcoholic suspension drinks containing lactic acid bacteria were prepared by the following method, and suspension stability The sex was verified.

  First, the cellulose composite was made into a pure water suspension at a concentration of 1% by mass and treated with a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”): rotational speed 15,000 rpm × 5 Minutes) to obtain a dispersion of cellulose composite.

  To 50 parts by mass of this dispersion, 50 parts by mass of commercially available makgeolli (Makuro Japan Co., Ltd., black bean makgeolli, 750 mL PET bottle, alcohol content 6%, pH 4.4) with well-shaken contents. In addition, the mixture was stirred for 10 minutes at 8000 rpm with a high-shear homogenizer (Special Machine Co., Ltd. TK homogenizer) and charged into a 100 mL glass settling tube.

  Then, it preserve | saved for one week in the refrigerator and evaluated the suspension state. The results are shown in Tables 1 and 2.

By the way, when the cellulose composite was not added, and the product prepared by adding 50 parts by mass of ion-exchanged water to 50 parts by mass of makgeolli was evaluated in the same manner, separation: x, aggregation: x, sedimentation: x, viscosity: ◎ And the number of redispersions was 20 or more.
[Alcoholic suspension drink with turmeric]
Using the cellulose composites A to P and the cellulose composition N obtained in Example 1 and Comparative Examples 1 to 5, a turmeric-containing alcoholic suspension drink was prepared by the following method, and suspension stability was improved. Verified.

First, the cellulose composite was made into a pure water suspension at a concentration of 1% by mass and treated with a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”): rotational speed 15,000 rpm × 5 Minutes) to obtain a dispersion of cellulose composite.
Next, turmeric (made by Orihiro, trade name: autumn turmeric powder 100%) is added to this dispersion so as to be 0.06% by mass, and stirred at room temperature for 20 minutes with a propeller 400 rpm. Next, this dispersion was subjected to a one-pass treatment with a high-pressure homogenizer (Manton Gorin homogenizer manufactured by APV) under the condition of adding 5 MPa as a secondary pressure to a primary pressure of 15 MPa.

  50 parts by mass of an aqueous solution having an ethanol concentration of 20% by mass was added to 50 parts by mass of this aqueous dispersion, and the mixture was stirred at 8000 rpm for 10 minutes with a high shear homogenizer (Special Machine Co., Ltd. TK homogenizer), and 100 mL of glass sediment Prepared the tube.

  Then, it preserve | saved for one week in the refrigerator and evaluated the suspension state. The results are shown in Tables 1 and 2.

By the way, what was prepared by adding an aqueous ethanol solution to an aqueous curcumin solution without adding a cellulose complex was evaluated as follows: separation: x, aggregation: x, sedimentation: x, viscosity: ◎, and number of redispersions Was 20 times or more.
[Evaluation of viscoelasticity measurement]
The result of the viscoelasticity measurement of the cellulose composite A (Example 1) and the cellulose composite L (Comparative Example 3) is shown in FIGS.

  From FIG. 1, it can be seen that the cellulose composite A has a higher storage elastic modulus in the vicinity of 20% of the strain in the acidic aqueous dispersion than in the pure water dispersion (pure water: 0.02 Pa → pH 4: 0. 58 Pa). Further, from FIG. 2, the cellulose composite L (the cellulose composite obtained by the production method according to the example of Patent Document 3) is approximately 20% strain in the acidic aqueous dispersion as compared with the pure water dispersion. It can be seen that the storage elastic modulus is low (pure water: 0.24 Pa → pH 4: 0.01 Pa).

  In the cellulose composite kneaded with ordinary energy, the storage modulus in acidity is lower than that in pure water, and the suspension stability is lowered. On the other hand, in the cellulose composite kneaded with high energy, it can be seen that the storage elastic modulus at acidic or high salt concentration is increased and the suspension stability is improved.

  The present invention relates to an alcoholic suspension beverage containing a water-insoluble component such as lactic acid bacteria and fruits and exhibiting a stable dispersed state and suspended state. In particular, it is possible to provide an alcoholic suspension beverage that is acidic and has long-term stability and good flavor.

Claims (6)

  A cellulose composite containing cellulose and a hydrophilic gum, the storage composite containing the cellulose composite having a storage elastic modulus (G ′) of 0.06 Pa or more in a pH 4 aqueous dispersion containing 1% by mass of the cellulose composite. Alcoholic suspension drink.   The alcoholic suspension beverage according to claim 1, wherein the cellulose composite contains 50 to 99% by mass of cellulose and 1 to 50% by mass of a hydrophilic gum.   The alcoholic suspension beverage according to claim 1 or 2, wherein the hydrophilic gum is psyllium seed gum.   (1) to (3), wherein the cellulose composite further includes a water-soluble gum different from the hydrophilic gum, and a mass ratio of the hydrophilic gum to the water-soluble gum is 30/70 to 99/1. ) The alcoholic suspension beverage according to any one of the above.   The alcoholic suspension beverage according to claim 4, wherein the water-soluble gum is at least one selected from the group consisting of sodium carboxymethylcellulose, LM pectin, sodium alginate, and gellan gum.   pH is 6 or less, The alcoholic suspension drink as described in any one of Claims 1-5.