JP6434777B2 - Cellulose composite - Google Patents

Description

  The present invention relates to a cellulose composite containing cellulose and an anionic polysaccharide, and a method for producing the same.

  Cellulose composites composed of cellulose and anionic polysaccharide are widely used in the fields of foods, pharmaceuticals, cosmetics, paints, ceramics, resins, catalysts, and other industrial products. Since the cellulose composite forms a cellulose colloid in an aqueous medium and exhibits good suspension stability, the cellulose composite is not limited to a stabilizer such as a suspension stabilizer, an emulsion stabilizer, a thickening stabilizer, a tissue imparting agent, The cellulose composite is used for the purpose of dee agent, whiteness improvement, fluidity improvement, polishing agent, dietary fiber, fat and oil replacement. For example, in a cocoa beverage, the cellulose composite is added for the purpose of suspension stability of cocoa powder, which is a water-insoluble component having a large specific gravity.

  Various studies have been made so far in order to further improve the suspension stability of the cellulose composite.

  Patent Document 1 describes a cellulose composite containing cellulose and a polysaccharide, and having a median diameter measured by a dynamic scattering method of 0.85 μm or more. Moreover, the cellulose composite whose storage elastic modulus is 0.50 Pa or more in the 1 mass% aqueous dispersion is described. In addition, it is described that sodium carboxymethylcellulose is preferable as the polysaccharide. In addition, there is a description of a method for producing a cellulose composite in which a solid content is 35% by mass or more and a temperature is 80 ° C. or less in a step of wet co-processing a mixture containing cellulose, a polysaccharide and an aqueous medium. It is described that the water-dispersible composition using the cellulose composite is excellent in suspension stability in beverages containing cocoa, coffee extract and the like.

  Patent Documents 2 and 3 disclose water-dispersible composites containing cellulose and two types of sodium carboxymethyl cellulose having different degrees of substitution. Patent Document 2 describes a cellulose composite having a gel strength of 25 Pa or more in a 3% dispersion. It is described that the water-dispersible composition is excellent in suspension stability in chocolate beverages.

  Patent Document 4 discloses the production of a cellulose composite in which a solid content is treated at 42% by mass or more in a wet co-treatment of a mixture containing cellulose, sodium carboxymethyl cellulose having a low viscosity and low substitution degree, and an aqueous medium. There is a description of the method. In addition, a cellulose composite having a gel strength of 20 Pa or more in a 2.6% aqueous dispersion is described. It is described that the water-dispersible composition is excellent in suspension stability in chocolate beverages.

WO2013 / 022090 pamphlet US Patent Application Publication 2013/0064953 WO2013 / 052114 pamphlet WO2013 / 052118 pamphlet

  In recent years, along with changes in people's lifestyle, products with high protein content for nutritional supplements have been developed in cans or beverages containing PET in addition to cocoa and coffee. In addition, food and drink products including beans and cereals have been developed as protein sources. The problem with such a product is that it feels sticky and sticky because of the high protein content. For this reason, in the drink in which protein was blended at a high concentration, there has been a demand for a cellulose composite exhibiting an effect that is excellent in throating and mouthfeel. In particular, in beverages containing peanuts and oats, gelation of components after sterilization treatment is a problem, and a cellulose composite that solves this problem has been desired.

  However, the above problems have not been sufficiently solved even in a cellulose composite composed of conventional cellulose and anionic polysaccharide. That is, even if a conventional cellulose composite was used, it was not possible to make a beverage excellent in throat and mouthfeel in a beverage containing a high concentration of protein.

  For example, when the cellulose composite described in Patent Documents 1, 2, 3, or 4 is used, in a cocoa beverage having a low protein concentration, an amount of the cellulose composite is added to obtain sufficient suspension stability. However, there was no problem over the throat or mouth. However, in beverages with a high concentration of protein in the beverage, adding a cellulose complex in an amount that provides sufficient suspension stability is compatible with improving throat, mouthfeel, and stickiness. There was a problem that I could not.

  Therefore, the main subject of this invention is providing the cellulose composite which can produce the drink which is excellent in the mouth and the throat, when protein is mix | blended with high concentration in the drink. Another object of the present invention is to provide a cellulose composite that is less viscous when mixed with a beverage.

  On the other hand, as described above, in a cocoa beverage having a low protein concentration, there was no problem of throat over or mouthfeel even when an amount of a cellulose complex with sufficient suspension stability was added. Even in a cocoa beverage having a relatively low protein concentration, a cellulose composite capable of improving suspension stability against sedimentation, aggregation, separation and the like with a smaller amount is still desired. That is, one of the specific problems of the present invention is to provide a cellulose composite capable of improving suspension stability with a smaller amount even in such a beverage having a relatively low protein concentration.

  The inventors of the present invention highly complexed cellulose and anionic polysaccharide, and have characteristic first rheological properties (the rheological properties relating to the retention rate of storage elastic modulus described in (1) below), and / or Or the cellulose composite which shows a 2nd rheological characteristic (Rheological characteristic regarding loss tangent (tan (delta)) described in the following (2)) was obtained. And it discovered that it became a drink excellent in a mouth and a throat by mix | blending a small amount of the cellulose composite which shows a 1st rheological characteristic in the drink with high protein concentration, and it came to make 1st this invention. Similarly, when a small amount of a cellulose composite exhibiting the second rheological property is blended in a beverage having a high protein concentration, the beverage was found to be less sticky, leading to the second invention.

  In addition, the present inventors satisfy the first and / or second rheological characteristics including a step of adding anionic polysaccharide to cellulose in three or more stages and adding it to cellulose to perform a wet co-treatment. The inventors have found a suitable method for producing a cellulose composite, and have made the third aspect of the present invention.

That is, the present invention is as follows.
(1) A cellulose composite containing cellulose and anionic polysaccharide, wherein the composite is dispersed in ion-exchanged water at a concentration of 1.0% by mass, at a strain of 1% at 25 ° C. The storage elastic modulus G ′ (1) and the storage elastic modulus G ′ (20) at a strain of 20% have a storage elastic modulus retention rate defined by G ′ (20) × 100 / G ′ (1). A cellulose composite of 92.2% or less.
(2) A cellulose composite containing cellulose and anionic polysaccharide, wherein the composite is dispersed in ion-exchanged water at a concentration of 1.0% by mass, at a strain of 1% at 25 ° C. A cellulose composite having a loss tangent (tan δ) of less than 0.42.
(3) A cellulose composite containing cellulose and anionic polysaccharide, wherein the composite is dispersed in ion-exchanged water at a 1.0% by mass concentration in an aqueous dispersion having a strain of 1% at 25 ° C. The storage elastic modulus G ′ (1) and the storage elastic modulus G ′ (20) at a strain of 20% have a storage elastic modulus retention rate defined by G ′ (20) × 100 / G ′ (1). A cellulose composite having a loss tangent (tan δ) of 92.2% or less at a strain of 1% at 25 ° C. of less than 0.42.
(4) In a 1.0% by mass aqueous dispersion obtained by dispersing the composite in ion-exchanged water, the storage elastic modulus (G ′ (1)) at a strain of 1% at 25 ° C. is 4.3 Pa or more. The cellulose composite according to any one of (1) to (3).
(5) Any of (1) to (4), wherein the anionic polysaccharide is sodium carboxymethyl cellulose having a viscosity at 25 ° C. exceeding 200 mPa · s when an aqueous dispersion having a concentration of 1.0% by mass is used. A cellulose composite according to any one of the above.
(6) A method for producing a cellulose composite containing cellulose and anionic polysaccharide, wherein the anionic polysaccharide is added to the cellulose in three or more stages and co-processed wet. The manufacturing method of the cellulose composite in any one of (1)-(5) including a process.
(7) Food / beverage products containing the cellulose composite in any one of said (1)-(5).

  The cellulose composite of the first aspect of the present invention makes it possible to produce a beverage that is excellent in mouth-feeling and throating when protein is blended at a high concentration in the beverage. Moreover, the cellulose composite of 2nd this invention makes it possible to produce a drink with little stickiness, when protein is mix | blended with high concentration in a drink.

  The present invention will be specifically described below.

  As used herein, “suspension stability” refers to a water-insoluble component other than the cellulose composite, such as cocoa particles and calcium particles in the aqueous medium. This means that the active ingredient is suspended and stabilized. Specifically, not only cellulose but also the occurrence of separation, aggregation, sedimentation and the like of the particles of the water-insoluble component, and a uniform appearance.

  Further, “complexing” as used in the present specification means that at least a part of the surface of cellulose is coated with an anionic polysaccharide by chemical bonds such as hydrogen bonds.

  The cellulose composite of the first aspect of the present invention is a cellulose composite containing cellulose and an anionic polysaccharide, wherein the composite is dispersed in ion-exchanged water at a concentration of 1.0% by mass. The storage elastic modulus G ′ (1) at a strain of 1% at 25 ° C. and the storage elastic modulus G ′ (20) at a strain of 20% are defined as G ′ (20) × 100 / G ′ (1). The retention rate of the storage elastic modulus is 92.2% or less.

  The cellulose composite of the second aspect of the present invention is a cellulose composite containing cellulose and an anionic polysaccharide, wherein the composite is dispersed in ion-exchanged water at a concentration of 1.0% by mass. The loss tangent (tan δ) at a strain of 1% at 25 ° C. is less than 0.42.

<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. It is possible to use one kind of natural cellulosic material among these as a raw material or a mixture of two or more kinds.

<Average degree of polymerization of cellulose>
The cellulose used in the present invention is preferably crystalline cellulose having an average degree of polymerization 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, it is preferable in the step of compounding with the anionic polysaccharide because the cellulose-based substance is easily subjected to physical treatment such as stirring, pulverization, and grinding, and the compounding is easily promoted. . 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.

<Hydrolysis of cellulose>
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, the hydrolysis process removes impurities such as hemicellulose and lignin in addition to the above-described amorphous cellulose, so that the inside of the fiber becomes porous. Thereby, in the process of giving mechanical shearing force to cellulose and anionic polysaccharide, such as a kneading process, the cellulose is easily subjected to mechanical treatment, and the cellulose is easily refined. As a result, the surface area of the cellulose increases, and the complexation with the anionic polysaccharide can be easily controlled.

  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 degree can be easily obtained by adding an appropriate amount of protonic acid, carboxylic acid, Lewis acid, heteropolyacid, and the like while stirring the cellulose-based material in an aqueous medium and stirring the mixture. Can be controlled. 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.

<Particle shape of cellulose (L / D)>
The cellulose in the cellulose composite of the present invention preferably has a fine particle shape. As for the particle shape of cellulose, the cellulose composite of the present invention 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”) Processing conditions: Rotation An aqueous dispersion dispersed at several 15,000 rpm × 5 minutes) is diluted to 0.1 to 0.5% by mass with pure water, cast on mica, and air-dried. A high-resolution scanning microscope ( SEM) or the ratio (L / D) of the major axis (L) and minor axis (D) of the particle image obtained when measured with an atomic force microscope (AFM), 100 to 150 Calculated as the average of individual particles.

  L / D is preferably less than 20 in terms of suspension stability, 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. The lower limit of L / D is 1 from its definition.

<Anionic polysaccharide>
The polysaccharide in the present invention refers to a compound in which a monosaccharide is α- or β-bonded to constitute a main chain or a side chain. In addition to sugars such as glucose, galactose, mannose, and xylose, monosaccharides include amino sugars such as deoxy sugars and N-acetylglucosamine, thio sugars, sugar acids such as gluconic acid, galacturonic acid, and mannuronic acid, and sugar alcohols. . A polysaccharide in which a cation is released in water and becomes an anion itself is called an anionic polysaccharide. In the present invention, the use of an anionic polysaccharide is preferable because the complexation with cellulose is further promoted.

  The following are preferable as the anionic polysaccharide. For example, water-soluble chemical synthesis such as psyllium seed gum, karaya gum, carrageenan, alginic acid, sodium alginate, HM pectin, LM pectin, Azotobacter vinelanzie gum, xanthan gum, gellan gum and the like, carboxymethylcellulose sodium, etc. The polysaccharide which becomes. Among these anionic polysaccharides, sodium carboxymethylcellulose (hereinafter also referred to as “CMC-Na”) and xanthan gum are preferable. Moreover, these anionic polysaccharides may combine 2 or more types.

<Carboxymethylcellulose sodium>
Among the above anionic polysaccharides, CMC-Na is particularly preferable because it is easily complexed with cellulose. CMC-Na here is composed of an anionic polymer in which some or all of the hydrogen atoms of the hydroxyl group of cellulose are substituted with —CH ₂ COO groups (carboxymethyl groups) and Na cations. It has a linear chemical structure with -1,4 bonds. CMC-Na is obtained, for example, by a production method in which pulp (cellulose) is dissolved with a sodium hydroxide solution and etherified with monochloroacetic acid (or a sodium salt thereof).

  In particular, it is preferable from the viewpoint of compositing to use CMC-Na whose substitution degree and viscosity are prepared in the following specific ranges. The degree of substitution is the degree to which a carboxymethyl group is ether-bonded to a hydroxyl group (having three hydroxyl groups per glucose unit) in CMC-Na, and is preferably 0.6 to 2.0 per glucose unit. If the degree of substitution (hereinafter also referred to as “the degree of etherification”) is within the above range, the higher the degree of substitution, the easier it becomes complexed with cellulose, the storage elastic modulus of the cellulose composite increases, and the high salt concentration aqueous solution ( For example, a 10% by mass sodium chloride aqueous solution) is preferable because high suspension stability can be exhibited. More preferably, the degree of substitution is 0.9 to 1.8, and most preferably 1.1 to 1.5.

The degree of substitution is measured by the following method. A sample (anhydrous) 0.5 g is accurately weighed, wrapped in filter paper and incinerated in a magnetic crucible. After cooling, transfer this to a 500 mL beaker, add about 250 mL of water and 35 mL of 0.05 M sulfuric acid and boil for 30 minutes. This is cooled, phenolphthalein indicator is added, excess acid is back titrated with 0.1 M potassium hydroxide, and calculated by the following formula.
A = ((af−bf1) / sample anhydride (g)) − alkalinity (or + acidity)
Degree of substitution = (162 × A) / (10000-80A)
here,
A: Amount of 0.05 M sulfuric acid consumed by alkali in 1 g of sample (mL)
a: Amount of 0.05 M sulfuric acid used (mL)
f: titer of 0.05M sulfuric acid b: titration volume of 0.1M potassium hydroxide (mL)
f1: Power of 0.1M potassium hydroxide number 162: molecular weight of glucose _80: Molecular weight of CH 2 COONa-H

Measuring method of alkalinity (or acidity): 1 g of sample (anhydride) is accurately measured in a 300 mL flask, and about 200 mL of water is added and dissolved. To this is added 5 mL of 0.05 M sulfuric acid, boiled for 10 minutes, cooled, added with phenolphthalein indicator, and titrated with 0.1 M potassium hydroxide (SmL). At the same time, a blank test is performed (BmL), and the following formula is used.
Alkalinity = ((B−S) × f2) / sample anhydride (g)
Here, f2 is the titer of 0.1M potassium hydroxide. When the value of (B−S) × f2 is (−), the acidity is determined.

  The viscosity of CMC-Na is preferably 50 mPa · s or more in a 1% by mass pure aqueous solution. The viscosity here is measured by the following method. First, using CMC-Na powder as 1% by mass, 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), Disperse in pure water to prepare an aqueous solution. Next, about 3 hours after dispersion | distribution (25 degreeC preservation | save) about the obtained aqueous solution, it sets to a B-type viscosity meter (rotor rotation speed 60rpm), and after leaving still for 60 seconds, it is rotated for 30 seconds and measured. However, the rotor can be appropriately changed according to the viscosity.

  As the viscosity of CMC-Na is higher, the storage elastic modulus G ′ (1) at a strain of 1% at 25 ° C. of the cellulose composite described later tends to increase. In addition, the storage elastic modulus G ′ (20) × 100 / G ′ (1) is maintained with respect to the storage elastic modulus G ′ (1) and the storage elastic modulus G ′ (20) at 20% strain. The rate tends to be small. The viscosity of CMC-Na is more preferably 200 mPa · s or more, further preferably 1000 mPa · s or more, and most preferably 2500 mPa · s or more.

<Blending ratio of cellulose and anionic polysaccharide>
The blending ratio of cellulose and anionic polysaccharide in the cellulose composite of the present invention is preferably cellulose / anionic polysaccharide = 50 to 99 parts by mass / 1 to 50 parts by mass. By making this compounding ratio within the above range, the compounding ratio is promoted and the storage elastic modulus G ′ (1) is likely to increase. The compounding ratio of cellulose and anionic polysaccharide is 70 to 99 parts by mass / 1-30 mass parts is more preferable, 75-95 mass parts / 5-25 mass parts is further more preferable, and 80-90 mass parts / 10-20 mass parts is especially preferable. In addition, the compounding quantity of a cellulose and anionic polysaccharide shall be a value based on the mass in the state which does not contain a water | moisture content, respectively.

<Storage elastic modulus of cellulose composite>
Next, the storage elastic modulus G ′ (1) of the cellulose composite of the present invention will be described.
The cellulose composite of the present invention has a storage elastic modulus G ′ (1) of 4 at a strain of 1% at 25 ° C. in a 1.0% by mass pure water dispersion obtained by dispersing the composite in pure water. It is preferably 3 Pa or more.

  The storage elastic modulus G ′ (1) expresses the rheological elasticity of the aqueous dispersion, and is composed of cellulose and anionic polysaccharide, or cellulose and anionic polysaccharide and other water-soluble substances. It represents the degree of compounding with gum. The higher the storage elastic modulus G ′ (1), the more complex the cellulose and the anionic polysaccharide, or the cellulose and the anionic polysaccharide and other water-soluble gums. This means that the network structure in the dispersion is rigid. The more rigid the network structure, the better the gelation inhibiting ability and suspension stability of the cellulose composite.

  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 pure water. That is, an elastic component that holds the stress stored in the cellulose composite network structure when the aqueous dispersion is distorted is expressed 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 1.0 mass% aqueous dispersion. The obtained aqueous dispersion is allowed to stand at room temperature for 3 hours. The strain dependence of the stress of this water dispersion was measured using a viscoelasticity measuring device (TA Instruments, ARES-G2 type, geometry: Double Wall Couette type, temperature: 25.0 ° C constant, angular velocity: 20 rad / sec, strain: Sweeping within a 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 10 minutes, measurement is started in the Dynamic Strain mode). The storage elastic modulus G ′ (1) in the present invention is a value of 1% strain on the strain-stress curve obtained by the above measurement. The larger the value of the storage elastic modulus G ′ (1), the more elastic the structure of the aqueous dispersion formed by the cellulose composite, and the composite of cellulose and anionic polysaccharide, or cellulose and anion. It shows that the functional polysaccharide and other water-soluble gums are highly complexed.

  The storage elastic modulus G ′ (1) of the cellulose composite is preferably 0.5 Pa or more, more preferably 2.0 Pa or more, more preferably 4.3 Pa or more, more preferably 10.0 Pa or more, and 13.5 Pa or more. More preferably, 18.0 Pa or more is particularly preferable, and 20.0 Pa or more is most preferable.

  The upper limit of the storage elastic modulus G ′ (1) is not particularly set, but is 100.0 Pa or less in consideration of ease of drinking in the case of a beverage. The amount of the cellulose composite that can sufficiently obtain suspension stability when it is 100.0 Pa or less (depending on the beverage, for example, a favorite beverage such as coffee, cocoa, and tea, or 0.1 to 0.1 for peanut beverages, etc. 1.0 mass%) is preferable because the drinking mouth is light.

<Maintenance rate of storage elastic modulus of cellulose composite>
Next, the maintenance modulus of the storage elastic modulus of the cellulose composite of the present invention will be described.
The cellulose composite of the present invention preferably has a storage modulus retention of 92.2% or less in a 1.0% by mass pure water dispersion obtained by dispersing the composite in pure water.

The maintenance modulus of the storage elastic modulus is a value calculated by the following formula.
Storage modulus maintenance rate (%) = G ′ (20) × 100 / G ′ (1)
G ′ (20): Storage elastic modulus value when strain is 20% G ′ (1): Storage elastic modulus value when strain is 1% As the retention rate of storage elastic modulus is smaller, the water dispersion of the cellulose composite It means that the network structure in the body is easily broken by stress. The more easily the network structure collapses due to stress, the better the throat and mouthfeel of food and drink containing cellulose composites. In addition, as the network structure is more easily broken, the texture change increases from the moment the food / beverage product containing the cellulose composite is included in the mouth until it is swallowed, and a plurality of food textures can be enjoyed.

  The storage modulus of the storage modulus of the cellulose composite is preferably 92.2% or less. If it is 92.2% or less, it becomes a beverage excellent in throating and mouthfeel. Moreover, a plurality of textures can be enjoyed. The maintenance modulus of the storage elastic modulus is more preferably 90.0% or less, further preferably 80.0% or less, and most preferably 77.0% or less. Although a minimum is not set in particular, it is 30.0% or more. If it is 30.0% or more, it is possible to enjoy a throat that is sufficient as a beverage.

  The cellulose composite of the present invention preferably has a storage modulus maintenance rate of 92.2% or less and a storage modulus G ′ (1) of 4.3 Pa or more. That is, a beverage using a cellulose composite having a low storage elastic modulus G ′ (1) is excellent in throat and mouthfeel, but is inferior in suspension stability. Beverages using the cellulose composite described in the prior art document with a high storage elastic modulus G ′ (1) and a high storage elastic modulus retention rate are excellent in suspension stability, but poor in throat and mouthfeel, and change in texture Nor. On the other hand, the beverage using the cellulose composite of the present invention having a high storage elastic modulus G ′ (1) and a low storage elastic modulus retention rate is excellent in suspension stability and can be used over the throat and in the mouth. It can be set as the drink which is excellent and has a texture change.

<Loss tangent of cellulose composite (tan δ)>
Next, the loss tangent (tan δ) of the cellulose composite of the present invention will be described.
The cellulose composite of the present invention has a loss tangent (tan δ) at a strain of 1% at 25 ° C. of less than 0.42 in a 1.0% by mass pure water dispersion obtained by dispersing the composite in pure water. It is preferable that

  The loss tangent (tan δ) is a value represented by loss tangent = loss elastic modulus / storage elastic modulus. The larger the value, the stronger the tendency of viscosity. The smaller the loss tangent (tan δ), the better the stickiness of the beverage containing the cellulose composite.

  In the present invention, the loss tangent (tan δ) is a value obtained by dynamic viscoelasticity measurement of an aqueous dispersion in which a cellulose composite is dispersed in pure water. That is, the ratio of the loss elastic modulus and the storage elastic modulus inside the cellulose composite network structure when a specific strain is applied to the aqueous dispersion is expressed as a loss tangent (tan δ).

  As a method for measuring the loss tangent (tan δ), first, the cellulose composite was treated with a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”) treatment condition: 15,000 rpm × 5 minutes. ) To be dispersed in pure water to prepare a 1.0 mass% aqueous dispersion. The obtained aqueous dispersion is allowed to stand at room temperature for 3 hours. The strain dependence of the stress of this water dispersion was measured using a viscoelasticity measuring device (TA Instruments, ARES-G2 type, geometry: Double Wall Couette type, temperature: 25.0 ° C constant, angular velocity: 20 rad / sec, strain: Sweeping within a 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 10 minutes, measurement is started in the Dynamic Strain mode). The loss tangent in the present invention is the ratio of the loss elastic modulus to the storage elastic modulus at a strain of 1% on the strain-stress curve obtained by the above measurement. The smaller the loss tangent value, the more elastic the structure of the aqueous dispersion formed by the cellulose composite.

  The loss tangent of the cellulose composite is preferably less than 0.42, more preferably 0.35 or less, further preferably 0.30 or less, and most preferably 0.26 or less.

  The lower limit of the loss tangent is not particularly set, but is preferably 0.01 or more.

  The cellulose composite of the present invention preferably has a loss tangent of less than 0.42 and a storage elastic modulus G ′ (1) of 4.3 Pa or more. That is, a beverage using a cellulose composite having a low storage elastic modulus G ′ (1) does not feel sticky but has poor suspension stability. A beverage using the cellulose composite described in the prior art document having a high storage elastic modulus G ′ (1) and a high loss tangent is excellent in suspension stability but feels sticky. In contrast, a beverage using the cellulose composite of the present invention having a high storage elastic modulus G ′ (1) and a low loss tangent is excellent in suspension stability and can be made a beverage that does not feel sticky. .

  The cellulose composite of the present invention has a storage modulus maintenance rate of 92.2% or less, a loss tangent of less than 0.42, and a storage modulus G ′ (1) of 4.3 Pa or more. preferable. Beverages using the cellulose composite of the present invention having a high storage elastic modulus G ′ (1), a low storage elastic modulus retention rate, and a low loss tangent are excellent in suspension stability, and can be used over the throat and in the mouth. It can be made into a beverage that is excellent, has a texture change, and does not feel sticky.

<Colloidal cellulose composite content of cellulose composite>
The cellulose composite of the present invention preferably contains 50% by mass or less of the colloidal cellulose composite. The colloidal cellulose composite content here is a cellulose composite made into a pure water suspension at a concentration of 0.5% by mass, a high shear homogenizer (trade name “Excel Auto Homogenizer, manufactured by Nippon Seiki Co., Ltd.). ED-7 ”treatment conditions: Dispersed at 15,000 rpm × 5 minutes) and centrifuged (trade name“ 6800 type centrifuge ”rotor type RA-400, manufactured by Kubota Corporation), treatment conditions: centrifuge The supernatant obtained by centrifugation at a force of 39200 m ² / s for 10 minutes is collected, and this supernatant is further centrifuged at 116000 m ² / s for 45 minutes.) The solid content (cellulose and anion) remaining in the supernatant after centrifugation is collected. The percentage of the mass of the active polysaccharide. When the content of the colloidal cellulose composite is 50% by mass or less, it becomes a cellulose composite that is excellent in the mouth and the throat. Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, Most preferably, it is 20 mass% or less. The lower the colloidal cellulose complex content is, the better the mouth and throat is. Therefore, the lower limit is not particularly limited, but the preferred range is 1% by mass or more.

<Method for producing cellulose composite>
Next, the manufacturing method of the cellulose composite of this invention is demonstrated.
The cellulose composite of the present invention can be obtained by a production method including a co-treatment step in which a composition containing cellulose and an anionic polysaccharide is sufficiently kneaded to composite each component. In the co-processing step, it is preferable to impart mechanical shearing force to the kneaded material containing cellulose and anionic polysaccharide to make the cellulose finer and to complex the anionic polysaccharide on the cellulose surface. At that time, a water-soluble gum other than the anionic polysaccharide, a hydrophilic substance, and other additives may be added to the composition. You may have a drying process after the above-mentioned co-processing process as needed. The method for producing a cellulose composite of the present invention may be a method that does not include a drying step or a method that includes a drying step as long as the method includes the above-described coprocessing step.

  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, it is preferable to knead while removing this 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.

  The lower the kneading temperature, the better the deterioration of the anionic polysaccharide is suppressed, and the resulting storage modulus G ′ (1) of the cellulose composite becomes higher. The kneading temperature is preferably 0 to 100 ° C, more preferably 90 ° C or less, particularly preferably 70 ° C or less, further preferably 60 ° C or less, and most preferably 50 ° C or less. In order to maintain the above kneading temperature under high energy, it is preferable to devise slow heating such as jacket cooling and heat dissipation.

  The ratio of the solid content excluding moisture during kneading is preferably 20% by mass or more. Kneading in a semi-solid state where the viscosity of the kneaded material is high is preferable because the kneaded material does not become loose, the kneading energy described below is easily transmitted to the kneaded material, and compounding is promoted. The solid content at the time of kneading is more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% 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. Furthermore, in order to bring the solid content of the kneaded material into the above range, the required amount of water to be added to the composition may be added before the co-processing step or may be added in the middle of the co-processing step. You may do both.

  The multi-stage combination in the present invention will be described.

  Multi-stage complexing means that the ionic polysaccharide is added to cellulose in three or more stages in the above-mentioned co-processing step and wet-co-processed. It is preferable to perform the addition of the ionic polysaccharide in a plurality of times because the balance between the refinement of cellulose and the complexing with the ionic polysaccharide is significantly improved. That is, it is preferable because anionic polysaccharides can be effectively combined with the cellulose surface newly emerged by refining the cellulose surface. Moreover, since the thickness of the layer of the anionic polysaccharide complexed on the cellulose surface becomes uniform, it is preferable.

  As multi-stage complexation, it is preferable to add an anionic polysaccharide in an amount equivalent to one-third of the total amount in multiple stages. More preferably, one-tenth amount is added uniformly in multiple stages, and it is most preferable to add one-twentieth amount equally in multiple stages. Although the upper limit is not particularly limited, it is preferable to add 1/100 of the realistic range equally in multiple stages because of the complexity of work. The amount added to each time does not need to be equal, for example, the amount may be increased each time the times are repeated, or may be decreased each time the times are repeated. Moreover, although the interval of anionic polysaccharide addition of each time can be set arbitrarily, it is preferable to set it as 10 to 1000 second, for example.

The shear rate in the present invention will be described. The shear rate is, for example, calculated by the following formula in a biaxial extruder.
Shear rate (γ) = πDN / h
D: Rotor outer diameter (mm)
N: Rotor speed (1 / sec)
h: Tip clearance (mm)

  In the present invention, the shear rate is preferably 740 (1 / Sec) or more. When the shear rate is 740 (1 / Sec) or more, the grindability of the kneaded product is increased, the complexing of cellulose and anionic polysaccharide is promoted, and the storage elastic modulus G ′ (1) is 4 It becomes possible to easily obtain a cellulose composite of 3 Pa or more. In particular, complexing with sodium carboxymethyl cellulose having high viscosity efficiently proceeds as an anionic polysaccharide. Preferably, the shear rate is 1,000 (1 / Sec) or more, more preferably 1,500 (1 / Sec) or more, and most preferably 3,000 (1 / Sec) or more. . The higher the shear rate, the easier it is for the composite to proceed. However, if the shear rate is too large, the equipment becomes industrially excessive and the equipment is excessively loaded, so the upper limit of the shear rate is 10,000 ( 1 / Sec) is preferable.

  Cellulose and anionic polysaccharide are preferably co-treated at the above shear rate for 5 minutes or more. By co-processing for 5 minutes or more, the grindability imparted to the kneaded product is increased, the complexing of cellulose and anionic polysaccharide is promoted, and the suspension stability of the neutral cellulose complex is improved. Preferably, it is 10 minutes or more, more preferably 20 minutes or more, and most preferably 25 minutes or more. The longer the co-processing time, the more the compounding progresses and the value of the storage elastic modulus G ′ (1) increases. However, if the co-processing time is too long, the value of the storage elastic modulus G ′ (1) is reversed. Decrease. Therefore, after investigating the relationship of the storage elastic modulus G ′ (1) to the coprocessing time, it is preferable to operate within the coprocessing time in which the value of the storage elastic modulus G ′ (1) is 4.3 Pa or more.

  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 200 Wh / kg or more. If the kneading energy is 200 Wh / kg or more, the grindability imparted to the kneaded product is high, and complexing of cellulose and anionic polysaccharide, or cellulose, anionic polysaccharide, and other water-soluble gums is possible. The value of the storage elastic modulus G ′ (1) is improved. More preferably, it is 500 Wh / kg or more, More preferably, it is 1,000 Wh / kg or more, Most preferably, it is 1,500 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 10,000 Wh / kg.

  The raw material charging method during kneading is a method in which cellulose and anionic polysaccharide are simultaneously charged and compounded, a method in which cellulose alone is kneaded and then anionic polysaccharide is charged and compounded, an anionic polysaccharide alone The method of adding cellulose and combining it after kneading is most preferable, but the most preferable method is to simultaneously add cellulose and anionic polysaccharide to make them complex, and then knead them further to advance the composite. . Moreover, you may perform the above-mentioned method in multistep, respectively.

  In obtaining the cellulose composite of the present invention, when drying the kneaded product obtained from the above-mentioned co-processing step, such as shelf-type drying, spray drying, belt drying, fluid bed drying, freeze drying, microwave drying, etc. A known 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% by mass 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 mass% or less, Most preferably, it is 10 mass% or less. Further, by setting the water content to 1% by mass or more, dispersibility does not deteriorate due to excessive drying. More preferably, it is 1.5 mass% 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 grind so as to pass through a sieve having an opening of 425 μm and to have an average particle size (weight average particle size) of 10 to 250 μm. In these dry powders, fine particles of the cellulose composite are aggregated to form secondary aggregates. This secondary aggregate is disintegrated when stirred in water and dispersed in the above-mentioned cellulose composite fine particles. The apparent weight average particle size of the secondary agglomerates is 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 JIS standard sieve (Z8801-1987). Is the cumulative weight 50% particle size in the particle size distribution obtained by.

  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 neutral, 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.

<Protein>
The protein in the present invention is a polymer compound mainly composed of a polypeptide comprising L-α-amino acid. Proteins can be divided into simple proteins consisting only of amino acids and complex proteins containing nucleic acids, phosphates, lipids, sugars, metals, etc. In the present invention, either one may be used alone, You may use both together. Proteins are classified into fibrous proteins and globular proteins based on their molecular shapes. In the present invention, either one may be used alone, or both may be used in combination.

  Foods rich in protein include meat, seafood, potatoes, cereals, beans, dairy products, eggs, tree nuts, mushrooms, etc., and proteins derived from potatoes, cereals, beans, dairy products, tree nuts, mushrooms Is suitable for beverages. In particular, proteins derived from cereals, beans, dairy products and nuts are preferred, and proteins derived from cereals, dairy products and nuts are more preferred. Examples of cereals include wheat, barley, oats, wheat, rye, glutinous, glutinous, naked wheat, oats, rice, brown rice, buckwheat, corn, sweet potato, and chick. Examples of dairy products include milk, skim milk powder, whole milk powder, cheese, butter, whey and the like. Examples of nuts include peanuts, cashews, almonds, macadamia nuts, pistachios, walnuts, pine nuts, chestnuts, and ginkgo.

<Oats>
The oat in the present invention is a plant belonging to the genus Oataceae. Although it may be called oats, oats, oats, maracas wheat and oats as aliases, any of them may be used in the present invention. In the present invention, oats may be used before threshing, after threshing, after milling with pressed wheat, cracked wheat, etc., shaped into flakes, or enzymatically decomposed. When used in beverages, the oat particle size is preferably 1 cm or less. From the relationship between ease of drinking and throat, 5 mm or less is more preferred, 3 mm or less is more preferred, and 1 mm or less is most preferred. As a compounding quantity in a drink, it is preferable that 0.1 mass% or more of oats is included. Sufficient nutrition can be replenished if it contains 0.1 mass% or more. From the viewpoint of nutritional supplementation, 1.0% or more is more preferable, 2.5% or more is further preferable, and 4.0% or more is most preferable. The upper limit is not particularly set, but is preferably 10.0% or less from the viewpoint of the throat of the beverage.

<Protein content>
The high protein-containing beverage in the present invention preferably contains 0.3% by mass or more of protein. By containing 0.3% by mass or more of protein, a sufficient nutritional supplement effect can be expected. More preferably, it is 0.5% or more, More preferably, it is 1.0% or more, More preferably, it is 1.2% or more, More preferably, it is 1.5% or more, More preferably, it is 2. It is 0% or more, and most preferably 5.0% or more. The upper limit is preferably 10.0% by mass or less from the viewpoint of the viscosity of the beverage.

<Application>
The cellulose composite of the present invention can be used for various foods. Examples include beverages such as coffee, tea, matcha, cocoa, juice, and juice, milk, processed milk, lactic acid bacteria, soy milk, and other nutritional drinks, calcium-enriched drinks, peanut drinks, oat drinks, and other nutritional enhancements. Beverages and beverages including dietary fiber-containing beverages, ice cream, ice milk, soft cream, ice shakes such as milk shake, sherbet, butter, cheese, yogurt, coffee whitener, whipping cream, custard cream, pudding Dairy products such as mayonnaise, margarine, spreads, fats and other processed foods such as spreads, shortenings, various soups, stews, sauces, sauces, dressings and other seasonings, various kneaded spices, such as kneaded rice, jam, Various fillings typified by flower paste, various ants and jelly Mu-gel / paste-like foods, bread, noodles, pasta, pizza, cereal foods including various premixes, candy, cookies, biscuits, hot cakes, chocolate, candy Representative fishery products such as ham, sausage, hamburg, etc., cream croquettes, Chinese annuities, gratin, gyoza etc. Tube fluid foods. Among these, in particular, in a composition having a high concentration of components, the problem of texture is solved by its smooth mouth and throat, so it should be used for a wide range of food applications other than those described above. Is also possible.

  In these applications, the cellulose composite of the present invention has a texture improving agent, a suspension stabilizer, an emulsion stabilizer, a thickening stabilizer, a foam stabilizer, a cloudy agent, a tissue imparting agent, a fluidity improving agent, a retention agent. It acts as a low calorie base such as a form, a water separation inhibitor, a dough modifier, a powdered base, a dietary fiber base, and a fat and oil substitute. In addition, the effects of the present invention can be exhibited even when the above-mentioned foods are different in form such as retort foods, powdered foods, frozen foods, foods for microwave ovens, or processing methods prepared at the time of use.

  When the cellulose composite of the present invention and the “thickening polysaccharide” are used in combination, the suspension stability is improved by the interaction of the cellulose composite and the thickening polysaccharide as compared with the case where the cellulose composite is used alone. The thickening polysaccharides include locust bean gum, guar gum, casein and casein sodium, tamarind seed gum, quince seed gum, karaya gum, chitin, chitosan, gum arabic, tragacanth gum, gati gum, arabinogalactan, agar, carrageenan (ι, λ , Κ), alginic acid and its salts, propylene glycol alginate, fur celerane, pectin, tara gum, almond gum, aeromonas gum, azotobacter vinelandie gum, amased gum, welan gum, psyllium seed gum, xanthan gum, curdlan, pullulan, gellan gum, gelatin, water soluble And soy polysaccharides. These thickening polysaccharides may be used alone, or a plurality may be selected. Among the above-mentioned thickening polysaccharides, carrageenan, xanthan gum and gellan gum are preferable. These are preferably used in combination with the cellulose composite and blended in the beverage in an amount of 0.001% by mass or more. The addition amount of the thickening polysaccharide is preferably 0.1% by mass or less because it is excellent in passing through the throat. More preferably, it is 0.05 mass% or less, More preferably, it is 0.025 mass% or less.

  When the cellulose composite of the present invention is used in food, the same equipment as that generally used in the production of each food is used, and in addition to the main ingredients, a flavor, a pH adjuster, an increase What is necessary is just to mix | blend with a viscosity stabilizer, salts, saccharides, fats and oils, protein, an emulsifier, a sour agent, a pigment | dye etc., and to perform operations, such as mixing, kneading | mixing, stirring, emulsification, and heating.

  In particular, since the cellulose composite of the present invention has a high effect of preventing gelation of beverage components, it is particularly suitable as a suspension stabilizer for beverages containing a large amount of protein. It is particularly suitable when storing at high temperatures.

<Method for adding cellulose composite>
The following method is mentioned as a method of adding the cellulose composite of this invention to food-drinks. 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 colorant, a flavoring agent, a sour agent and a thickener.

  In addition, when the dry powder of the cellulose composite is dispersed in an aqueous medium, the suspension stability of the cellulose composite is better when the cellulose composite is once dispersed in water and then added to the desired 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 extruder, a turbulizer, or the like can be used. Two or more kneaders may be used in combination. Dispersion is easier when performed while heating.

<Amount added to food and drink>
Although there is no restriction | limiting in particular as addition amount of the cellulose composite with respect to food-drinks, For example, in coffee, a cocoa, a peanut drink, an oat drink, 0.01 mass% or more is preferable. 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 0.05% by mass or more, more preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.5% by mass or more, Preferably it is 1.0 mass% or more, Most preferably, it is 2.5 mass% or more. By making the addition amount of the cellulose composite 5% by mass or less, aggregation or separation is not caused, and also 5% by mass or less is preferable from the viewpoint of drinking mouth (ease of drinking, rough tongue). .

<Sterilization of food and drink>
In the present invention, any sterilization method commonly used may be used for sterilization of food and drink. For example, sterilization methods usually used for food and drink include retort sterilization using an autoclave, UHT sterilization, electromagnetic wave sterilization, ultraviolet sterilization, radiation (X-ray, gamma ray) sterilization, filter sterilization, and ozone sterilization. In particular, when UHT sterilization is used as a beverage sterilization method, it tends to be preferred because it becomes a beverage with excellent flavor even after sterilization. In general, UHT sterilization is processed in the range of 120-145 ° C. and in the range of 1-60 minutes. In recent years, in the case of UHT sterilization, a hot pack in which a beverage is filled in a container in a state of 30 ° C. or higher after heat treatment is preferred. Since the hot pack can be filled in the container in a high temperature state, the risk of bacterial contamination is lower than in the case of filling after cooling, which is preferable from the viewpoint of hygiene. 40 degreeC or more is preferable, 50 degreeC or more is more preferable, 60 degreeC or more is still more preferable, and 70 degreeC or more is the most preferable. Although an upper limit is not set in particular, 100 degrees C or less is preferable from a viewpoint of the flavor of a drink. However, some high protein-containing beverages typified by oat-containing beverages have a problem that gel is generated when hot-packing is performed.

  The term “gel” as used herein refers to a product obtained by aggregating water-insoluble components other than the cellulose composite in an aqueous medium, for example, a protein or a functional food material. Specifically, it means a material that does not pass through a sieve having a mesh size of 5 mm under normal temperature and normal pressure. However, a component having a particle size of 5 mm or more before aggregation, for example, a nut or fruit of 5 mm or more, does not correspond to the gel referred to in this specification.

<Insoluble component>
The cellulose composite of the present invention is particularly suitable for a neutral food or drink containing 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 sieve with an opening of 5 mm, and further preferably passes through a sieve with an opening of 2 mm. The water-insoluble component becomes unstable in neutrality, but excellent suspension stability can be obtained by adding the cellulose composite of the present invention.

  Water-insoluble components include protein in foods and beverages, lactic acid bacteria contained in fruit scraps, lactic acid bacteria beverages, pulp content in vegetable juice beverages, milk calcium, calcium carbonate, beta glucan, protein (soy protein, milk Proteins, 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 water such as ceramide compounds Examples include functional food materials with low specific gravity.

  The functional food material described above is preferably added in an amount of 0.01% by mass or more based on the daily intake of the beverage and the effect of the material. More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more.

<Applications other than food>
The cellulose composite of the present invention uses a characteristic that the network structure in the aqueous dispersion of the cellulose composite is firm when there is no stress, but easily collapses due to stress, in addition to food and drink, syrups, liquids, and Pharmaceutical products such as ointments, cosmetics such as lotions, emulsions, detergents, food / industrial detergents and treatment materials, household (clothing, kitchen, dwelling, tableware, etc.) detergent materials, paints, pigments, ceramics , Aqueous latex, for emulsification (polymerization), for agricultural chemicals, for fiber processing (refining agents, dyeing aids, softeners, water repellents), antifouling agents, admixtures for concrete, for printing inks, for lubricating oils, Industrial products such as antistatic agents, antifogging agents, lubricants, dispersants, and deinking agents can be used as applications.

  The invention is illustrated by the following examples. However, these do not limit the scope of the present invention.

<Method for measuring average polymerization degree of cellulose>
The average degree of polymerization of cellulose was measured by a reduced specific viscosity method using a copper ethylenediamine solution defined in the crystalline cellulose confirmation test (3) of “14th revised Japanese pharmacopoeia” (published by Yodogawa Shoten).

<Viscosity of sodium carboxymethyl cellulose (CMC-Na)>
(1) CMC-Na powder at 1.0% by mass, high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7” treatment condition: 15,000 rpm × 5 minutes) Was used to prepare an aqueous solution.
(2) About 3 hours after dispersion | distribution (25 degreeC preservation | save) about the obtained aqueous solution, it set to the B-type viscosity meter (rotor rotation speed 60rpm), left for 60 seconds, rotated for 30 seconds, and measured. However, the optimal rotor was used according to the viscosity.

<Degree of substitution of sodium carboxymethyl cellulose (CMC-Na)>
(1) 0.5 g of a sample (anhydride) was precisely weighed, wrapped in filter paper and incinerated in a magnetic crucible.
(2) After cooling, this was transferred to a 500 mL beaker, and about 250 mL of water and 35 mL of 0.05 M sulfuric acid were added and boiled for 30 minutes. This was cooled, phenolphthalein indicator was added, excess acid was back titrated with 0.1M potassium hydroxide, and the following formula was calculated.
A = ((af−bf1) / sample anhydride (g)) − alkalinity (or + acidity)
Degree of substitution = (162 × A) / (10000-80A)
here,
A: Amount of 0.05 M sulfuric acid consumed by alkali in 1 g of sample (mL)
a: Amount of 0.05 M sulfuric acid used (mL)
f: titer of 0.05M sulfuric acid b: titration volume of 0.1M potassium hydroxide (mL)
f1: 0.1M Potassium hydroxide titer 162: Glucose molecular weight 80: CH ₂ COONa-H molecular weight Alkalinity (or acidity) measurement method: 1 g of sample (anhydride) was accurately measured in a 300 mL flask, About 200 mL of water was added and dissolved. To this was added 5 mL of 0.05 M sulfuric acid, boiled for 10 minutes, cooled, added with phenolphthalein indicator, and titrated with 0.1 M potassium hydroxide (SmL). At the same time, a blank test was performed (BmL), and the following formula was used.
Alkalinity = ((B−S) × f) / sample anhydride (g)
Here, f is the titer of 0.1M potassium hydroxide. When the value of (B−S) × f was (−), the acidity was determined.

<Storage elastic modulus of cellulose composite>
(1) The cellulose composite is dispersed 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 1.0% by weight pure water dispersion was prepared. The obtained aqueous dispersion was allowed to stand at 25 ° C. for 3 hours.
(2) Measure the strain dependence of the stress of this water dispersion with a viscoelasticity measuring device (TA Instrument, ARES-G2 type, geometry: Double Wall Couette type, strain is swept in the range of 1 → 794%) did. In the present invention, the storage elastic modulus G ′ (1) is a value of 1% strain on the strain-stress curve obtained by the above measurement.

<Maintenance rate of storage elastic modulus of cellulose composite>
(1) The cellulose composite is dispersed 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 1.0% by weight pure water dispersion was prepared. The obtained aqueous dispersion was allowed to stand at 25 ° C. for 3 hours.
(2) Measure the strain dependence of the stress of this water dispersion with a viscoelasticity measuring device (TA Instrument, ARES-G2 type, geometry: Double Wall Couette type, strain is swept in the range of 1 → 794%) And calculated by the following formula.
Storage modulus maintenance rate (%) = G ′ (20) × 100 / G ′ (1)
G ′ (20): Storage elastic modulus value when strain is 20% G ′ (1): Storage elastic modulus value when strain is 1%

<Loss tangent of cellulose composite (tan δ)>
(1) The cellulose composite is dispersed 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 1.0% by weight pure water dispersion was prepared. The obtained aqueous dispersion was allowed to stand at 25 ° C. for 3 hours.
(2) Measure the strain dependence of the stress of this water dispersion with a viscoelasticity measuring device (TA Instrument, ARES-G2 type, geometry: Double Wall Couette type, strain is swept in the range of 1 → 794%) did. In the present invention, the loss tangent (tan δ) is the ratio of the loss elastic modulus and storage elastic modulus at a strain of 1% on the strain-stress curve obtained by the above measurement.

Example 1
After cutting commercially available dissolving pulp (DP pulp), hydrolyzing in 2.5 mol / L hydrochloric acid at 105 ° C for 15 minutes, washing with water and filtering to produce wet cake-like cellulose with a solid content of 50% by mass (The average degree of polymerization was 220).

  Next, the wet cake-like cellulose and commercially available CMC-Na (viscosity of 1% dissolved solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and Compound 15 (manufactured by DSM Xplore) is prepared with cellulose. (Hereinafter referred to as MCC) / CMC-Na mass ratio (based on a value obtained by measuring the weight and the amount of moisture and converting to the weight of the component not containing moisture. Using a scientific laboratory, model: FD-240), measurement was performed under the conditions of 105 ° C., Automatic mode, and monitoring time of 60 seconds.In this specification, unless otherwise noted, other components and cellulose The same applies to the composite.) Was added so as to be 82.5 / 17.5, and water was added so that the solid content was 50% by mass. CMC-Na is not added all at once, but after adding 1/3 of the total amount, kneading for 30 seconds, and then adding 1/3 of the total amount again and mixing for 30 seconds until the entire amount is charged. The method was repeated in a repeated manner.

  The composition was kneaded at a shear rate of 3925 (1 / Sec) for a total of 22 minutes to obtain a cellulose composite A. The measured value of kneading energy was 2200 Wh / kg. As for the kneading temperature, the temperature of the kneaded material was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite A has a storage elastic modulus G ′ (1) of 16.4 Pa, a colloidal cellulose composite content of 10% by mass, and a storage elastic modulus maintenance ratio of 83.2. The loss tangent (tan δ) was 0.36. The results are shown in Table 1.

(Example 2)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and a commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass. CMC-Na is not added all at once, but after adding 1 / 15th of the total amount, kneading for 30 seconds, and then adding 1 / 15th of the total amount again and kneading for 30 seconds, the whole amount is added. The method was repeated in a repeated manner.

  The composition was kneaded at a shear rate of 3925 (1 / Sec) for a total of 20 minutes to obtain a cellulose composite B. The measured value of kneading energy was 2000 Wh / kg. As for the kneading temperature, the temperature of the kneaded material was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite B has a storage elastic modulus G ′ (1) of 19.5 Pa, a colloidal cellulose composite content of 8 mass%, and a storage elastic modulus maintenance factor of 79.8. The loss tangent (tan δ) was 0.29. The results are shown in Table 1.

Example 3
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and a commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass. CMC-Na is not added all at once, but after adding 1/25 of the total amount, kneading for 30 seconds, then adding 1/25 of the total amount again and mixing for 30 seconds is performed. The method was repeated in a repeated manner.

  The composition was kneaded for 18 minutes at a shear rate of 3925 (1 / Sec) to obtain a cellulose composite C. The measured value of kneading energy was 1800 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite C has a storage elastic modulus G ′ (1) of 23.3 Pa, a content of the colloidal cellulose composite of 5 mass%, and a storage elastic modulus maintenance factor of 75.8. The loss tangent (tan δ) was 0.26. The results are shown in Table 1.

(Example 3A)
The cellulose composite C obtained in Example 3 was added to ion-exchanged water so as to have a concentration of 1.0%, and the mixture was stirred at 10,000 rpm for 30 minutes using a homomixer MARK II (manufactured by Primics). Slurried. The dryer had a chamber diameter of 3 m and a height of 4 m (manufactured by Okawara Chemical Industries Co., Ltd.), and the slurried cellulose composite C was powdered under the following drying conditions. The disc is an M-type pin disc, the rotational speed is 20,000 rpm, the slurry throughput is 49.8 kg / hr, the temperature is 25 ° C., the inlet temperature is 180 ° C., the outlet temperature is 80 ° C., and the air flow rate is 1566 m ³ / h. Met.

  Cellulose composite CA which is the obtained dried product (powder) has a storage elastic modulus G ′ of 23.2 Pa, a content of colloidal cellulose composite of 5 mass%, and a storage elastic modulus retention rate. The loss tangent (tan δ) was 0.26, which was the same physical property as the cellulose composite C before spray drying.

(Example 3B)
Cellulose composite C obtained in Example 3 was manually reduced to a diameter of about 2 mm, placed in a stainless steel container, and shelf-dried. The dryer is a ventilated oven (Espec Corp. PV-211). Drying conditions were as follows: 100% damper for 30 minutes. 30 g of the dried product was pulverized with a miller (Iwatani IFM-800DG) for 5 seconds, and passed through a sieve opening of 180 μm.

  The obtained cellulose composite CB which is a dried product (powder) has a storage elastic modulus G ′ of 23.1 Pa, a colloidal cellulose composite content of 5 mass%, and maintains the storage elastic modulus. The rate was 75.5% and the loss tangent (tan δ) was 0.26, which was the same physical property as the cellulose composite C before spray drying.

(Example 4)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and a commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass.

  The above composition was kneaded at a shear rate of 745 (1 / Sec) for 22 minutes to obtain a cellulose composite D. The measured value of kneading energy was 250 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite D has a storage elastic modulus G ′ (1) of 4.4 Pa, a colloidal cellulose composite content of 49 mass%, and a storage elastic modulus maintenance factor of 92.1. The loss tangent (tan δ) was 0.45. The results are shown in Table 1.

(Example 5)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and a commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass.

  The composition was kneaded at a shear rate of 3925 (1 / Sec) for a total of 22 minutes to obtain a cellulose composite E. The measured value of kneading energy was 1500 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite E has a storage elastic modulus G ′ (1) of 13.4 Pa, a content of the colloidal cellulose composite of 25% by mass, and a storage elastic modulus maintenance factor of 89.1. The loss tangent (tan δ) was 0.40. The results are shown in Table 1.

(Example 6)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and a commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass.

  The composition was kneaded at a shear rate of 7975 (1 / Sec) for 22 minutes to obtain a cellulose composite F. The measured value of kneading energy was 3500 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite F has a storage elastic modulus G ′ (1) of 15.3 Pa, a colloidal cellulose composite content of 15% by mass, and a storage elastic modulus maintenance factor of 87.2. The loss tangent (tan δ) was 0.26. The results are shown in Table 1.

(Example 7)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and a commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (measured by weight and water content, based on the value converted to the weight of the component not containing water) is 90/10, and the solid content is 50% by mass. Water was added. CMC-Na is not added all at once, but after adding 1/25 of the total amount, kneading for 30 seconds, then adding 1/25 of the total amount again and mixing for 30 seconds is performed. The method was repeated in a repeated manner.

  The composition was kneaded at a shear rate of 3925 (1 / Sec) for 18 minutes to obtain a cellulose composite G. The measured value of kneading energy was 700 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite G has a storage elastic modulus G ′ (1) of 14.5 Pa, a colloidal cellulose composite content of 20% by mass, and a storage elastic modulus maintenance factor of 93.0. The loss tangent (tan δ) was 0.22. The results are shown in Table 1.

(Example 8)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and a commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on the value of the weight and moisture content measured and converted to the weight of the component without water) is 75/25, and the solid content is 50% by mass. Water was added. CMC-Na is not added all at once, but after adding 1/25 of the total amount, kneading for 30 seconds, then adding 1/25 of the total amount again and mixing for 30 seconds is performed. The method was repeated in a repeated manner.

  The above composition was kneaded at a shear rate of 3925 (1 / Sec) for a total of 18 minutes to obtain a cellulose composite H. The measured value of kneading energy was 2500 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite H has a storage elastic modulus G ′ (1) of 12.5 Pa, a colloidal cellulose composite content of 30% by mass, and a storage elastic modulus maintenance factor of 69.2. The loss tangent (tan δ) was 0.33. The results are shown in Table 1.

Example 9
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 1500 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass. CMC-Na is not added all at once, but after adding 1/25 of the total amount, kneading for 30 seconds, then adding 1/25 of the total amount again and mixing for 30 seconds is performed. The method was repeated in a repeated manner.

  The composition was kneaded at a shear rate of 3925 (1 / Sec) for 18 minutes to obtain a cellulose composite I. The measured value of kneading energy was 1600 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite I has a storage elastic modulus G ′ (1) of 17.8 Pa, a colloidal cellulose composite content of 9% by mass, and a storage elastic modulus maintenance factor of 81.2. The loss tangent (tan δ) was 0.23. The results are shown in Table 1.

(Example 10)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity of 500 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compound 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass. CMC-Na is not added all at once, but after adding 1/25 of the total amount, kneading for 30 seconds, then adding 1/25 of the total amount again and mixing for 30 seconds is performed. The method was repeated in a repeated manner.

  The composition was kneaded at a shear rate of 3925 (1 / Sec) for 18 minutes to obtain a cellulose composite J. The measured value of kneading energy was 1000 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite J has a storage elastic modulus G ′ (1) of 13.8 Pa, a colloidal cellulose composite content of 25 mass%, and a storage elastic modulus maintenance factor of 82.3. The loss tangent (tan δ) was 0.20. The results are shown in Table 1.

(Example 11)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 200 mPa · s, degree of etherification 1.3) are prepared, and Compound 15 (manufactured by DSM Xplore) is used as MCC. / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass. CMC-Na is not added all at once, but after adding 1/25 of the total amount, kneading for 30 seconds, then adding 1/25 of the total amount again and mixing for 30 seconds is performed. The method was repeated in a repeated manner.

  The composition was kneaded at a shear rate of 3925 (1 / Sec) for 18 minutes to obtain a cellulose composite K. The measured value of the kneading energy was 500 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite K has a storage elastic modulus G ′ (1) of 9.8 Pa, a colloidal cellulose composite content of 35 mass%, and a storage elastic modulus maintenance factor of 89.2. %, And loss tangent (tan δ) was 0.19. The results are shown in Table 1.

(Example 12)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, degree of etherification 0.7) are prepared, and Compound 15 (manufactured by DSM Xplore) is prepared with MCC. / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass. CMC-Na is not added all at once, but after adding 1/25 of the total amount, kneading for 30 seconds, then adding 1/25 of the total amount again and mixing for 30 seconds is performed. The method was repeated in a repeated manner.

  The composition was kneaded at a shear rate of 3925 (1 / Sec) for 18 minutes to obtain a cellulose composite L. The measured value of the kneading energy was 280 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite L has a storage elastic modulus G ′ (1) of 22.2 Pa, a colloidal cellulose composite content of 5 mass%, and a storage elastic modulus maintenance factor of 76.0. The loss tangent (tan δ) was 0.25. The results are shown in Table 1.

(Example 13)
After cutting commercially available dissolving pulp (DP pulp), hydrolyzing in 2.5 mol / L hydrochloric acid at 105 ° C for 15 minutes, washing with water and filtering to produce wet cake-like cellulose with a solid content of 50% by mass (The average degree of polymerization was 220).
Next, the wet cake-like cellulose and commercially available CMC-Na (viscosity of 1% dissolved solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and Compound 15 (manufactured by DSM Xplore) is prepared with cellulose. (Hereinafter referred to as MCC) / CMC-Na mass ratio (based on a value obtained by measuring the weight and water content and converting to the weight of the component not containing water) is 82.5 / 17.5. And watered to a solid content of 50% by mass. CMC-Na is not added all at once, but after adding 1 / 50th of the total amount, kneading for 30 seconds, and then adding 1 / 50th of the total amount again and mixing for 30 seconds until the entire amount is charged The method was repeated in a repeated manner.

The composition was kneaded at a shear rate of 710 (1 / Sec) for a total of 32 minutes to obtain a cellulose composite M. The measured value of kneading energy was 350 Wh / kg. As for the kneading temperature, the temperature of the kneaded material was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.
The obtained cellulose composite M has a storage elastic modulus G ′ (1) of 8.2 Pa, a colloidal cellulose composite content of 35 mass%, and a storage elastic modulus maintenance factor of 90.5. The loss tangent (tan δ) was 0.41. The results are shown in Table 1.

(Comparative Example 1)
After cutting a commercially available DP pulp in the same manner as in the Examples, hydrolysis was performed in 2.5 mol / L hydrochloric acid at 105 ° C. for 15 minutes, followed by washing with water and filtration, and wet cake-like cellulose having a solid content of 50% by mass. (Average degree of polymerization was 220).

  Next, the wet cake-like cellulose and commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and Compounder 15 (manufactured by DSM Xplore) is used. The mass ratio of MCC / CMC-Na (measured based on the weight and moisture content and converted to the weight of the component without water) was 82.5 / 17.5, and the solid Water was added so that the content became 50% by mass. CMC-Na was not added all at once, but after adding half of the total amount, kneading for 30 seconds, and then adding half of the total amount again.

  The composition was kneaded at a shear rate of 710 (1 / Sec) for 25 minutes to obtain a cellulose composite N. The measured value of kneading energy was 180 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite N has a storage elastic modulus G ′ (1) of 0.8 Pa, a colloidal cellulose composite content of 56 mass%, and a storage elastic modulus maintenance factor of 102.3. The loss tangent (tan δ) was 0.99. The results are shown in Table 1.

(Comparative Example 2)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose and a commercially available CMC-Na (viscosity of 1% solution at 25 ° C., viscosity 3000 mPa · s, etherification degree 1.3) are prepared, and MCC is added to Compounder 15 (manufactured by DSM Xplore). / CMC-Na mass ratio (based on a value obtained by measuring a weight and a water content and converting to a weight of a component not containing water) is 82.5 / 17.5, solid content Water was added to 50% by mass.

  The composition was kneaded at a shear rate of 350 (1 / Sec) for 360 minutes to obtain a cellulose composite O. The measured value of kneading energy was 90 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite O has a storage elastic modulus G ′ (1) of 0.7 Pa, a colloidal cellulose composite content of 70 mass%, and a storage elastic modulus maintenance factor of 105.2. The loss tangent (tan δ) was 1.01. The results are shown in Table 1.

(Comparative Example 3)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose, commercially available CMC-Na (1) (viscosity of 1% solution at 25 ° C., viscosity of 50 mPa · s, etherification degree 0.7) and commercially available CMC-Na (2) (1 % Dissolved solution at 25 ° C. with a viscosity of 200 mPa · s and a degree of etherification of 1.3), and the mass ratio of MCC / CMC-Na (1) / CMC-Na (2) to Compounder 15 (manufactured by DSM Xplore) (Based on a value obtained by measuring the weight and the amount of water and converting to the weight of the component not containing water) is 85 / 7.5 / 7.5, and the solid content is 42% by mass. So watered. CMC-Na was not added all at once, but after adding half of the total amount, kneading for 30 seconds, and then adding half of the total amount again.

  The composition was kneaded at a shear rate of 710 (1 / Sec) for 18 minutes to obtain a cellulose composite P. The measured value of kneading energy was 200 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite P has a storage elastic modulus G ′ (1) of 4.2 Pa, a colloidal cellulose composite content of 68 mass%, and a storage elastic modulus maintenance factor of 99.6. The loss tangent (tan δ) was 0.42. The results are shown in Table 1.

(Comparative Example 4)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose, commercially available CMC-Na (1) (viscosity of 1% solution at 25 ° C., viscosity of 50 mPa · s, etherification degree 0.7) and commercially available CMC-Na (2) (1 % Dissolved solution at 25 ° C. with a viscosity of 200 mPa · s and a degree of etherification of 1.3), and the mass ratio of MCC / CMC-Na (1) / CMC-Na (2) to Compounder 15 (manufactured by DSM Xplore) (Based on a value obtained by measuring the weight and the amount of water and converting to the weight of the component not containing water) is 81 / 14.2 / 4.8, and the solid content is 42% by mass. So watered. CMC-Na was not added all at once, but after adding half of the total amount, kneading for 30 seconds and then adding half of the total amount again.

  The composition was kneaded at a shear rate of 710 (1 / Sec) for 45 minutes to obtain a cellulose composite Q. The measured value of kneading energy was 30 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite Q has a storage elastic modulus G ′ (1) of 0.7 Pa, a colloidal cellulose composite content of 64 mass%, and a storage elastic modulus maintenance factor of 98.0. The loss tangent (tan δ) was 1.00. The results are shown in Table 1.

(Comparative Example 5)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake cellulose and commercially available CMC-Na (1) (viscosity of 1% solution at 25 ° C., viscosity of 50 mPa · s, etherification degree 0.7) are prepared, and Compounder 15 (manufactured by DSM Xplore) The mass ratio of MCC / CMC-Na (based on a value obtained by measuring the weight and water content and converting to the weight of the component not containing water) is 85/15, and the solid content is 43. It added water so that it might become mass%.

  The composition was kneaded at a shear rate of 710 (1 / Sec) for 18 minutes to obtain a cellulose composite R. The measured value of kneading energy was 25 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite R has a storage elastic modulus G ′ (1) of 1.2 Pa, a colloidal cellulose composite content of 68 mass%, and a storage elastic modulus maintenance factor of 96.4. The loss tangent (tan δ) was 0.66. The results are shown in Table 1.

(Comparative Example 6)
After cutting the 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 cellulose having a solid content of 50% by mass (average polymerization degree) Was 220).

  Next, the wet cake-like cellulose, commercially available CMC-Na (1) (viscosity at 25 ° C. of 1% solution, 200 mPa · s, etherification degree 1.3) and commercially available CMC-Na (2) (1 % Solution at 25 ° C. with a viscosity of 50 mPa · s and a degree of etherification of 1.3), and a mass ratio of MCC / CMC-Na (1) / CMC-Na (2) to Compounder 15 (manufactured by DSM Xplore) (Measured based on the weight and the amount of water and converted to the weight of the component not containing water) was 92/2/6, and was added to a solid content of 42% by mass. .

  The composition was kneaded at a shear rate of 710 (1 / Sec) for 18 minutes to obtain a cellulose composite S. The measured value of kneading energy was 250 Wh / kg. As for the kneading temperature, the temperature of the kneaded product was directly measured using a thermocouple, and was 20 to 40 ° C. throughout the kneading.

  The obtained cellulose composite S has a storage elastic modulus G ′ (1) of 2.6 Pa, a colloidal cellulose composite content of 54 mass%, and a storage elastic modulus maintenance rate of 92.3. The loss tangent (tan δ) was 0.53. The results are shown in Table 1.

(Peanut beverage)
Using the cellulose composites A to S obtained in the above examples and comparative examples, peanut beverages were prepared and evaluated by the following operations.

  240.0 g of sugar, 160.0 g of peanut powder (Minoya Peanut Roast Co., Ltd.), 80.0 g of skim milk powder, 8.0 g of sodium caseinate, 4.0 g of emulsifier, 8.0 g of cellulose complex, Ion exchange water warmed at 80 ° C. was added to make a total amount of 4000 g. In Example 14, gellan gum was further added so as to be 0.005% by mass to make a total amount of 4000 g. In Example 15, ι-carrageenan was further added so as to be 0.015% by mass to make a total amount of 4000 g. In Example 16, xanthan gum was further added so as to be 0.01% by mass to make a total amount of 4000 g.

  Then, after mixing and dispersing with a propeller stirrer (manufactured by Shinto Kagaku Co., Ltd., BL600, stirring blade: paddle cross, 500 rpm × 10 minutes, 80 ° C.), TK homomixer (Special Machine Industries Model Mark II 10,000 rpm × 10 minutes, 80 The mixture was further mixed and dispersed at [° C.] and then homogenized (15 + 5 MPa) with a piston type homogenizer. Thereafter, after heat sterilization (141 ° C. × 5 seconds), the mixture was cooled to room temperature and filled in a 250 ml heat-resistant bottle to obtain a peanut beverage. The protein contained in this beverage was 1.7% by mass. Then, it preserve | saved for one month in 50 degreeC atmosphere, and implemented the following method. The results are shown in Table 1. In addition, the evaluation result of the peanut beverage using the cellulose composites CA and CB was the same as that using the cellulose composite C.

<Sensory evaluation>
The sensory evaluation was carried out by 20 panelists (10 males and 10 females) using the following indices for beverages stored at 50 ° C. for 1 month.
(Mouth)
◎ (excellent): Very smooth mouth.
○ (Good): It is a smooth mouth.
Δ (possible): The mouth is slightly rough.
× (Not possible): The mouth is very rough.
(Over the throat)
◎ (excellent): Very light throat.
○ (Good): Light throat.
Δ (possible): It is over the throat with a slightly pasty feeling.
X (impossible): Strong pasty feeling, over heavy throat.
(Change in texture)
◎ (excellent): There is a big difference in texture between the moment you put it in your mouth and the time you swallow it.
○ (Good): There is a slight difference in texture between the moment you put it in your mouth and the time you swallow it.
△ (possible): There is a slight difference in texture between the moment of swallowing and swallowing.
X (impossible): There is no difference in texture between the moment of swallowing and swallowing.
(Stickiness)
◎ (excellent): Does not feel sticky when put in mouth.
○ (Good): Feels almost sticky when put in the mouth.
Δ (possible): Feels somewhat sticky when put in the mouth.
X (impossible): When put in the mouth, it is strongly sticky.

<Gelification>
The beverage after storage for 1 month was filtered through a sieve having an opening of 5 mm, and the presence or absence of gel (residual) that did not pass through the sieve was confirmed.
◎ (excellent): No gel.
X (impossible): gel exists.

<Suspension stability: Observation of appearance of food and drink>
In various beverages, the following items were determined and visually judged.
◎ (excellent): No precipitation, aggregation or separation of components.
○ (good): Slight precipitation, aggregation and separation of components, which can be eliminated by shaking once or twice.
Δ (possible): There is precipitation, aggregation, and separation of components, which can be resolved by shaking 3-5 times.
X (impossible): There is precipitation, aggregation and separation of components, which cannot be resolved by shaking five times.

(Cocoa drink)
Using the cellulose composites A to S obtained in the above examples and comparative examples, cocoa beverages were prepared and evaluated by the following operations.

  200.0 g sugar, 40.0 g cocoa powder (Banjoten cocoa, fat content 22-24%), 32.0 g whole milk powder, 2.0 g sodium chloride, 8.0 g cellulose complex, and 80 C. Ion exchange water warmed at 0.degree. C. was added to make the total amount 4000 g. In Example 14, gellan gum was further added so as to be 0.005% by mass to make a total amount of 4000 g. In Example 15, ι-carrageenan was further added so as to be 0.015% by mass to make a total amount of 4000 g. In Example 16, xanthan gum was further added so as to be 0.01% by mass to make a total amount of 4000 g.

Then, after further mixing and dispersing with a propeller stirrer (manufactured by Shinto Kagaku Co., Ltd., BL600, stirring blade: cruciform, 500 rpm × 10 minutes, 80 ° C.), homogenization treatment (15 + 5 MPa) was performed with a piston type homogenizer. It was. Thereafter, after heat sterilization (140 ° C. × 60 seconds), the mixture was cooled to room temperature and filled in a 250 ml heat-resistant bottle to obtain a cocoa beverage. The protein contained in this beverage was 0.3% by mass. Then, it left still for one month in the atmosphere of 50 degreeC, and evaluated by the method similar to a peanut drink. The obtained results are shown in Table 1. In addition, the evaluation result of the cocoa drink using the cellulose composites CA and CB was the same as that using the cellulose composite C.

(Oat drink)
Using the cellulose composites A to S obtained in the above examples and comparative examples, oat beverages were prepared and evaluated by the following operations.

  240.0 g of sugar, 180.0 g of oat powder (Japanese food production premium pure oatmeal), 112.0 g of whole milk powder, 28.0 g of palm oil, 1.2 g of ι-carrageenan, 8 of cellulose complex 0.0 g and ion exchange water at 25 ° C. were further added to make the total amount 4000 g. In Example 14, gellan gum was further added so as to be 0.005% by mass to make a total amount of 4000 g. In Example 15, in addition to the above 1.2 g of ι-carrageenan, ι-carrageenan was further added to a content of 0.015% by mass (total of 0.045% by mass) to make a total amount of 4000 g. In Example 16, xanthan gum was further added so as to be 0.01% by mass to make a total amount of 4000 g.

Then, after mixing and dispersing with a propeller stirrer (manufactured by Shinto Kagaku Co., Ltd., BL600, stirrer blades: 500 rpm × 10 minutes, 25 ° C.), TK homomixer (Model Mark II made by Tokushu Kika Kogyo Co., Ltd., 10,000 rpm × 10) Min., 25 ° C.), and further homogenized (15 + 5 MPa) with a piston type homogenizer. Then, after heat sterilization (140 ° C. × 60 seconds), it was filled in a 250 ml heat-resistant bottle at 80 ° C. to obtain an oat beverage. The protein contained in this beverage was 1.3% by mass. Then, it left still for one month in the atmosphere of 50 degreeC, and evaluated by the method similar to a peanut drink. The obtained results are shown in Table 1. In addition, the evaluation result of the oat drink using the cellulose composites CA and CB was the same as that using the cellulose composite C.

  For reference, with regard to MCG-811F (manufactured by JRS) and BV-1518 (manufactured by FMC), which are commercially available cellulose composites, the storage elastic modulus G ′ (1), the storage elastic modulus maintenance factor, the loss tangent (tan δ) Table 2 shows the results of measuring and the results of producing and evaluating peanut beverages in the same manner as the cellulose composites A to R.

  The cellulose composite of the present invention can be used as a stabilizer suitable for foods and drinks, particularly high protein beverages.

Claims (8)

A cellulose composite containing cellulose and anionic polysaccharide, which is a 1.0% by weight aqueous dispersion obtained by dispersing the composite in ion-exchanged water, and storage elasticity at 1% strain at 25 ° C. The storage elastic modulus retention rate defined by G ′ (20) × 100 / G ′ (1) is 92.2 with respect to the elastic modulus G ′ (1) and the storage elastic modulus G ′ (20) at a strain of 20%. % or less der is, the anionic polysaccharide, sodium carboxymethylcellulose, gellan gum, at least one der Ru cellulose composite selected from the group consisting of carrageenan and xanthan gum. Loss tangent at a strain of 1% at 25 ° C. in a cellulose composite containing cellulose and anionic polysaccharide, wherein the composite is dispersed in ion exchange water at a concentration of 1.0% by mass (tan [delta) is Ri der less than 0.42, the anionic polysaccharide, sodium carboxymethylcellulose, gellan gum, at least one der Ru cellulose composite selected from the group consisting of carrageenan and xanthan gum. A cellulose composite containing cellulose and anionic polysaccharide, which is a 1.0% by weight aqueous dispersion obtained by dispersing the composite in ion-exchanged water, and storage elasticity at 1% strain at 25 ° C. The storage elastic modulus retention rate defined by G ′ (20) × 100 / G ′ (1) is 92.2 with respect to the elastic modulus G ′ (1) and the storage elastic modulus G ′ (20) at a strain of 20%. % or less, Ri loss tangent (tan [delta) is der less than 0.42 when a strain of 1% at 25 ° C., the anionic polysaccharide is selected from the group consisting sodium carboxymethylcellulose, gellan gum, carrageenan and xanthan gum at least one der Ru cellulose composite that.   The storage elastic modulus G ′ (1) at a strain of 1% at 25 ° C. in a 1.0 mass% aqueous dispersion obtained by dispersing the composite in ion-exchanged water is 4.3 Pa or more. The cellulose composite as described in any one of 1-3.   The anionic polysaccharide is sodium carboxymethyl cellulose having a viscosity at 25 ° C of more than 200 mPa · s when an aqueous dispersion having a concentration of 1.0 mass% is used. Cellulose composite.   The cellulose as described in any one of Claims 1-5 whose compounding ratio of the said cellulose and the said anionic polysaccharide is a cellulose / anionic polysaccharide = 50-99 mass parts / 1-50 mass parts. Complex. A method for producing a cellulose composite comprising cellulose and an anionic polysaccharide, comprising the step of adding the anionic polysaccharide in three or more stages to the cellulose and co-processing in a wet process The manufacturing method of the cellulose composite as described in any one of Claims 1-6 . Food-drinks containing the cellulose composite as described in any one of Claims 1-6 .