JP2008118988A - Heat resistant gelling agent - Google Patents

Abstract

The present invention provides a gel-like material which is non-animal and is generally preferred for use in foods, etc., and can retain the contents such as solids and proteins as it is even under conditions such as retort sterilization. Provided is a gelling agent capable of forming a gel that can be held in a state and has excellent heat stability.
SOLUTION: A fine fibrous cellulose composite containing 50 to 95% by mass of fine fibrous cellulose as a first component and 5 to 50% by mass of a water-soluble polymer or hydrophilic substance, and xanthan gum as a second component; A gelling agent comprising one or more polysaccharides selected from the group consisting of glucomannan, galactomannan, alginic acids, and gellan gum, which are the third component.
[Selection figure] None

Description

  The present invention relates to a gelling agent that is frequently used when processing food or the like into a gel-like material, and particularly relates to a gelling agent that can obtain a gel that is non-animal and has excellent heat stability.

  Gelatin, agar, gellan gum and the like are known as commercially available gelling agents. In addition, it is possible to form a gel with a mixture of glucomannan and xanthan gum, or a mixture of locust bean gum and xanthan gum, but it has a texture like konjac jelly and provides the physical properties preferred for general foods. It is difficult.

  Gelatin has moderate elasticity and is one of the gelling agents whose physical properties and texture are most preferred. In particular, it is said that the physical properties of gelatin are suitable for nursing food for dysphagic persons with reduced swallowing function such as the elderly. In recent years, physical properties of gel-like swallowing food suitable for dysphagia have been studied by physical property analysis based on dynamic viscoelasticity measurement. In Non-Patent Document 1, G ′ (storage elastic modulus) 10 to 1000 Pa, tan δ (loss) The range of tangent) 0.1 to 1 is described in Patent Document 1, and the range of G′10 to 100 Pa and tan δ 0.1 to 1 is preferable. Since the gel in this range is greatly deformed by a small stress, the bolus can pass through the pharyngeal phase smoothly. However, since gelatin is animal, there is a risk of BSE, and the gel dissolves easily at room temperature. Agar is also one of the gelling agents whose physical properties and texture are preferred, but heat resistance is not as high as gelatin. Furthermore, gellan gum has relatively high heat resistance, but in retort sterilization, which is generally processed at a temperature of 105 ° C. or higher, the gel dissolves and retains contents such as solids and proteins as they are. It becomes difficult. Further, the physical properties of the gel have the disadvantage that it is very brittle and has a large amount of water separation after fracture.

  In other words, gelatin or agar-like texture that is derived from plants or microorganisms and formed by gelling agents retains solids and proteins as they are even after retort sterilization. There is a demand for a gelling agent that can be used and has excellent heat stability.

  Here, Patent Document 2 discloses a gelling agent containing a fine fibrous cellulose composite and a polysaccharide selected from galactomannan, glucomannan, and alginic acids. Patent Document 3 describes a heat-resistant gel using the same. However, since these gel-like compositions have low strength and poor elasticity, it is difficult to say that they are physical properties required for general foods. Furthermore, the gelling agent of Patent Document 2 is basically composed of only two components of a fine fibrous cellulose complex and one type of polysaccharide, and it is impossible to control the target gel texture. It was. Moreover, since the gel obtained by this combination shows very excellent heat resistance, once the gel is formed, it does not dissolve even when reheated at a high temperature of 120 ° C. or higher. .

Furthermore, Patent Document 4 requires three components: “heat-modified fine-particle milk protein”, “composition containing microcrystalline cellulose or microfibrous cellulose”, and “gelling agent for forming a gel”. There is a description of gel food as an ingredient, but this is an effect that is manifested only by utilizing the heat coagulation property of protein, and the use conditions are considerably limited.
JP 2004-159529 A JP 2004-411119 A JP 2004-248536 A JP 2004-340442 A Mitsuo Watase, “Study on the development of swallowing food for dysphagia and elderly people-14”, Food Industry, Vol. 44, No. 11, P. 74-85

  The present invention is non-animal, and when used in foods, the intended gel texture and gel dissolution temperature can be controlled, and even if retort sterilization is performed, contents such as solids and proteins remain intact. It is an object of the present invention to provide a gelling agent having excellent heat resistance stability that can be maintained in a state.

(1) a fine fibrous cellulose composite containing 50 to 95% by mass of fine fibrous cellulose as a first component and 5 to 50% by mass of a water-soluble polymer or a hydrophilic substance, and xanthan gum as a second component; A gelling agent comprising one or more polysaccharides selected from the group consisting of glucomannan, galactomannan, alginic acids, and gellan gum as the third component.
(2) The above (1) description, wherein the mass ratio of the total content of the fine fibrous cellulose composite and the polysaccharide and the content of the xanthan gum is 70:30 to 98: 2. Gelling agent.
(3) The gelling agent according to (1) or (2) above, wherein the polysaccharide is glucomannan or galactomannan.
(4) When a standard gel having a breaking load of 1.4 N to 1.5 N is formed, the breaking strain rate is 33 to 45%, and the brittle strain rate is 1 to 10%. The gelling agent according to any one of (1) to (3) above.
(5) When a standard gel having a breaking load of 1.4 N to 1.5 N is formed, the breaking strain rate is 7 to 20%, and the brittle strain rate is 2 to 15%. The gelling agent according to any one of (1) to (3) above.
(6) A gel composition obtained by dispersing the gelling agent according to any one of (1) to (5) in an aqueous medium.
(7) The gel composition as described in (6) above, wherein the storage elastic modulus is 10 to 1000 Pa and the loss tangent is 0.05 to 1.
(8) Using the gelling agent according to any one of (1) to (5) above, adjusting the concentration of the gelling agent so as to have a target gel breaking load and dispersing the gelling agent in an aqueous medium A first step of obtaining a sample; a second step of measuring the fracture strain rate and brittleness strain rate of the obtained gel sample; and the measured values of the obtained fracture strain rate and brittleness strain rate; A method for controlling physical properties of a gel-like composition comprising sequentially performing a third step of changing the composition of the gelling agent on the basis of a difference between a fracture strain rate and a brittle strain rate targeted in advance.

  Since the gelling agent of the present invention is non-animal and excellent in heat stability, it is possible to greatly improve the flowability and safety of gel-like products using it. It is also possible to obtain a gel with high strength. Furthermore, since the gel properties such as texture and dissolution temperature can be controlled by using three specific components as components of the gelling agent, it is possible to design a product that meets the needs of customers and consumers.

  Hereinafter, embodiments of the present invention will be specifically described. The inventor is selected from the group consisting of a fine fibrous cellulose composite as the first component, a small amount of xanthan gum as the second component, and a galactomannan, glucomannan, alginic acid, and gellan gum as the third component. By blending polysaccharides, a gelling agent that is non-animal and can retain solids, proteins, and other contents as they are even after retort sterilization, and can provide a gel with excellent heat stability In addition, the present inventors have found that the structure of the gelling agent can control the texture of the gel obtained and the physical properties at the dissolution temperature.

  The fine fibrous cellulose used for the fine fibrous cellulose composite of the first component uses so-called cellulose having a β-1,4 glucan structure as a raw material. In order to stably supply an inexpensive product, it is preferable to use a cellulosic material originating from plant cell walls as a raw material. Among these, a grass-derived pulp using bagasse, rice straw, wheat straw, bamboo and the like is particularly preferable. Cotton, papyrus grass, ridges, honey, and ganpi can also be used, but it is preferable because it is difficult to secure a stable raw material, the content of components other than cellulose is large, and handling is difficult. There may not be. The same applies to the soft cell-derived raw materials such as beet pulp and fruit fiber pulp. In addition, regenerated cellulose such as rayon or cellulose produced by microorganisms may be used as a raw material.

  The fine fibrous cellulose is preferably crystalline in order to improve the heat stability of the gel. Specifically, it is preferable that the degree of crystallinity as measured by the X-ray diffraction method (Segal method) exceeds 50%. More preferably, the crystallinity is 55% or more. However, the fine fibrous cellulose composite also contains other components other than the fine fibrous cellulose, and these other components are often amorphous. Therefore, when the crystallinity is measured using the fine fibrous cellulose composite as a sample, the value obtained is lower than the correct crystallinity of the fine fibrous cellulose itself. For example, if the crystallinity measured for a fine fibrous cellulose composite is 50%, it can be said that the crystallinity of the fine fibrous cellulose is 50% or more. However, if a value of 49% is obtained as the crystallinity of the fine fibrous cellulose composite, for example, the crystallinity must be measured again after separating only the fine fibrous cellulose from the other components. I must.

  In the fine fibrous cellulose, most of the cellulose fibers, that is, 90% or more are “fine fibrous”. This “fine fibrous form” means that when a cellulose fiber is observed and measured with an optical microscope or an electron microscope, the length (major axis) of the cellulose fiber is 5 nm to 5 mm, and the width (minor axis) is 1 nm to 200 μm. It means that the ratio of the width to the width (major axis / minor axis) is 5 to 10,000. By using such fine fibrous cellulose, the gelling ability of the gelling agent is improved and the gel breaking strength is increased. Among them, the preferred “fine fibrous cellulose” has a length (major axis) of 0.5 μm to 1 mm, a width (minor axis) of 2 nm to 60 μm, and a ratio of the length to the width (major axis / minor axis) of 5 to 400. belongs to.

  The fine fibrous cellulose composite is a composite formed by once passing through a dry state from a slurry liquid state of fine fibrous cellulose and a water-soluble polymer or a hydrophilic substance. A dry composition in which a water-soluble polymer or a hydrophilic substance is combined. By using such a complex, the reason is unknown, but the gelling ability of the gelling agent is greatly improved. Each amount ratio is fine fibrous cellulose: water-soluble polymer or hydrophilic substance = 50: 50 to 95: 5 (however, 100 in total). Within this range, the balance between gel breaking strength and dispersibility is excellent.

Preferably, fine fibrous cellulose, a water-soluble polymer and a hydrophilic substance are combined. The respective mass ratios in this case are within the range of 3 to 47 for the water-soluble polymer and 3 to 47 for the hydrophilic substance with respect to 50 to 94 for the fine fibrous cellulose (however, 100 in total).
Within this range, the dispersibility of the gelling agent in water is good, and the gelation performance is also good. More preferably, the fine fibrous cellulose is within the range of the mass ratio of 10 to 30 for the water-soluble polymer and 5 to 40 for the hydrophilic substance (however, 100 in total).

  The form of this dry composition takes various forms such as granules, granules, powders, scales, pieces, and sheets. It does not limit at all about the drying method at the time of obtaining a dry composition. After drying, if necessary, it may be pulverized with a cutter mill, hammer mill, pin mill, jet mill or the like.

  The water-soluble polymer has a function of preventing keratinization between celluloses at the time of drying. By passing through a dry state once from a slurry liquid state of fine fibrous cellulose and a water-soluble polymer, fine fibers A cellulose composite is formed. This improves the redispersibility when the gelling agent is introduced into water, and improves the gelation ability when the gelling agent is used for unknown reasons.

  Specific examples of water-soluble polymers include gum arabic, arabinogalactan, alginic acid and its salts, curdlan, gati gum, carrageenan, caraya gum, agar, xanthan gum, guar gum, enzymatically degraded guar gum, quince seed gum, gellan gum, One or two selected from tamarind seed gum, indigestible dextrin, tragacanth gum, farcellulan, pullulan, pectin, locust bean gum, water-soluble soybean polysaccharide, sodium carboxymethylcellulose, methylcellulose, sodium polyacrylate, etc. More than seed material is used.

  Among them, it is preferable to use sodium carboxymethyl cellulose because dispersibility is improved. As carboxymethylcellulose sodium, the substitution degree of the carboxymethyl group is preferably 0.5 to 1.5, more preferably 0.5 to 1.0, still more preferably 0.6 to 0.8. It is.

  The viscosity of a 1% by weight aqueous solution of the water-soluble polymer is preferably about 5 to 9000 mPa · s, more preferably about 1000 to 8000 mPa · s, and still more preferably 2000 to 6000 mPa · s. It is to be used at a degree. Within this range, there is no problem in handling properties, and the performance of the gelling agent is also in a good range.

  The hydrophilic substance functions as a disintegrant or a water-conducting agent when the gelling agent is added to water. By using the hydrophilic substance, the fine fibrous cellulose composite is more easily dispersed in water. . A hydrophilic substance is a substance that is highly soluble in cold water, hardly causes viscosity, and is solid or liquid at room temperature. For example, dextrin (including branched dextrin, cyclodextrin, etc.), water-soluble saccharide (glucose, fructose, sucrose, lactose, oligosaccharide, isomerized sugar, xylose, trehalose, coupling sugar, palatinose, sorbose, reduced starch saccharified starch , Maltose, lactulose, fructooligosaccharide, galactooligosaccharide, etc.) and sugar alcohols (xylitol, maltitol, mannitol, sorbitol, etc.), and one or more substances selected from these. By the way, some hydrophilic substances have a little function as a water-soluble polymer, such as dextrins. Even when such a hydrophilic substance is used, it is desirable to use a water-soluble polymer in combination, but it is also possible not to use a water-soluble polymer.

  As for hydrophilic substances, low molecular weight substances tend to have better particle disintegration / dispersibility in water, but on the other hand, they tend to be inferior in dryness during production, hygroscopicity of products, and stability over time. . For example, glucose, sucrose, trehalose, and the like exhibit good properties, but the substance with the best balance is dextrin having a DE (dextrose equivalent) of 20 or more.

  The fine fibrous cellulose composite may contain other components other than the fine fibrous cellulose, the water-soluble polymer, and the hydrophilic substance as long as the effect is not impaired. For example, starches, fats and oils, proteins, peptides, amino acids, surfactants, preservatives, shelf life improvers, pH adjusters, salt, salts such as various phosphates, emulsifiers, acidulants, sweeteners, flavors Ingredients such as a dye, an antifoaming agent, a foaming agent, an antibacterial agent, and a disintegrating agent may be appropriately blended.

  The fine fibrous cellulose composite preferably contains 30% by mass or more of “a component that is stably suspended in water” in the total cellulose. When the content of this component is 30% by mass or more, the gel forming function is more excellent. The larger the content, the better, but 50 to 100% by mass is more preferable. As used herein, “a component that is stably suspended in water” is stable in water without precipitation even when the gelling agent is made into a 0.1% by weight aqueous dispersion and then centrifuged at 1000 G for 5 minutes. It is shown by the ratio with respect to the total cellulose amount of the cellulose suspended in. (The method for measuring “a component that is stably suspended in water” will be described later.)

  Such components have a length (major axis) of 0.5 to 30 μm, a width (minor axis) of 2 to 600 nm, and a length and width that are observed and measured with a high resolution scanning electron microscope (high resolution SEM). The ratio (major axis / minor axis ratio) is preferably 20 to 400, more preferably the width (minor axis) is 100 nm or less, more preferably 50 nm or less.

  The fine fibrous cellulose composite preferably has a loss tangent (tan δ) of less than 1 measured under the conditions of a strain of 10% and a frequency of 10 rad / s in an aqueous dispersion having a concentration of 0.5% by mass. When it is less than 1, the gel forming function is excellent. Preferably it is less than 0.6.

  In order to make the loss tangent of the fine fibrous cellulose composite less than 1, it is necessary to take out the fine fibrous cellulose that is a constituent of the fine fibrous cellulose composite, that is, the microfibril of the cellulose without cutting it short. However, with the current technology, it is not possible to perform only “miniaturization” without “shortening the fiber” (here, “shortening fiber” means that the fiber is cut short or the state of the shortened fiber) In addition, “miniaturization” means that the fiber is thinned by an action such as tearing, or the state of the thinned fiber. That is, in order to make the loss tangent less than 1, it is important to advance the “miniaturization” while minimizing the “shortening” of the cellulose fiber. Examples of preferable methods for this purpose are shown below, but are not limited to these methods.

  When selecting a cellulosic substance originating from the plant cell wall as a raw material, in order to advance the “miniaturization” while minimizing the “shortening” of the cellulose fiber, the average degree of polymerization is 400 to 12000, In addition, it is preferable to select an α-cellulose content (%) of 60 to 100% by mass, more preferably an average degree of polymerization of 400 to 12000 and an α-cellulose content (%) of 60 to 85% by mass. Is to choose one.

  Further, a high-pressure homogenizer is preferable as an apparatus used for advancing “miniaturization” while minimizing “shortening” of cellulose fibers. Specific examples of the high-pressure homogenizer include Emulflex (AVESTIN, Inc.), Optimizer System (manufactured by Sugino Machine Co., Ltd.), Nanomizer System (manufactured by Nanomizer Co., Ltd.), Microfluidizer (manufactured by MFIC Corp.), There are valve type homogenizers (manufactured by Sanwa Machinery Co., Ltd., manufactured by Invensys APV, manufactured by Niro Soavi, manufactured by Izumi Food Machinery). The processing pressure of the high-pressure homogenizer is preferably about 60 to 414 MPa.

  The xanthan gum used as the second component of the gelling agent has a structure in which the main chain has a β-1,4 bond to D-glucose, and D-mannose, D-glucuronic acid, D -The side chain consisting of mannose is bound. The 6-position of D-mannose attached to the main chain is acetylated and has a highly branched structure in which the terminal D-mannose is acetal-bonded to pyruvic acid. Xanthan gum does not gel by itself, but plays a very important role from the viewpoint of controlling physical properties such as texture and dissolution temperature in a gelling agent.

  The polysaccharide which is the third component of the gelling agent is selected from the group consisting of glucomannan, galactomannan, alginic acids, and gellan gum according to the desired physical properties of the gel.

  Glucomannan is a polysaccharide having a structure in which D-glucose and D-mannose are linked by β-1,4, and the ratio of glucose to mannose is about 2: 3. Since glucomannan has a unique irritating odor when the degree of purification is low, it is desirable to use one with a high degree of purification, but konjac powder or konjac mannan may be used depending on the application.

  Galactomannan is a polysaccharide having a structure composed of a main chain in which β-D-mannose is bonded with β-1,4 and a side chain in which α-D-galactose is bonded with α-1,6. Examples of galactomannans include guar gum, locust bean gum, tara gum, etc. The ratio of mannose to glucose is about 2: 1 for guar gum, about 4: 1 for locust bean gum, and about 3: 1 for tara gum.

  Alginic acid means alginic acid, alginates such as sodium alginate, or propylene glycol alginate. Among the alginic acids, it is preferable to use sodium alginate which is a water-soluble polysaccharide in which alginic acid is neutralized with sodium. Alginic acid is a 1,4-bond block copolymer consisting of β-D-mannuronic acid (abbreviated as M) and α-L-guluronic acid (abbreviated as G). A block composed of M (MMMGM), a block composed of G (GGGGG), and a block in which both residues are alternately mixed (MGGG) , And consists of three segments. These alginic acids may be used by controlling pH and salt concentration.

  There are two types of gellan gum: deacetylated gellan gum and native gellan gum. The structure is linearly linked by four sugar repeating units, glucose, glucuronic acid, glucose and L-rhamnose. Glucose having 1/2 residue of acetyl group at C-6 position and glyceryl group at C-2 position is native gellan gum, and purified by deacetylation of this is It is called acetylated gellan gum. Gellan gum as used herein refers to this deacetylated gellan gum.

  Further, the term “animality” as used herein means that it is derived from a higher animal (mammals, birds, seafood, etc.) and does not mean that it is derived from a plant or a microorganism. That is, the fine fibrous cellulose composite, xanthan gum and polysaccharide, which are constituents of the gelling agent, are all non-animal because they are derived from plants or microorganisms.

  The gelling agent is used by blending the fine fibrous cellulose composite as the first component, the second component xanthan gum, and the third component polysaccharide. As a result, the physical properties of the gel can be controlled. In other words, as a second component, by adding a small amount of xanthan gum that does not gel by itself, it is possible to control the texture of the gel using the fracture strain rate and brittle strain rate as described below as an index, and further to suit workability. It is possible to change the dissolution temperature of the gel.

  The mass ratio of the total content of the first component and the third component described above and the content of the second component xanthan gum is “first component (fine fibrous cellulose composite) + third component (polysaccharide)”. : “Second component (xanthan gum)” = 70:30 to 98: 2, preferably 80:20 to 95: 5, more preferably 85:15 to 90:10. Within this range, a gel having excellent heat stability can be obtained.

  Furthermore, the mass ratio of the fine fibrous cellulose composite as the first component and the polysaccharide as the third component is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. More preferably, it is 3: 7 to 7: 3.

  The gel formed from the gelling agent obtained by mixing the above components surprisingly has a markedly improved gel breaking strength. Although the reason for this is unknown, gelation does not occur when only the fine fibrous cellulose composite as the first component and the xanthan gum as the second component are mixed, while the fine fibrous cellulose as the first component When only the complex and the polysaccharide that is the third component are mixed, a gel having excellent heat resistance that does not dissolve even at a high temperature of 120 ° C. or higher is formed. Further, the xanthan gum that is the second component and the polysaccharide that is the third component When mixing only, the gelation occurs although the gel strength is weak, and the bond between the first component and the third component and between the second component and the third component acts synergistically. Therefore, it is considered that the strength of the entire gel is increased.

  Next, the properties of the gel formed from the gelling agent will be described in more detail. First, the gelling agent was dispersed in ion-exchanged water, and the standard gel for evaluation was formed so that the breaking load obtained according to the measurement conditions described later at 5 ° C. was 1.4 N to 1.5 N. To do. In order to adjust the breaking load of the standard gel, the concentration of the gelling agent may be adjusted as appropriate. However, when gellan gum is included in the constituents of the gelling agent, it is preferable to use a calcium salt (calcium lactate, calcium chloride, etc.) in combination. Thus, the reason why the breaking load of the standard gel is adjusted within a certain range is to make the preconditions for evaluating gel physical properties uniform.

The gel formed from the gelling agent is excellent in heat resistance stability. In the present invention, the heat stability refers to a state in which the contents (sometimes referred to as particles) in the gel are uniformly dispersed even if the gel is once dissolved by performing a high temperature treatment such as retort sterilization. A function that is fixed and held as it is without changing the position in the gel. The heat-resistant stability here can be evaluated by calculating the particle immobilization index in the standard gel by the following formula (1). The particle immobilization index is the ratio (%) of the immobilized particles in all particles. When the particle immobilization index is 60% or more, it is determined that the heat stability is excellent.
Particle immobilization index (%) = [{α− (β + γ)} / α] × 100 (1)
(Α: total number of particles, β: number of particles floating on the liquid surface, γ: number of particles precipitated on the bottom surface)

Here, the breaking strain rate in the standard gel refers to the ratio of the breaking deformation amount to the original thickness of the standard gel sample, and is obtained by substituting the value measured by the method described later into the following formula (2). .
Breaking strain rate (%) = breaking deformation (mm) / sample thickness (mm) × 100 (2)
(Breaking deformation (mm) means the deformation distance of the breaking point.)

The brittle strain rate in the standard gel refers to the ratio of brittle deformation to the original thickness of the standard gel sample, and is obtained by substituting the value measured by the method described later into the following formula (3). .
Brittleness strain rate (%) = brittleness deformation (mm) / sample thickness (mm) × 100 (3)
(The brittle deformation (mm) means the deformation distance from the breaking point to the brittle point.)

The gelling agent preferably has a breaking strain rate of 33 to 45% and a brittle strain rate of 1 to 10% when the standard gel is formed using the gelling agent. The gel exhibiting such physical properties is a gel exhibiting gelatin-like physical properties and can provide a texture that is more preferred as a general food. For this purpose, it is preferable to select and use glucomannan or galactomannan as the third component polysaccharide, and among the galactomannan, it is preferable to select locust bean gum. In order to show a more preferable texture like gelatin, a more preferable breaking strain rate of the standard gel is preferably 36 to 42%.
In particular, G ′ (storage elastic modulus) obtained by dynamic viscoelasticity measurement is 10 to 1000 Pa, and tan δ (loss tangent) is 0.05 to 0.05 in order to show gel properties suitable for nursing food for dysphagia patients. It is preferable to prepare the gel so as to be in the range of 1.

  In addition, the gelling agent preferably has a fracture strain rate of 7 to 20% and a brittle strain rate of 2 to 15% when the standard gel is formed using the gelling agent. . The gel exhibiting such physical properties is a gel exhibiting agar-like physical properties, and can provide a texture that is more preferred as a general food. For this purpose, it is preferable to use gellan gum as the third component polysaccharide, and then select and use galactomannan or glucomannan. Among the galactomannans, it is preferable to select locust bean gum. In order to show an even more agar-like texture, the more preferred breaking strain rate of the standard gel is preferably 13 to 18%.

  The gelling agent of the present invention can control the dissolution temperature of the gel formed by changing the mass ratio of the first component, the second component, and the third component. This depends on the type of polysaccharide used, but the total content of the first component (fine fibrous cellulose complex) and the third component (glucomannan or galactomannan) and the content of the second component (xanthan gum) In the mass ratio of 70:30 to 98: 2, the lower the xanthan gum content, the higher the dissolution temperature of the gel formed, and it may not dissolve even at 100 ° C. or higher. On the other hand, the higher the xanthan gum content, the lower the melting temperature of the gel formed, and it tends to dissolve in the range of 60 ° C to 80 ° C. This makes it possible to select a gel physical property suitable for the process, whether to maintain a gel state or a fluid sol state under each temperature condition.

  In addition to the first component, the second component, and the third component, other components may be appropriately blended in the gelling agent. Examples of other ingredients include pectin, carrageenan, tamarind seed gum, carboxymethylcellulose sodium, methylcellulose, chitin chitosan, soy polysaccharide, psyllium seed gum, gum arabic, tragacanth gum, karaya gum, gati gum, arabinogalactan, farcel Thickening polysaccharides such as orchid, curdlan and pullulan, auxiliary components required for gelation (inorganic salts, acids, alkalis, saccharides, etc.), starches, dextrins, fats and oils, proteins, peptides, amino acids, surface activity Agent, preservative, shelf life improver, pH adjuster, salt, salt such as various phosphates, emulsifier, acidulant, sweetener, saccharide, sugar alcohol, oligosaccharide, fragrance, pigment, antifoaming agent, foaming Agents, antibacterial agents, disintegrants and the like.

  In producing the gelling agent, the fine fibrous cellulose composite, xanthan gum and polysaccharide may be blended at a predetermined ratio and sufficiently mixed in a dry state. Usually, it is desirable to use the fine fibrous cellulose composite as it is, but it may be used after being dispersed in an aqueous medium to be liquid. The same applies to xanthan gum and polysaccharides.

  Next, the gel composition adjusted using the gelling agent will be described. The gel composition is obtained by dispersing a gelling agent in an aqueous medium. Although the compounding quantity of the gelatinizer in a gel-like composition is not specifically defined, about 0.1-5 mass% is preferable. Within this range, a gel having a gel breaking strength generally desired for foods and the like can be obtained. More preferably, it is about 0.3-1.5 mass%.

  The gel composition is usually mixed with other materials such as food ingredients. The order in which the gelling agent and other materials are added when preparing such a gel composition is not particularly limited, but some other materials may inhibit gel formation. It is desirable to prepare a liquid composition containing a gelling agent after preparing other ingredients and mixing them. The temperature of the aqueous medium when dispersing the gelling agent is not particularly specified, but a temperature suitable for the combination of the constituents of the gelling agent is selected.

  This gel-like composition can be a generally preferred physical property when used in foods and the like, and can retain contents such as solids and proteins as they are even after retort sterilization. Since it also has heat resistance stability, it is possible to greatly improve the distribution and merchandise of products.

  Examples of the ingredients other than water and the gelling agent to be blended in the gel composition include, for example, food materials (livestock meat, fish meat, beans / cereals and pulverized products thereof, milk / dairy products, fermented milk, vegetables, fruits, fruit juices) , Edible oils and fats), beverages (coffee, teas, juices, milk drinks, soy milk, etc.), seasonings (miso, soy sauce, sugar, salt, sodium glutamate, etc.), sweeteners, sugars, sugar alcohols, flavors, Dyes, spices, acidulants, emulsifiers, surfactants, preservatives, shelf-life improvers, antibacterial agents, disintegrants, antifoaming agents, foaming agents, pH adjusters, thickening stabilizers, dietary fiber, nutrient enhancers ( Vitamins, minerals, amino acids, etc.), extracts, proteins, starches, peptides, alcohols, organic solvents, plasticizers, fats and oils, buffers, fuels, explosives / explosives, acids, alkalis, ionic substances, microcapsules , Beauty ingredients (beauty Ingredients, moisturizing ingredients, etc.), bioactive substances, medicinal ingredients, pharmaceutical additives, agricultural chemicals, fertilizers, deodorants, insecticides, metals, catalysts, ceramics, paints, inks, pigments, abrasives, synthetic polymers (plastics) , Rubber, synthetic fibers, etc.), naturally derived polymers (collagen, hyaluronic acid, natural fibers, etc.), paper and the like. That is, the gelling agent and the gel-like composition can be applied not only to food applications but also to pharmaceutical and medical products, cosmetics, and industrial products. Further, these gel-like compositions may be used after being cooled and hardened, or subjected to treatment such as cold thawing and drying.

  Examples of foods that can be applied include “desserts such as pudding and jelly”, “yogurts including fruit yogurt and nutrient-enriched yogurt (Ca-enriched etc.)”, “frozen desserts such as ice cream, soft cream, and sherbet”, “ Ingredients added as an accent to beverages, honey bees, yogurts, etc. ”,“ Japanese confectionery such as buns, kuzukiri, yokan, candy ”,“ confectionery such as gummy candy, candy, caramel, gum, chocolate ”,“ `` Baked sweets such as cookies, biscuits, rice crackers '', `` Fillings '', `` Batter mixes '', Shortenings '', `` Food for people with dysphagia, nursing food, chopped food, thick food, etc. '', `` Jelly drinks, seasonings such as sauce, sauce, dressing, mayonnaise, kneading Various kinds of knead seasonings represented by bean paste, “noodles”, “skins such as dumplings, spring rolls, Chinese buns”, “fruit and vegetable preparations represented by fruit sauce, fruit preparation, jam”, “food "Different liquid foods", "Health foods and nutrition-enriched foods", "Gel foods such as tea steamed and tofu", "Kamaboko and other paste products", "Sausage, ham and other livestock foods", "Spread, cheese, Dairy products such as whipped cream ”,“ vegetables / bento ”,“ normal beverages (coffee, tea, isotonic beverages, milk, milk beverages, acidic milk beverages, soy milk, soy beverages, matcha tea, cocoa, shirako, juice, Gelled products "," pet foods ", etc., which are ingested as beverages containing pulp, etc.). Common foods are often provided at a pH of 3 to 8 and a salt concentration of about 0.01 to 20%, and the gelling agent exhibits a preferable function even under these conditions. In addition, the form or the processing method of preparation at the time of use may differ like retort food, frozen food, food for microwave ovens, etc.

  In addition to the above-described examples, by using a gelling agent, it is possible to provide a new food form that is not generally distributed on the market. Examples of new food forms include tea fumigation that uses a gelling agent instead of eggs, `` new allergen-removing foods '' such as pudding and mayonnaise, and `` wheat-like foods that use a gelling agent instead of rice '' There are new low-calorie foods and soups and miso soup that can be warmed and consumed.

  Examples of medicinal products that can be applied include “oral drugs, nasal drugs such as hormonal drugs, enteral drugs, skin drugs, transdermal drugs, etc.”, contrast media, and “pharmaceuticals” Liquid foods, "Medicinal cosmetics, vitamin-containing health agents, hair preparations, medicated toothpastes, bath preparations, insecticides / insecticides, odor control agents, mouth fresheners, etc.", "artificial cartilage, Drug carriers, DNA carriers, bioadhesives, wound dressings, biomaterials such as artificial organs ", patching agents, coating agents, capsules and the like.

  Examples of cosmetics that can be applied include: “Beauty ingredient-containing gel cosmetics, packs, moisture creams, massage creams, cold creams, cleansing creams, facial cleansers, vanishing creams, emollient creams, hand creams, sunscreen cosmetics. Skin cosmetics such as foundation, lipstick, lip balm, cheeks, sunscreen cosmetics, eyelash cosmetics such as eyebrows, mascara, and cosmetics for finishing such as nail polish and nail polish cosmetics, etc. "Shampoos, hair rinses, hair treatments, pomades, tics, hair creams, balms, hair styling agents, hair styling agents, hair sprays, hair dyes, hair cosmetics such as hair restorers and hair nourishing agents", and even cleaners like hand cleaners , Bath cosmetics, shaving cosmetics, fragrances Toothpaste, ointments, and plasters and the like.

  Examples of industrial products that can be applied include pigments, paints, inks, deodorants and fragrances, antibacterial and antifungal agents, adhesives, coating agents, surfactants, "sanitary materials such as disposable diapers", "cells" Culture materials such as bacteria and viruses, experimental materials such as gels for electrophoresis, chromatographic columns or packing materials, agricultural and horticultural supplies such as soil conditioners and water retention materials for plant cultivation, artificial snow, filtration Materials, detergents, liquid soaps, explosives / explosives, and fuel.

  Next, a method for controlling the physical properties of the gel composition obtained from the gelling agent will be described. Gel-like compositions are widely used in foods, but are a group of products with strong customer preference, and are required to provide physical properties and textures according to customer requirements. In addition, simply adjusting the concentration of the gelling agent may affect the taste and texture of food when the amount of the gelling agent is large, so the gelling agent concentration remains below a certain level. It is desirable that the gel properties can be adjusted.

  The gelling agent is composed of the first component fine fibrous cellulose composite, the second component xanthan gum, and the third component polysaccharide, so that a gel with high gel strength can be obtained. In addition, the degree of freedom of adjustment by changing the composition is relatively large, and it is possible to obtain a gel with favorable characteristics by adjusting the composition of the gelling agent even if the concentration of the gelling agent remains below a certain level. It is. Therefore, it is easy to obtain a gel-like composition having desired physical properties such as gel texture and dissolution temperature.

  Specifically, in a state where the above-described breaking load described in relation to the standard gel is made constant, the composition of the gelling agent is changed and adjusted while using the breaking strain rate and the brittle strain rate as indices. Good. First, a first step of obtaining a gel sample by dispersing and gelling in an aqueous medium while adjusting the concentration of the gelling agent so as to have a target breaking load. Next, a second step of measuring the fracture strain rate and brittleness strain rate of the obtained gel sample under predetermined conditions. Furthermore, a third step of changing the composition of the gelling agent based on the difference between the measured value obtained in the previous step and the fracture strain rate and brittle strain rate set in advance as targets. And the 4th step which obtains a gel sample again using the gelatinizer of the changed composition, and remeasures and confirms a fracture strain rate and a brittle strain rate. The composition of the gelling agent can be adjusted by sequentially executing these first to third steps and, if necessary, the fourth step. Furthermore, if necessary, the third step and the fourth step can be repeated to further optimize the composition of the gelling agent. In many cases, in addition to the first to fourth steps, the gel of the target property can be obtained by repeating the third and fourth steps one or two times to optimize the composition of the gelling agent. Can do.

Next, the present invention will be described in more detail with reference to examples. Various physical properties were evaluated according to the following methods.
<Average degree of polymerization of cellulosic material>

ASTM Designation: D 1795-90 “Standard Test Method for Intrinsic Visibility of Cellulose”.
<Α-cellulose content of cellulosic material>

It is carried out according to JIS P8101-1976 (“dissolving pulp test method” 5.5 α cellulose).
<Crystallinity of cellulosic material>

It is calculated by the Segal method from the diffraction intensity value of the X-ray diffraction diagram obtained by the X-ray diffraction apparatus specified in JIS K 0131-1996 (“General Rules for X-ray Diffraction Analysis”), and is defined by the following equation.
Crystallinity (%) = {(Ic−Ia) / Ic} × 100
(Here, Ic: diffraction intensity at diffraction angle 2θ = 22.5 degrees in X-ray diffraction diagram, Ia: baseline intensity (minimum intensity) around diffraction angle 2θ = 18.5 degrees). )
<Shape of cellulose fiber (or cellulose particle) (major axis, minor axis, major axis / minor axis ratio)>

  Since the size range of cellulose fibers (or cellulose particles) is wide, it is impossible to observe all with one kind of microscope. Therefore, an optical microscope and a scanning microscope (medium resolution SEM, high resolution SEM) are appropriately selected according to the size of the fibers (particles), observed as follows, photographed and measured.

  When using an optical microscope, weigh out the sample and pure water so that an aqueous dispersion with a solid content concentration of 0.25% by mass is obtained, and a stirrer (Excel Auto Homogenizer (trade name), manufactured by Nippon Seiki Co., Ltd.). The dispersion dispersed at 15000 rpm for 15 minutes is adjusted to an appropriate concentration, placed on a slide glass, and further covered with a cover glass for observation and photography.

  In addition, when using a medium resolution SEM (JSM-5510LV, manufactured by JEOL Ltd.), the sample aqueous dispersion adjusted in the same manner as in the case of the optical microscope is placed on the sample stage, air-dried, and then Pt-Pd is reduced to about After deposition of 3 nm, observation and photography are performed.

  When using a high-resolution SEM (S-5000, manufactured by Hitachi Science Systems, Ltd.), place a similar sample aqueous dispersion on the sample stage, air dry, and deposit Pt-Pd about 1.5 nm. Observe and photograph.

The major axis, minor axis, and major axis / minor axis ratio of the cellulose fibers (or cellulose particles) were measured by selecting 15 (pieces) or more fibers from the photograph taken. Some fibers were almost straight or curved like hair, but none were round like lint. The short diameter (thickness) was varied among single fibers, but a plurality of locations were measured and an average value was adopted. The high-resolution SEM was used when observing a fiber having a minor axis of several nm to 200 nm, but one fiber was too long to fit in one field of view. Therefore, photography was repeated while moving the field of view, and then the pictures were synthesized and analyzed.
<Loss tangent (= loss elastic modulus / storage elastic modulus)>

(1) The test sample and water are weighed so that the solid concentration is 0.5% by mass, and dispersed with an ace homogenizer (manufactured by Nippon Seiki Co., Ltd., AM-T type) at 15000 rpm for 15 minutes. To do.
(2) Subsequently, it is left to stand in an atmosphere at 25 ° C. for 3 hours to obtain a test sample solution.
(3) After placing the test sample solution in the dynamic viscoelasticity measuring apparatus, the sample is allowed to stand for 5 minutes and then measured under the following conditions to determine the loss tangent (tan δ) at a frequency of 10 rad / s.
Apparatus: ARES (100FRTN1 type, manufactured by TA Instruments)
Geometry: Double Wall Couette
Temperature: 25 ° C
Distortion: 10% (fixed)
Frequency: 1 → 100 rad / s (increased over about 170 seconds)
<Content of “component that is stably suspended in water”>

It calculates | requires from the following (1)-(5) or (1)-(2) and (3 ')-(5').
(1) The test sample and pure water are weighed out so that the solid concentration of the test sample such as the gelling agent is 0.1% by mass, and an ace homogenizer (manufactured by Nippon Seiki Co., Ltd., AM-T The sample solution is prepared by dispersing at 15000 rpm for 15 minutes.
(2) Put 20 g of sample solution into a centrifuge tube and centrifuge at 1000 G for 5 minutes in a centrifuge.
(3) The upper liquid portion generated by centrifugation is removed, and the mass a (g) of the lower sedimentation portion is measured.
(4) Next, the sedimentation part is absolutely dried, and the mass b (g) of the solid content is measured.
(5) The content rate c (mass%) of "the component stably suspended in water" is calculated using the following formula.
c = 5000 × (k1 + k2)
(However, k1: amount of “fine fibrous cellulose” contained in the upper liquid portion, k2: amount of “fine fibrous cellulose” contained in the lower sedimented portion, and w1: contained in the upper liquid portion. The amount of water, w2: the amount of water contained in the sedimented portion of the lower layer, and s2: the amount of “water-soluble polymer + hydrophilic substance” contained in the sedimented portion of the lower layer.
Here, k1 and k2 are calculated and used using the following equations.
k1 = 0.02−b + s2
k2 = k1 × w2 / w1

Moreover, w1, w2, and s2 are calculated | required with the following formula | equation. The ratio of the total amount of water-soluble polymer and hydrophilic substance blended in the test sample: d (g) divided by the total amount of cellulose component blended in the test sample: f (g) d / f.
w1 = 19.98−a + b−0.02 × d / f
w2 = a−b
s2 = 0.02 × (d / f) × w2 / (w1 + w2)
d / f = (blending amount of water-soluble polymer + blending amount of hydrophilic substance) / blending amount of cellulose

By the way, when the content of the “component that is stably suspended in water” is very large, the weight of the sedimentation portion becomes a small value, so that the measurement accuracy is lowered by the above method. In that case, the procedure after the above (3) is performed as follows.
(3 ′) The upper liquid portion is obtained and the mass a ′ (g) is measured.
(4 ′) Next, the upper layer component is completely dried, and the mass b ′ (g) of the solid content is measured.
(5 ') The content rate c (mass%) of "the component stably suspended in water" is calculated using the following formula.
c = 5000 × (k1 + k2)
K1 and k2 in this are calculated and used using the following formula.
k1 = b′−s2 × w1 / w2
k2 = k1 × w2 / w1
Moreover, w1, w2, and s2 are calculated | required with the following formula | equation.
w1 = a′−b ′
w2 = 19.98−a ′ + b′−0.02 × d / f
s2 = 0.02 × (d / f) × w2 / (w1 + w2)
If the boundary between the upper liquid portion and the settled portion is not clear by the operation (3) or (3 ′) and separation is difficult, the same operation may be performed by appropriately reducing the cellulose concentration.
<Heat-resistant stability of gel>

(1) The gelling agent is measured so that the breaking load at 5 ° C. measured by the method described later is within the range of 1.4N to 1.5N. However, when gellan gum is used as the third component polysaccharide of the gelling agent, a calcium salt (calcium lactate, calcium chloride, etc.) is used in combination as appropriate.
(2) Using the gelling agent dispersion obtained by dispersing the gelling agent in ion-exchanged water as a test sample, paper-made plate-like particles (major axis 5 mm, minor axis 5 mm square, thickness 0.3 mm) were added. And mix evenly. If necessary, add calcium salt and disperse. The dispersion conditions (stirring device, temperature, etc.) at this time are appropriately selected according to the gelling agent.
(3) Pour and fill into a cylindrical glass container with an inner diameter of about 45 mm until the height is about 45 mm so that there are 20 paper plate-like particles per filling container.
(4) Heat treatment is performed at 120 ° C. for 30 minutes.
(5) After completion of the heat treatment, keep the stationary state, and after cooling at 25 ° C. for 3 hours, count the number of particles floating on the gel surface and the number of particles settling on the bottom surface.
(6) Determination of heat stability: Based on the number of particles counted in (5), an immobilization index is obtained using the following formula. When the immobilization index is 60% or more, it is determined that there is heat resistance stability.
Immobilization index (%) = [α− (β + γ)] / α × 100
(Α: total number of particles, β: number of particles floating on the liquid surface, γ: number of particles settling on the bottom surface)
<Heat resistant stability of gel composition>

(1) The gelling agent is weighed out so as to obtain the target gel breaking load. However, when gellan gum is used as the third component polysaccharide of the gelling agent, a calcium salt (calcium lactate, calcium chloride, etc.) is used in combination as appropriate.
(2) The gelling agent is dispersed in ion-exchanged water, and the gelling agent dispersion liquid, in which other components are added and mixed, is used as a test sample, and arbitrary particles are added and mixed uniformly. If necessary, add calcium salt and disperse. The dispersion conditions (stirring device, temperature, etc.) at this time are appropriately selected according to the gelling agent.
(3) Pour and fill a cylindrical glass container with an inner diameter of about 45 mm until the height is about 45 mm so that the number of arbitrary particles is the same per filled container.
(4) Heat at 105 ° C. for 30 minutes or 95 ° C. for 10 minutes.
(5) After completion of the heat treatment, keep the stationary state, and after cooling at 25 ° C. for 3 hours, count the number of particles floating on the liquid surface of the gel composition and the number of particles settling on the bottom surface.
(6) Determination of heat stability: Based on the number of particles counted in (5), an immobilization index is obtained using the following formula. When the immobilization index is 60% or more, it is determined that there is heat resistance stability.
Immobilization index (%) = [α− (β + γ)] / α × 100 (α: total number of particles, β: number of particles floating on the liquid surface, γ: number of particles settling on the bottom surface)
<Measurement of breaking load, breaking strain rate, and brittle strain rate of standard gel>

(1) A heat-resistant wrap is attached to one side of an opening of a stainless steel cylinder having an inner diameter of about 45 mm and a height of 5 cm, and fastened with a rubber band to prepare a container for gel filling.
(2) The gelling agent dispersion used in (1) to (2) of the heat stability stability evaluation of the gel is used as a test sample, and is poured and filled into the container until the height is about 40 mm.
(3) Put a heat-resistant wrap on the container, fasten it with a rubber band, and seal it.
(4) The container containing the gel is heated in a water bath at 80 ° C. for 1 hour and then cooled at 5 ° C. for 24 hours.
(5) Remove the top and bottom wraps of the container and place the entire container on the rheometer sample stage with the top and bottom inverted so that the bottom of the gel is on top.
(6) Gently pull out the container, measure the thickness (mm) of the standard gel sample with only the gel placed on the sample stage, and measure under the following conditions.
Apparatus: Rheometer (RE-33005-1 type) (manufactured by Yamaden Co., Ltd.)
Mode: Breaking strength analysis Load cell: 2kg
Pushing speed: 1mm / sec
Pushing jig: 12 mmφ × 25 mm cylindrical shape Measurement temperature: 5 ° C.
(7) From the obtained fracture pattern, the “breaking load (N)” which is the load value at the breaking point is read and confirmed to be 1.4 to 1.5N. Thereafter, “breaking deformation (mm)” and “brittleness deformation (mm)” are read. Here, “breaking deformation (mm)” indicates the deformation distance at the breaking point, and “brittleness deformation (mm)” indicates the deformation distance from the breaking point to the brittle point. FIG. 1 shows how to read the fracture pattern.
(8) From the thickness of the standard gel sample measured in (6) and the fracture deformation (mm) obtained in (7), the fracture strain rate is obtained according to the following equation.
Breaking strain rate (%) = breaking deformation (mm) / sample thickness (mm) × 100
(9) The brittle strain rate is the ratio of brittle deformation to the original thickness of the sample. From the sample thickness measured in (6) and the brittle deformation (mm) obtained in (7), It is obtained according to the following formula.
Brittleness strain rate (%) = brittleness deformation (mm) / sample thickness (mm) × 100
<Measurement of breaking load, breaking strain rate, brittle strain rate of gel-like composition>

(1) A heat-resistant wrap is attached to one side of an opening of a stainless steel cylinder having an inner diameter of about 45 mm and a height of 5 cm, and fastened with a rubber band to prepare a container for gel filling.
(2) The gelling agent dispersion used in (1) to (2) of the heat stability evaluation of the gel composition is used as a test sample, and is poured and filled into the above container until the height is about 40 mm. To do.
(3) The subsequent operations are performed according to the procedure for measuring the breaking load, breaking strain rate, and brittleness strain rate of the standard gel.
<Storage elastic modulus G ′ of standard gel, loss tangent tan δ>

(1) A gel prepared by the same procedure as (1) to (6) in measuring the breaking load, breaking strain rate, and brittle strain rate of a standard gel is thinly sliced into 30 mm × 30 mm square and 2 mm thick.
(2) The sliced gel is set in a dynamic viscoelasticity measuring apparatus and allowed to stand for 5 minutes, and then measured under the following conditions to determine a storage elastic modulus G ′ and a loss tangent tan δ at a frequency of 2 rad / s.
Apparatus: ARES (100FRTN1 type, manufactured by TA Instruments)
Geometry: 25mm Parallel Plate
Temperature: 15 ° C
Distortion: 5% (fixed)
Frequency: 0.05 → 2 rad / s
<Gel dissolution temperature>

The gel prepared by the same procedure as (1) to (6) for measuring the breaking load, breaking strain rate, and brittleness strain rate of the standard gel is placed on a hot plate heated to 60 ° C. If the gel shape is maintained by heating for 30 minutes, the temperature of the hot plate is raised by 5 ° C. and heated in the same manner, and repeated until a fluid sol is obtained. The temperature at which the fluidized sol is obtained is defined as the gel melting temperature.
<PH of gel composition>

  A gel composition blank solution was prepared without adding a gelling agent or a calcium salt, and measured with a pH meter (“HM-50G type” manufactured by Toa DKK Corporation).

Next, the fine fibrous cellulose composites, xanthan gum, glucomannan, locust bean gum, and gellan gum used in Examples and Comparative Examples are collectively shown in the following (1) to (7).
(1) Preparation of fine fibrous cellulose composite: commercially available bagasse pulp (average degree of polymerization = 1320, α-cellulose content = 77%) was cut into 6 × 16 mm squares to obtain pulp chips, and solid content Water was added so that the concentration was 77% by mass.

  Care was taken not to separate water and pulp chips as much as possible, and the sample was passed once through a cutter mill (cutting head / horizontal blade gap: 2.03 mm, impeller rotation speed: 3600 rpm). Cutter mill processed product, carboxymethylcellulose sodium (1 mass% aqueous solution viscosity: about 3400 mPa · s) and water are weighed so that the cellulose concentration is 2 mass% and the concentration of carboxymethylcellulose sodium is 0.118 mass%. These were mixed and stirred until there was no entanglement of fibers.

  The obtained aqueous dispersion was directly subjected to 9 passes with a high-pressure homogenizer (treatment pressure 90 MPa) to obtain a fine fibrous cellulose slurry. When observed with an optical microscope and medium resolution SEM, fine fibrous cellulose having a major axis of 10 to 500 μm, a minor axis of 1 to 25 μm, and a major axis / minor axis ratio of 5 to 190 was observed. The loss tangent was 0.32. The “component stably suspended in water” was 99% by mass. When the “component that is stably suspended in water” was observed with a high-resolution SEM, a very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 10 to 400 nm, and a major axis / minor axis ratio of 20 to 300 was obtained. Observed.

  Fine fibrous cellulose: carboxymethylcellulose sodium: dextrin: rapeseed oil = 68: 12: 19.7: 0.3 (parts by weight not containing water) carboxymethylcellulose sodium ( 1% by weight aqueous solution viscosity: about 3400 mPa · s) and dextrin (DE: about 28) were added, and 15 kg was stirred with a stirring homogenizer (Primics Co., Ltd., “TK AUTO HOMO MIXER”) at 8000 rpm for 10 minutes. After stirring and mixing, 20 MPa and 1 pass treatment were performed with the above-described high-pressure homogenizer to obtain a fine fibrous cellulose slurry.

The fine fibrous cellulose slurry is dried with a drum dryer, scraped off with a scraper, and the resulting product is pulverized with a cutter mill (manufactured by Fuji Powdal Co., Ltd.) to the extent that it almost passes through a sieve with 2 mm openings. A fine fibrous cellulose composite was obtained. The crystallinity of the fine fibrous cellulose composite was 57% or more, the loss tangent was 0.52, and the “component stably suspended in water” was 100% by mass. When the “component that is stably suspended in water” was observed with a high-resolution SEM, a very fine fibrous cellulose having a major axis of 1 to 15 μm, a minor axis of 10 to 330 nm, and a major axis / minor axis ratio of 20 to 250 was obtained. Observed.
(2) Xanthan gum (Dainippon Pharmaceutical Co., Ltd.)
(3) Glucomannan (manufactured by Shimizu Chemical Co., Ltd.)
(4) Locust bean gum (Made by Unitech Foods)
(5) Gellan gum (deacetylated gellan gum) (manufactured by Saneigen FFI Co., Ltd.)
(6) Gelatin (Miyagi Chemical Co., Ltd.)
(7) Agar (for general use) (made by Ina Food Industry Co., Ltd.)
[Example 1]

A gelling agent was prepared according to the following (1) to (16), and a standard gel was obtained and evaluated.
(1) The above-mentioned fine fibrous cellulose composite as the first component, xanthan gum as the second component, glucomannan as the polysaccharide of the third component, first component: second component: third component = 50: 10 Is mixed at a mass ratio of 40 to obtain a gelling agent a.
(2) Add to ion exchange water at 25 ° C. so that the concentration of the gelling agent a is 0.92% by mass, and disperse for 5 minutes with a household mixer (manufactured by Sanyo Co., Ltd.) at about 11000 rpm. An agent dispersion was obtained.
(3) In order to confirm the heat resistance stability, a gelling agent dispersion is used as a test sample, and a plurality of paper plate-like particles (major axis 5 mm, minor axis 5 mm square, thickness 0.3 mm) are added to form a spatula. And evenly mixed.
(4) A cylindrical glass container having an inner diameter of about 45 mm was poured and filled to a height of about 45 mm so that the number of paper plate-like particles was 20 per filled container, and sealed.
(5) Heat treatment was performed at 120 ° C. for 30 minutes.
(6) After completion of the heat treatment, the mixture was kept stationary and cooled at 25 ° C. for 3 hours, and then the number of particles floating on the liquid surface of the standard gel and the number of particles settling on the bottom surface were counted.

(7) Determination of heat stability: Based on the number of particles counted in (6), an immobilization index was determined using the following equation. The results are shown in Table 1.
Immobilization index (%) = [α− (β + γ)] / α × 100
(Α: total number of particles, β: number of particles floating on the liquid surface, γ: number of particles settling on the bottom surface)
(8) Next, in order to measure the breaking load, breaking strain rate, and brittle strain rate of the standard gel, a heat-resistant wrap is attached to one side of the opening of a stainless steel cylinder having an inner diameter of about 45 mm and a height of 5 cm, It was fastened with a rubber band to prepare a container for gel filling.
(9) The gelling agent dispersion used in (1) to (2) above was used as a test sample, and was poured and filled into the container until the height was about 40 mm.
(10) The container was covered with a heat-resistant wrap, fastened with a rubber band, and sealed.
(11) The container containing the standard gel was heated in an 80 ° C. water bath for 1 hour and then cooled at 5 ° C. for 24 hours.
(12) The top and bottom wraps of the container were removed, and the container was placed on the sample stage of the rheometer with the top and bottom inverted so that the bottom surface of the standard gel was up.

(13) The container was gently removed, and the sample thickness (mm) was measured with only the standard gel placed on the sample stage, and the measurement was performed under the following conditions.
Apparatus: Rheometer (RE-33005-1 type) (manufactured by Yamaden Co., Ltd.)
Mode: Breaking strength analysis Load cell: 2kg
Pushing speed: 1mm / sec
Pushing jig: 12 mmφ × 25 mm cylindrical shape Measurement temperature: 5 ° C.
(14) When the “breaking load (N)” was read from the obtained breaking pattern, it was 1.40 N. Thereafter, “breaking deformation (mm)” and “brittleness deformation (mm)” were read.
(15) From the sample thickness measured in (13) and the fracture deformation (mm) obtained in (14), the fracture strain rate in the standard gel was determined according to the following formula. The results are shown in Table 1.
Breaking strain rate (%) = breaking deformation (mm) / sample thickness (mm) × 100
(16) The brittle strain rate in the standard gel is the ratio of the brittle deformation to the original thickness of the sample, the sample thickness measured in (13), and the brittle deformation (mm) obtained in (14) From this, it was determined according to the following equation. The results are shown in Table 1.
Brittleness strain rate (%) = brittleness deformation (mm) / sample thickness (mm) × 100

Next, in order to measure the storage elastic modulus G ′ and loss tangent tan δ of the standard gel, the gel obtained in the above (8) to (11) was thinly sliced into 30 mm × 30 mm square and 2 mm thick. The sliced gel was set in a dynamic viscoelasticity measuring apparatus, allowed to stand for 5 minutes, and measured under the following conditions to determine the storage elastic modulus G ′ and loss tangent tan δ at a frequency of 2 rad / s. Was 212 Pa, and the loss tangent was 0.08.
Apparatus: ARES (100FRTN1 type, manufactured by TA Instruments)
Geometry: 25mm Parallel Plate
Temperature: 15 ° C
Distortion: 5% (fixed)
Frequency: 0.05 → 2 rad / s

Furthermore, when the melt | dissolution temperature of gel was investigated, it was 85 degreeC.
From the results shown in Table 1, it was found that the obtained gel showed gelatin-like gel properties and gel properties suitable for nursing food for dysphagia patients. Furthermore, it was found that a gel having excellent heat stability was obtained that can maintain a solid as it is even in a fluid sol state even at a temperature corresponding to retort sterilization. .
[Example 2]

  The above-mentioned fine fibrous cellulose composite as the first component, xanthan gum as the second component, locust bean gum as the third component polysaccharide, first component: second component: third component = 35: 15: 50 To obtain a gelling agent b. A standard gel was prepared and evaluated in the same manner as in Example 1 so that the concentration of the gelling agent b was 1% by mass.

The breaking load was 1.42N. Table 1 shows the measurement results of the immobilization index, fracture strain rate, and brittle strain rate for determining heat stability. Furthermore, the storage elastic modulus was 145 Pa, the loss tangent was 0.12, and the dissolution temperature was 70 ° C.
From the results shown in Table 1, it was found that the obtained gel had gelatin-like properties, was suitable for a nursing food for dysphagia, and was excellent in heat stability.
[Example 3]

The above-mentioned fine fibrous cellulose composite as the first component, xanthan gum as the second component, locust bean gum and gellan gum as the third component polysaccharide, first component: second component: third component = 40: 10 Is mixed at a mass ratio of 50 to obtain a gelling agent c. (Here, the ratio of locust bean gum: gellan gum in the polysaccharide which is the third component is a mass ratio of 35:15.)

  It is added to ion exchange water at 25 ° C. so that the concentration of the gelling agent c is 0.96% by mass, dispersed for 5 minutes with the household mixer used in Example 1, and further stirred with a propeller stirring blade. And warmed to 95 ° C. In addition to this, a mixture obtained by adding 0.25% calcium lactate and stirring was used as a gelling agent dispersion, and a standard gel was prepared and evaluated in the same manner as in Example 1.

The breaking load was 1.37N. Table 1 shows the measurement results of the immobilization index, fracture strain rate, and brittle strain rate for determining heat stability. Although the obtained gel had agar-like characteristics, a gel excellent in heat stability was obtained.
[Example 4]

  The above-mentioned fine fibrous cellulose composite as the first component, xanthan gum as the second component, glucomannan as the polysaccharide of the third component, first component: second component: third component = 50: 15: 35 It mixed by mass ratio and was set as the gelatinizer d. Peach jelly was made and evaluated using gelling agent d. In addition, pH of the blank solution prepared without adding a gelling agent was 6.3.

  A gelling agent dispersion was prepared in the same manner as in Example 1 so that the concentration of the gelling agent d was 1% by mass. While stirring the gelling agent dispersion with a propeller stirring blade, 5% by mass of granulated sugar (Daiichi Sugar Industry Co., Ltd.) was added and mixed to obtain a peach jelly solution.

  Using this peach jelly solution as a test sample, 7 mm square dice cut yellow peach particles were added and mixed uniformly with a spatula. It was poured and filled in a cylindrical glass container having an inner diameter of about 45 mm until the height was about 45 mm so that the number of particles was 10 per filling container, sealed, and heated at 105 ° C. for 30 minutes. After heating, keep stationary, cool at 25 ° C for 3 hours, count the number of particles floating on the surface of the fruit juice jelly and the number of particles settling on the bottom, and fix in the same way as in the example The index of chemicalization was obtained.

Next, the breaking load, breaking strain rate, and brittleness strain rate of peach jelly were measured. The peach jelly solution was used as a test sample and evaluated in the same manner as in Example 1. The breaking load was 1.38N. The immobilization index was 90% and was judged to be excellent in heat stability. The fracture strain rate was 43% and the brittle strain rate was 2%. A gelatinous composition excellent in heat stability was obtained.
[Example 5]

  A fruit juice jelly was prepared and evaluated using the gelling agent c used in Example 3. The pH of the blank solution prepared without adding the gelling agent and calcium lactate was 4.2.

  A gelling agent dispersion was prepared in the same manner as in Example 3 so that the concentration of the gelling agent c was 0.93% by mass. While stirring the gelling agent dispersion with a propeller stirring blade, warm to 95 ° C., add 5% by weight granulated sugar (Daiichi Sugar Co., Ltd.) and 10% by weight raspberry puree, and mix. A jelly solution was used.

  Using this fruit juice jelly solution as a test sample, blueberry particles (diameter 10 mmφ) were added and mixed uniformly with a spatula. It was poured and filled into a cylindrical glass container having an inner diameter of about 45 mm so that the number of particles was 5 per filling container until the height was about 45 mm, sealed, and heated at 95 ° C. for 10 minutes. After heating, keep stationary, cool at 25 ° C for 3 hours, count the number of particles floating on the surface of the fruit juice jelly and the number of particles settling on the bottom, and fix in the same way as in the example The index of chemicalization was obtained.

  Next, the breaking load, breaking strain rate, and brittleness strain rate of fruit juice jelly were measured. The said fruit juice jelly liquid was evaluated by the method similar to Example 1 using it as a test sample. The breaking load was 1.46N.

The immobilization index was 80% and was judged to be excellent in heat stability. A gel-like composition having agar-like characteristics was obtained with a fracture strain rate of 13% and a brittle strain rate of 12%.
[Comparative Example 1]

Glucomannan as the first component fine fibrous cellulose composite and the third component polysaccharide were mixed at a mass ratio of first component: third component = 70: 30 to obtain a comparative gelling agent e. A standard gel was prepared and evaluated in the same manner as in Example 1 so that the concentration of the comparative gelling agent e was 1.2% by mass. At this time, the thickening by the comparative gelling agent was intense, and a standard gel having a concentration higher than 1.2% by mass could not be prepared. Further, the breaking load is 0.51 N, and the breaking load, which is the premise for measuring the breaking strain rate, the brittle strain rate, the storage elastic modulus, and the loss tangent with only two components, is 1.4 to 1. A 5N standard gel could not be prepared. When the dissolution temperature of the obtained gel was examined, the gel did not dissolve even when heated at 250 ° C. for 30 minutes, and the shape was maintained.
[Comparative Example 2]

The fine fibrous cellulose composite of the first component and locust bean gum as the third component polysaccharide were mixed at a mass ratio of first component: third component = 50: 50 to obtain a comparative gelling agent f. A standard gel was prepared and evaluated in the same manner as in Example 1 so that the concentration of the comparative gelling agent f was 1.2% by mass. At this time, the thickening by the comparative gelling agent was intense, and a standard gel having a concentration higher than 1.2% by mass could not be prepared. The breaking load is 0.37 N, and with only two components, the breaking load is 1.4 to 1.5 N, which is a premise for measuring the breaking strain rate, brittle strain rate and storage elastic modulus, and loss tangent. A standard gel could not be prepared.
[Comparative Example 3]

Instead of the gelling agent of Example 1, 2.5% by mass of gelatin was added to 95 ° C. ion-exchanged water and dissolved by stirring with a propeller stirring blade for 10 minutes. A standard gel was prepared using this gelatin solution and evaluated in the same manner as in Example 1. The breaking load was 1.4N. The immobilization index was 0% and there was no heat stability. The fracture strain rate was 39%, the brittle strain rate was 2%, the storage elastic modulus was 173 Pa, and the loss tangent was 0.10.
[Comparative Example 4]

Instead of the gelling agent of Example 1, 0.63% by mass of agar was added to ion-exchanged water at 95 ° C. and dissolved by stirring with a propeller stirring blade for 10 minutes. A standard gel was prepared using this agar solution and evaluated in the same manner as in Example 1. The breaking load was 1.45N. The immobilization index was 0% and there was no heat stability. The fracture strain rate was 16%, and the brittle strain rate was 7%.
[Comparative Example 5]

Instead of the gelling agent of Example 1, 0.11% by mass of gellan gum was added to 95 ° C. ion exchange water, and dissolved by stirring with a propeller stirring blade for 10 minutes. Further, 0.1% by mass of calcium lactate was added as an outer split. A standard gel was prepared using this gellan gum solution and evaluated in the same manner as in Example 1. The breaking load was 1.41N. The immobilization index was 20% and there was no heat stability. Further, a very brittle gel having a breaking strain rate of 13% and a brittle strain rate of 1% was formed.
[Comparative Example 6]

Xanthan gum as the second component and locust bean gum as a polysaccharide as the third component were mixed at a mass ratio of second component: third component = 30: 50 to obtain a comparative gelling agent g. A standard gel was prepared and evaluated in the same manner as in Example 1 so that the concentration of the comparative gelling agent g was 0.55% by mass. The breaking load was 1.44N. The immobilization index was 10% and there was no heat resistance stability. Further, it showed a cocoon-like physical property having an excessively large elongation, with a fracture strain rate of 57% and a brittle strain rate of 2%.
[Comparative Example 7]

Peach jelly was prepared in the same manner as in Example 4 except that 2.6% by mass gelatin was used instead of the gelling agent d in Example 4. However, gelatin was dissolved in ion exchange water at 95 ° C. and stirred for 10 minutes with a propeller stirring blade. The breaking load was 1.47N. The immobilization index was 0% and there was no heat stability. The fracture strain rate was 40%, and the brittle strain rate was 2%.
[Comparative Example 8]

  A fruit juice jelly was prepared in the same manner as in Example 5 except that 0.15% by mass gellan gum was used instead of the gelling agent c of Example 5. However, 0.15% by mass of calcium lactate was added as an external split. The immobilization index was 10% and there was no heat resistance stability. The breaking load was 1.46 N (reference value), but the gel content of the raspberry puree was not uniform, and it was possible to accurately measure the breaking load, breaking strain rate, and brittleness strain rate. It was impossible.

It is the schematic diagram which showed how to read the breaking load, the breaking deformation, and the breaking strain in the example of the breaking pattern of the gel.

Claims (8)

  A fine fibrous cellulose composite containing 50 to 95% by mass of fine fibrous cellulose as a first component and 5 to 50% by mass of a water-soluble polymer or hydrophilic substance, xanthan gum as a second component, and a third component A gelling agent comprising one or more polysaccharides selected from the group consisting of glucomannan, galactomannan, alginic acids, and gellan gum.   The gelling agent according to claim 1, wherein a mass ratio of the total content of the fine fibrous cellulose composite and the polysaccharide and the content of the xanthan gum is 70:30 to 98: 2. .   The gelling agent according to claim 1 or 2, wherein the polysaccharide is glucomannan or galactomannan.   When a standard gel having a breaking load of 1.4 N to 1.5 N is formed, the breaking strain rate is 33 to 45%, and the brittle strain rate is 1 to 10%. The gelling agent in any one of 1-3.   When a standard gel having a breaking load of 1.4 N to 1.5 N is formed, the breaking strain rate is 7 to 20%, and the brittle strain rate is 2 to 15%. The gelling agent in any one of 1-3.   A gel-like composition obtained by dispersing the gelling agent according to any one of claims 1 to 5 in an aqueous medium.   The gel composition according to claim 6, wherein the storage elastic modulus is 10 to 1000 Pa and the loss tangent is 0.05 to 1.   A first step of obtaining a gel sample by using the gelling agent according to any one of claims 1 to 5 and adjusting the concentration of the gelling agent so as to have a target gel breaking load and dispersing the gelling agent in an aqueous medium. A second step of measuring the fracture strain rate and brittleness strain rate of the obtained gel sample, measured values of the obtained fracture strain rate and brittleness strain rate, and a target fracture strain in advance The physical property control method of a gel-like composition characterized by sequentially passing through a third step of changing the composition of the gelling agent based on the difference between the rate and the brittle strain rate.

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