JP2008106178A - Water-soluble polymer dry composition - Google Patents

Abstract

Disclosed is a dry composition having good dispersibility and improved stability by adding fine fibrous cellulose to a water-soluble polymer, a thickening gelling agent, a liquid composition and a gel using the same A composition is provided.
SOLUTION: A dry composition comprising 1 to 49% by mass of crystalline fine fibrous cellulose and 51 to 99% by mass of a water-soluble polymer using plant cell walls as raw materials. It is preferred to use sodium and dextrin or carboxymethylcellulose sodium and dextrin. Furthermore, a polysaccharide is added to this to obtain a thickening or gelling agent.
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Description

  The present invention relates to a dry composition in which fine fibrous cellulose is added to a water-soluble polymer to improve dispersibility and stability, a thickening gelling agent, a liquid composition and a gel-like composition using the dry composition.

  Patent Documents 1 and 2 describe a composition comprising an additive selected from carboxycellulose, natural polysaccharides and polyols, cellulose nanofibrils having a crystallinity of 50% or less, and optional auxiliary additives. The cellulose nanofibril shown here has a crystallinity of 50% or less and is different from the crystalline fine fibrous cellulose of the present invention. As a result, the physical properties of the dry composition are also different.

Patent Documents 3 and 4 disclose a dry composition comprising 50 to 95% by mass of fine fibrous cellulose and 5 to 50% by mass of a water-soluble polymer and / or a hydrophilic substance. Patent Document 5 discloses a highly dispersible cellulose composition comprising 57 to 78% by mass of fine fibrous cellulose, 5 to 20% by mass of sodium carboxymethylcellulose, and 12 to 28% by mass of a hydrophilic substance. There is a description. However, the main component of these dry compositions is cellulose, and water-soluble polymers and hydrophilic substances are merely used as a coating agent for cellulose. That is, the present invention is different from the present invention in that the stability is improved by adding fine fibrous cellulose to a thickening stabilizer mainly composed of a water-soluble polymer.
Further, in Patent Document 5, the composition is remarkably excellent in dispersibility, and may be mixed with tap water or food raw materials to disperse particles. However, in practice, the dispersibility has not reached a practical level. The function of the composition is not sufficient.

Special Table 2000-503703 JP 2000-503704 gazette JP 2004-411119 A WO2004 / 007558 JP 2006-8857 A

  The present invention provides a dry composition having good dispersibility and improved stability by adding fine fibrous cellulose to a water-soluble polymer, a thickening gelling agent, a liquid composition and a gel using the same It is to provide a composition.

The present inventor has discovered that by adding fine fibrous cellulose to a water-soluble polymer, a dry composition having good dispersibility and further improved stability can be produced, and the present invention has been made. . That is, the present invention is as follows.
(1) A dry composition comprising 1 to 49% by mass of crystalline fine fibrous cellulose and 51 to 99% by mass of a water-soluble polymer using plant cell walls as raw materials.
(2) The dry composition according to (1), wherein the water-soluble polymer is carboxymethylcellulose sodium and dextrin.
(3) The dry composition according to (1), wherein the water-soluble polymer is xanthan gum and dextrin.
(4) The dried composition of (1) to (3), glucomannan, galactomannan, alginic acid, xanthan gum, tamarind seed gum, pectin, carrageenan, gellan gum, agar, carboxymethylcellulose sodium, soybean water-soluble polysaccharide, A composition containing at least one polysaccharide selected from karaya gum, psyllium seed gum, pullulan, gum arabic, tragacanth gum, gaddy gum, arabinogalactan, curdlan, and dry composition: polysaccharides = 1: 99 Thickening gelling agent characterized by containing by mass ratio of -99: 1.
(5) The thickening gelling agent according to (4), wherein the polysaccharide is selected from the group consisting of glucomannan, galactomannan and alginic acids.
(6) The thickening gelling agent according to claim 4, comprising xanthan gum and at least one selected from the group consisting of glucomannan, galactomannan and alginic acids as the polysaccharide.
(7) A liquid composition comprising the dry composition according to any one of (1) to (3).
(8) A gel composition containing the dry composition according to any one of (1) to (3).
(9) A liquid composition comprising the thickening gelling agent according to any one of (4) to (6).
(10) A gel composition comprising the thickening gelling agent according to any one of (4) to (6).

The dry composition of the present invention is excellent in stability and dispersibility as compared with the prior art. Therefore, stability can be imparted while suppressing stickiness. Moreover, since it is excellent in dispersibility, even if it mixes with a tap water and a food raw material, it is highly practical in manufacture of a product.
Furthermore, by combining with a specific polysaccharide, it is possible to provide a novel thickening gelling agent and a liquid or gel composition containing the same.

Hereinafter, the present invention will be specifically described with a focus on preferred embodiments.
The water-soluble polymer of the present invention refers to a polymer that dissolves in water at room temperature. Specific examples of water-soluble polymers include gum arabic, carrageenan, caraya gum, agar, xanthan gum, gellan gum, tamarind seed gum, indigestible dextrin, pectin, water-soluble soybean polysaccharide, sodium carboxymethylcellulose, methylcellulose, poly One or two or more substances selected from sodium acrylate, dextrins and the like are used. Among these, it is preferable to use carboxymethylcellulose sodium or xanthan gum in combination with dextrin. The weight ratio of carboxymethylcellulose sodium or xanthan gum and dextrin is (carboxymethylcellulose sodium or xanthan gum): dextrin = 5: 95 to 100: 0, preferably 10:90 to 30:70, more preferably 15:85. 40:60 (however, 100 in total).

  The sodium carboxymethylcellulose of the present invention has a linear structure in which the hydroxyl group of cellulose is substituted with monochloroacetic acid and D-glucose is linked by β-1,4. As carboxymethylcellulose sodium, the degree of substitution 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. Moreover, it is preferable to use the viscosity of 1 mass% aqueous solution at about 5-9000 mPa * s, More preferably, it is used at about 1000-8000 mPa * s, More preferably, it is used at about 2000-6000 mPa * s. is there. Within this range, there is no problem in handling properties, and the performance of the thickening gelling agent is also in a good range.

In the xanthan gum of the present invention, the main chain has a structure in which D-glucose is linked by β-1,4, and the side chain composed of D-mannose, D-glucuronic acid, and D-mannose is added to the anhydroglucose of the main chain. It is a combination. 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.
The dextrin of the present invention is a general term for substances in which several α-glucoses are polymerized by glycosidic bonds, and is usually a linear compound obtained by chemically or enzymatically degrading starch. In the dry composition, the substance having the best balance between function and dispersibility is a dextrin having a DE (dextrose equivalent) of 20 or more. Moreover, you may use the cyclodextrin etc. which are obtained by making an enzyme act.

The fine fibrous cellulose of the present invention is made of plant cell walls as a raw material, is crystalline, and has a fine fibrous shape. For example, “water-dispersible cellulose” disclosed in JP-A-2004-41119 or WO2004 / 007558 can be used.
Plant cell walls used as raw materials are cellulosic materials that can be used industrially, such as wood (conifers, hardwoods), cotton linters, kenaf, manila hemp (avaca), sisal hemp, jute, sabaigrass, esparto grass, bagasse, rice Pulp based on natural cellulose such as straw, wheat straw, straw, bamboo is used. Among these, bagasse pulp, rice straw pulp, wheat straw pulp and bamboo pulp originating from the cell wall of the grass family are preferred. Unlike wood pulp and hemp pulp, these pulps are very easily refined, so that high-performance products can be efficiently produced. However, raw materials derived from soft cells such as microbial cellulose and beet pulp and fruit fiber pulp are not included.

  As the plant cell wall of the raw material, it is preferable to use a cellulosic material having an average degree of polymerization of 400 or more and an α-cellulose content of 60 to 100% by mass. However, even within that range, those having an average degree of polymerization of less than 1300 and an α-cellulose content exceeding 90% by mass are not included. More preferably, the α-cellulose content is 85% by mass or less, and most preferably 75% by mass or less.

  The fine fibrous cellulose used in the present invention is crystalline. Specifically, the crystallinity as measured by the X-ray diffraction method (Segal method) exceeds 50%. Preferably it is 55% or more. The substance of the present invention contains components other than cellulose, but these components are amorphous and are counted as amorphous. Therefore, as a result of the measurement, if the crystallinity is 50%, it can be said that the crystallinity of cellulose is 50% or more. In the case of 49%, for example, fine fibrous cellulose must be separated from other components and measured.

In this specification, “fine fibrous” means that the length (major axis) is 0.5 μm to 1 mm and the width (minor axis) is 2 nm to 60 μm as observed and measured with an optical microscope and an electron microscope. This means that the ratio of length to width (major axis / minor axis) is 5 to 400.
The fine fibrous cellulose of the present invention 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 less than 30% by mass, functions such as the above-described thickening are not sufficiently exhibited. The higher the content, the more preferable, but 50% by mass or more is more preferable. In the present specification, the “component that is stably suspended in water” specifically refers to an aqueous dispersion having a concentration of 0.1% by mass, which is centrifuged at 9800 m / s ² for 5 minutes. Is a component having the property of being stably suspended in water without settling, and is expressed as a percentage of the total amount of cellulose. (The method for measuring “a component that is stably suspended in water” will be described later.)

  The component has a length (major axis) of 0.5 to 30 μm and a width (minor axis) of 2 to 600 nm observed and measured with a high resolution scanning electron microscope (high resolution SEM). It consists of a fibrous cellulose whose ratio (major axis / minor axis ratio) is 20-400. The width is preferably 100 nm or less, more preferably 50 nm or less.

  The fine fibrous cellulose of the present invention preferably has a loss tangent (tan δ) of less than 1 measured under conditions of a strain of 10% and a frequency of 10 rad / s when an aqueous dispersion having a concentration of 0.5% by mass is used. . More preferably, it is less than 0.6. When the loss tangent is 1 or more, the stability, the thickening interaction with other polysaccharides described later, and the gel forming ability are inferior. If it is less than 0.6, the performance is further improved.

The mass ratio in the dry composition of the present invention is fine fibrous cellulose: water-soluble polymer = 1 to 49:51 to 99 (however, 100 in total).
The mass ratio of fine fibrous cellulose: water-soluble polymer is not particularly limited as long as it is within the above range, but is preferably 15 to 49:51 to 85, and more preferably 35 to 45:55 to 65. At that time, a dry composition having an excellent balance between dispersibility and stability is obtained, and as a result, a thickening gelling agent comprising the composition as a constituent also exhibits an excellent function.
The form of this dry composition takes various forms such as granules, granules, powders, scales, pieces, and sheets.

The drying method for obtaining the dry composition is not limited in any way, for example, freeze-drying method, spray drying method, shelf-type drying method, drum drying method, belt drying method, thinly extending to a glass plate, etc. and drying Or a fluidized bed drying method, a microwave drying method, a heating fan type vacuum drying method, or the like. Dispersibility deteriorates when dried for a long time at high temperature. This seems to be because keratinization between cellulose particles (fibers) proceeds strongly. The temperature is preferably 120 ° C. or lower, particularly 110 ° C. or lower from the viewpoint of water dispersibility. Desirably, the drying time is short, and when the moisture reaches a predetermined value, it is desirable to finish drying immediately. The water content after drying is preferably 15% by mass or less in consideration of handleability and stability over time. More preferably, it is 10 mass% or less. Most preferably, it is 6 mass% or less. When the amount is less than 2% by mass, static electricity is charged and it may be difficult to handle the powder.
After drying, if necessary, it may be pulverized with a cutter mill, hammer mill, pin mill, jet mill or the like.

  When a hydrophilic substance is added to the dry composition of the present invention in addition to the water-soluble polymer and fine fibrous cellulose, the function is further improved. A hydrophilic substance is a substance that is highly soluble in cold water, has little viscosity and is solid at room temperature, and is a water-soluble saccharide (glucose, fructose, sucrose, lactose, isomerized sugar, xylose, trehalose, coupling One or more selected from sugar, palatinose, sorbose, reduced starch saccharified starch, maltose, lactulose, oligosaccharides (fructooligosaccharide, galactooligosaccharide, etc.), sugar alcohols (xylitol, maltitol, mannitol, sorbitol, etc.) Low molecular weight substances tend to be more effective in improving dispersibility, and glucose, sucrose, trehalose, etc. show better properties, but dryness during production, hygroscopicity of products, stability over time There is a tendency to be inferior.

  In addition to the water-soluble polymer, fine fibrous cellulose, and hydrophilic substances, the dry composition includes starches, fats and oils, proteins, salt, various phosphate salts, emulsifiers, acidulants, and sweeteners. Ingredients such as fragrances and pigments may be appropriately blended. In particular, dispersibility of fats and oils and surfactants may be further improved by blending them.

  The oils and fats mentioned here are soybean oil, palm oil, corn oil, camellia oil, palm oil, palm kernel oil, linseed oil, salad oil, sesame oil, cottonseed oil, rapeseed oil, olive oil, sunflower oil, babasou oil, cacao oil, rice Oil, safflower oil, mustard oil, ginger oil, peanut oil, tung oil, castor oil, whale oil, beef tallow, lard, hardened oil, milk fat, butter, etc., animal and plant oils, glycerin fatty acid esters and derivatives thereof Monoglyceride derivatives such as acetic acid monoglyceride, succinic acid monoglyceride, citric acid monoglyceride, polyglycerin fatty acid ester, polyglycerin condensed ricinoleic acid ester, lecithin, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Surface activity of Fatty acids such as oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and their esters, higher alcohols such as lauryl alcohol, cetyl alcohol, ceryl alcohol, carnauba wax, candelilla wax, rice bran wax, shellac One or a combination of two or more selected from waxes such as beeswax and lanolin, hydrocarbons such as paraffin wax, liquid paraffin and squalene, and silicone oils such as polydimethylsiloxane are used. 0.05 to 1% by mass is preferable.

  In the case of a surfactant, the HLB value is preferably 13 or less. Fats and oils can be added as they are, but they may be added after making the form of an emulsion obtained by adding a surfactant, water or the like to animal and vegetable oils and homogenizing them. Moreover, you may mix | blend with forms, such as margarine and fresh cream containing fats and oils.

  This composition is characterized in that when it is put into an aqueous medium and mechanical shearing force is applied, the particles collapse and develop viscosity. If the composition range is exceeded, the disintegration / dispersibility of the particles in the aqueous medium is remarkably reduced, and there is no need to take measures such as lowering the ion concentration, stirring at a high temperature, or stirring for a long time. In various industries, especially in the food industry, it cannot withstand use except for specific purposes.

When the dry composition of the present invention is stirred in a 0.01% calcium chloride aqueous solution, the particles easily disintegrate and disperse and develop functions. The degree is expressed by a dispersibility index (%) calculated by the following equation, and a sample having a dispersibility index of 50% or more is determined to be “dispersibility”. This is determined from the ratio of “0.01% calcium chloride water viscosity” to “ion exchange water viscosity” at 0.25 mass%.
Dispersibility index (%) = (0.01% calcium chloride water viscosity / ion exchange water viscosity) × 100
The 0.01% calcium chloride aqueous solution has a numerical value expressed as “hardness” of tap water of “90”, which is the highest level of ion concentration in tap water in Japan. In the presence of such ions, it is known to affect the swelling and solubility of water-soluble polymers such as carboxymethylcellulose and sodium, which promotes particle disintegration and dispersion. The property to do will fall remarkably. That is, it is required that the composition be a dry composition that exhibits its function even under such conditions.

  The polysaccharide of the present invention is glucomannan, galactomannan, alginic acid, xanthan gum, tamarind seed gum, pectin, carrageenan, gellan gum, agar, sodium water-soluble polysaccharide, caraya gum, psyllium seed gum, pullulan, gum arabic , Tragacanth gum, gaddy gum, arabinogalactan and curdlan, preferably at least one selected from the group consisting of glucomannan, galactomannan, alginic acids, xanthan gum, tamarind seed gum and pectin. The type of galactomannan is preferably guar gum, locust bean gum or tara gum.

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. If the degree of purification is low, there is a peculiar irritating odor. Therefore, it is desirable to use one having a high degree of purification, but konjac powder or konjac mannan can also 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.

Xanthan gum has a structure in which the main chain has a β-1,4 bond with D-glucose, and a side chain composed of D-mannose, D-glucuronic acid, and D-mannose is bonded to the main chain anhydroglucose. Is. 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.
Tamarind seed gum is a xyloglucan having a main chain of glucose and xylose in the side chain.

  The main chain of pectin is that α-D-galacturonic acid is α-1,4 linked and is partially esterified with methanol. The molecule is twisted by β-L-rhamnose entering the main chain of galacturonic acid. In addition, there are cases where neutral araban, galactan, xylan, and the like are bonded as side chains and in some cases. Galacturonic acid constituting pectin exists in two forms, a methyl ester form and an acid form. The proportion of galacturonic acid present in the form of the ester is called the degree of esterification, and those having a degree of esterification of 50% or more are called HM pectin and those having a degree of less than 50% are called LM pectin.

Carrageenan has a structure in which β-1,4 bonds and α-1,3 bonds of β-D-galactose and α-D-galactose are alternately repeated and galactose units are bonded.
Gellan gum is a product in which four sugars, glucose, glucuronic acid, glucose and L-rhamnose, are linked in a straight chain by repeating units. Native gellan gum has a 3-5% acetyl group bonded to the C-6 position of this glucose and a glyceryl group bonded to the C-2 position. Deacetylated gellan gum is obtained by deacetylating native gellan gum and purifying it.

Agar is β-D-galactose and α-L-galactose β-1,4 bonds, agarose having α-1,3 bonds alternately repeated, and agaropectin which is an ionic polysaccharide other than agarose A polysaccharide consisting of
Carboxymethylcellulose sodium is obtained by etherifying a hydroxyl group of cellulose with monochloroacetic acid or monochloroacetic acid sodium salt, and has a linear structure in which D-glucose is linked by β-1,4.

The soybean water-soluble polysaccharide is composed of sugars such as galactose, arabinose, galacturonic acid, rhamnose, xylose, and glucose, and is presumed to have galactan and arabinan bound to the rhamnogalacturonic acid chain.
Karaya gum is a partially acetylated branched polysaccharide containing about 40% uronic acid and no more than 8% acetyl groups. There are rhamnose and galacturonic acid in the main chain, and glucuronic acid is presumed to be in the side chain.

Psyllium seed gum has a highly branched structure with xylan as the main chain, and the side chain consists of arabinose, xylose, galacturonic acid, and rhamnose. This sugar composition is estimated to be about 64% D-xylose, about 20% L-arabinose, about 6.4% L-rhamnose, and about 9.4% D-galacturonic acid.
Pullulan has a linear structure in which maltotriose repeats α-1,6-glycosidic bonds.

Although the molecular structure of gum arabic has not been clarified, it is reported that its constituent sugar is 36% D-galactose, 31% L-arabinose, 13% L-rhamnose, 18% D-glucuronic acid and 2% protein. ing.
Tragacanth gum is obtained from the sap of leguminous tragacanth and is said to contain 70% tragacantic acid and 10% arabinogalactan.
Gaddy gum is composed of D-glucuronic acid, L-arabinose, D-galactose, D-mannose, and D-xylose, and the D-galactose residue constitutes the main chain.
With arabinogalactan, D-galactose is the main chain, and the ratio of L-arabinose in the side chain is about 5 to 6: 1. From the β1 → 3 linked galactan backbone, short side chains of β1 → 6 linked galactose and β1 → 3 linked arabinose emerge.
Curdlan is a linear glucan in which glucose is β-1,3-glucoside-bonded.

  Dry composition of the present invention, galactomannan, glucomannan, alginic acids, xanthan gum, tamarind seed gum, pectin, carrageenan, gellan gum, agar, carboxymethylcellulose sodium, soybean water-soluble polysaccharide, caraya gum, psyllium seed gum, pullulan, By containing at least one polysaccharide selected from gum arabic, tragacanth gum, gaddy gum, arabinogalactan, and curdlan, a thickening gelling agent having a particle-immobilizing action described later can be prepared. The mass ratio in the thickening gelling agent of the present invention is dry composition: polysaccharide = 1: 99 to 99: 1 (however, 100 in total). The mass ratio of the dry composition: polysaccharide is not limited as long as it is within the above range, but it is preferably 20:80 to 90:10, more preferably 50:50 to 70:30. Sometimes, it exhibits an excellent function as a thickening gelling agent. That is, it exhibits excellent functions as a thickener application having excellent stability described later, a gelling agent having excellent heat resistance, and the like.

The stability in the present invention is expressed based on an immobilization index. When the liquid immobilization index using the dry composition or the thickening gelling agent of the present invention is larger than the liquid immobilization index using only the polysaccharide, it is determined to have a particle immobilization action. The immobilization index mentioned here is the ratio (%) of the immobilized particles in all particles, and is represented by the following formula.
Immobilization index (%) = [{α− (β + γ)} / α] × 100 (Equation 1)
(Α: total number of particles, β: number of particles floating on the surface, γ: number of particles precipitated on the bottom surface)

  When at least one polysaccharide selected from the group consisting of glucomannan, galactomannan and alginic acids is mixed and stirred in water, the dry composition of the present invention exhibits a thickening synergistic effect described later. In addition, after mixing and stirring in water, a heat-resistant gel is formed by standing (heat treatment). Among them, the gel with glucomannan is frozen and thawed to obtain a “gel-like composition having a sponge-like structure. Form ".

As the galactomannan, it is preferable to select any of guar gum, locust bean gum, and tara gum, and among them, locust bean gum or tara gum is preferable when used as a gelling agent.
Furthermore, a thickening gel comprising at least three components of a dry composition as the first component, xanthan gum as the second component, and a polysaccharide selected from the group consisting of glucomannan, galactomannan and alginic acids as the third component. When the agent is mixed and stirred in water, the above-mentioned thickening synergistic effect and the gel breaking strength of the heat-resistant gel are further improved.

The mass ratio of the second component xanthan gum to the first component and the third component described above is “first component (dry composition) + 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 (however, in total, 100). Within this range, a heat resistant gel is obtained.
The heat-resistant gel of the present invention is a gel-like composition in which the gel does not dissolve and maintains a uniform structure even when subjected to heat treatment (sterilization treatment), and settling and floating of the charged particles are suppressed. Because of this function, it is possible to supply normal temperature circulating gel foods that require strong heat treatment (sterilization treatment), heat-stable multilayer gels, heat-stable solid-containing gels, and the like.

The heat resistance of the gel composition can be determined by the immobilization index shown below. First, a uniform aqueous dispersion containing 1% by mass of a gelling agent is prepared, and a predetermined amount of “particles” as described below is mixed and sufficiently stirred. Next, after filling this into a container, heat sterilization is performed, and the immobilization index after heat sterilization is measured, and when it is 40% or more, it is determined that it has heat resistance. The immobilization index is the ratio (%) of the immobilized particles in all particles, and is expressed by the following formula.
Immobilization index (%) = [α− (β + γ)] / α × 100 (Expression 2)
(Here, α is the total number of particles, β is the number of particles floating on the surface, and γ is the number of particles settling on the bottom surface.)

  The term “particles” as used herein refers to solid particles having a specific gravity of 0.1 to 3.5 and each particle having a size that can be visually recognized. Specifically, the particle having a size that can be visually discriminated refers to a particle having a major axis and a minor axis of 50 μm or more, which will be described later. When it is less than 50 μm, it is difficult to visually confirm the particles with human vision. If the major axis and the minor axis are 50 μm or more, the shape of the particles is not particularly limited. Specifically, a large number of pieces of paper, food ingredients and the like having a certain size can be used as particles. The degree of heat resistance of the gel-like composition depends on how much such particles can stably maintain the fixed position in the gel-like composition without settling or floating on the surface after the heat sterilization treatment. Determine.

  The gel composition using the gelling agent of the present invention has sufficient heat resistance, and can be heat sterilized when applied to foods and the like in a stable state that does not change the state of the food. . The heat sterilization temperature suitable for using the gel composition in foods and the like is preferably 80 ° C. or higher, more preferably 105 to 150 ° C., and further preferably 105 to 121 ° C. As a standard of the heating time, it is about 1 to 3 hours at 80 ° C., and about 30 minutes if it is 105 ° C. or more.

  When using the thickening gelling agent of the present invention, auxiliary agents (inorganic salts, saccharides, acids, etc.) necessary for thickening and gelation are used in combination, as appropriate, depending on the polysaccharide that is the component. . For example, calcium salt (calcium lactate, calcium chloride, etc.) may be used for gellan gum, calcium, saccharides, acid, etc. may be used for pectin, and milk components may be used for carrageenan.

  The liquid composition of the present invention is in the form of a liquid or paste at room temperature, and includes a processed liquid composition, such as ice cream produced by cooling the liquid composition. . The liquid composition includes a liquid food composition, a liquid cosmetic composition, a liquid pharmaceutical / medical product composition, a liquid industrial composition, and the like. The amount of the dry composition or thickening gelling agent added to these liquid compositions is not particularly limited, but is usually about 0.001 to 2% by mass, preferably 0.1 to 1% by mass. It is good to adjust the addition amount according to the purpose. For example, it is generally about 0.001 to 0.6% by mass for stabilizing beverages, and about 0.1 to 2% by mass for imparting viscosity to mayonnaise.

  Examples of the liquid food composition of the present invention include “coffee, black tea, Japanese tea, oolong tea, barley tea and other teas, matcha tea, cocoa, juice, juice, soy milk, soy beverage, etc.”, “raw milk, processed milk” Milk, fermented milk drinks, lactic acid bacteria drinks, milk-containing drinks such as milk drinks "," fermented milk "," Zenzai "," various drinks including nutrition-enriched drinks such as calcium-fortified drinks and dietary fiber-containing drinks " , "Frozen confectionery such as ice cream, soft cream, lact ice, ice milk, sorbet, frozen yogurt", "Dairy products such as coffee whitener, whipped cream, custard cream, cheese", "Japanese including soft candy, chocolate, etc."・ Western confectionery products, “Fat processed foods such as spreads and shortenings”, “Soups”, “Stews” , “Fillings”, “Batter mixes”, “Seasonings such as sauces, sauces, dressings”, “Various kneading seasonings represented by knead”, “Fruit sauce, fruit preparation, jam, strawberry "Processed fruit and vegetable products", "Delicates such as salted fish", "Pickles", "Food food such as tube feeding liquid food", "Liquid or pasty health foods" and " "Liquid or pasty pet foods" and the like are included, and even if the processing method of the form or preparation at the time of use is different, such as retort food, frozen food, food for microwave oven, etc., it is included in the present invention.

  Examples of liquid pharmaceutical products are “oral medicines such as syrups, vitamins, and tonics”, “nasal medicines such as hormones”, “infusions such as infusions, antitumor drugs, and chemotherapeutics”・ Tube medicines, enteral medicines, skin drugs, drugs and DNA carriers, “biomaterials such as artificial cartilage and bioadhesives”, “liquid foods such as tube liquid foods classified into pharmaceuticals”, "Quasi-drugs such as medicinal cosmetics, vitamin-containing health agents, hair preparations, medicated toothpastes, bath preparations, insecticides / insect repellents, odor control agents, mouth refreshing agents", patching agents, coating agents, etc. It is done.

Examples of liquid cosmetic compositions include: “skin lotion, emulsion, serum, pack, moisture cream, massage cream, cold cream, cleansing cream, face wash, vanishing cream, emollient cream, hand cream, sunscreen cosmetics, etc. `` Cosmetics for skin, '' `` Finishing cosmetics such as foundations, lipsticks, lip balms, cheeks, sunscreen cosmetics, eyelash cosmetics such as eyebrows and mascara, and nail cosmetics such as nail polish and light removal liquid '', `` Shampoos, hair rinses, hair tonics, hair treatments, pomades, tics, hair creams, perfume oils, hair styling agents, hair styling agents, hair sprays, hair dyes, hair cosmetics such as hair restorers and hair nourishing agents, and even hand cleaners Detergent, bath cosmetic, shaving cosmetic, good Agents, toothpaste, ointments, plasters and the like.

  Examples of liquid industrial compositions include pigments, paints, inks, "deodorants / fragrances, antibacterial / antifungal agents, sanitary materials, toothpaste and other toiletry products", adhesives, coating agents, surfactants , Culture materials, detergents / liquid soaps, catalysts, polymerization aids, explosives / explosives, fuels, etc.

  The gel composition of the present invention can be obtained by dispersing a thickening gelling agent in an aqueous medium. The gel composition takes a gel form at room temperature, and includes a gel food composition, a gel cosmetic composition, a gel pharmaceutical / medical product composition, a gel industrial composition, and the like. The amount of the dry composition or thickening gelling agent added to these gel compositions is not particularly limited, but is usually about 0.1 to 2% by mass, preferably 0.3 to 1%. It is about mass%.

  The gel composition may be a mixture of 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 inhibit gel formation. It is desirable to prepare a liquid composition containing a gelling agent after preparing other ingredients and mixing them. The gel composition may be used after being subjected to treatment such as freezing, cold thawing, and drying.

  Examples of gel food compositions that can be applied include “desserts such as pudding and jelly”, “yogurts such as hard yogurt, soft yogurt, fruit yogurt, calcium-enriched yogurt”, “ice cream” , Frozen desserts such as soft ice cream, lacto ice, ice milk, sorbet, frozen yogurt "," Japanese and Western confectionery including candy, gummy candy, cookies, biscuits, cornflakes, rice crackers, hot cakes, chocolate, gum, candy, etc. ", Ingredients added as an accent to beverages, bean paste, yogurt, etc. ”,“ Food for people with dysphagia, nursing foods, chopped foods, thick foods, etc. ”,“ jelly-like beverages ”,“ sauce, sauce , Dressing, mayonnaise, etc. `` Tastes '', `` Various kneading seasonings typified by kneading '', `` Noodles '', `` Fruit processed products and vegetable products typified by fruit sauce, fruit preparation, jam, strawberry '', `` Fillings '' , “Batter mixes”, “delicates such as salty spices”, “pickles”, “liquid foods classified into foods”, “health foods and fortified foods”, “gel foods such as steamed rice cakes and tofu” , “Kneaded products such as kamaboko”, “meat foods such as sausage, ham”, “dairy products such as whipped cream, butter, cheese”, “oiled and processed foods such as spreads, shortenings”, “vegetables / bento” “Gelated products of regular drinks (coffee, teas, isotonic drinks, milk, milk drinks, soy milk, matcha tea, cocoa, shiruko, juice, etc.)”, “pet foods” Etc., and the like.

  In addition to the examples described above, by using the gelling agent of the present invention, it is possible to provide a novel 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 warp-like foods that use this gelling agent instead of rice. There are "new low-calorie foods" and "meal substitute chuapak drinks" that can be heated by gelling soup and miso soup.

  Examples of gel-like pharmaceutical / medical product compositions are classified into “pharmaceuticals such as nasal drugs such as oral drugs and hormone drugs, enteral drugs, skin drugs, transdermal drugs”, 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, artificial organs, biosurfactants such as medical surfactants ", patching agents, coating agents and the like.

  Examples of gel cosmetic compositions 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, teeth Come, ointments, and plasters and the like.

  Examples of gel industrial compositions include pigments, paints, inks, deodorants / fragrances, antibacterial / 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, adsorbents, detergents / soaps, catalysts, polymerization aids, explosives / explosives, fuels, etc.

In addition to the thickener / gelling agent and water, other components may be blended in the liquid composition or the gel composition. For example, food materials (meat meat, fish meat, beans / cereals and pulverized products thereof, milk / dairy products, fermented milk, vegetables, fruits, fruit juices, edible fats and oils), beverages (coffee, teas, juices, milk drinks, soy milk) Etc.), seasonings (miso, soy sauce, sugar, salt, sodium glutamate, etc.), sweeteners, sugars, sugar alcohols, fragrances, pigments, spices, acidulants, emulsifiers, surfactants, preservatives, shelf life improvers , Antibacterial agents, disintegrating agents, antifoaming agents, foaming agents, pH adjusting agents, thickening stabilizers, dietary fiber, nutrient enhancers (vitamins, minerals, amino acids, etc.), extracts, proteins, starches, peptides, alcohol , Organic solvents, plasticizers, oils and fats, buffers, fuels, explosives and explosives, acids, alkalis, ionic substances, microcapsules, cosmetic ingredients (whitening ingredients, moisturizing ingredients, etc.), physiologically active substances, medicinal ingredients, pharmaceuticals Additive Pesticides, fertilizers, deodorants, insecticides, metals, catalysts, ceramics, paints, inks, pigments, abrasives, synthetic polymers (plastics, rubber, synthetic fibers, etc.), natural polymers (collagen, hyaluronic acid, Natural fibers, etc.), paper, etc. may be blended. 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. Further, the liquid composition or the gel composition may be used after being cooled and hardened, or after being subjected to a treatment such as cold thawing or drying treatment.
Since the liquid food composition and the gel food composition are usually supplied at a pH of 3 to 8 and a salt concentration of 0.001 to 20%, it is required to exhibit an effect under such conditions.

Next, the present invention will be described in more detail with reference to examples. The evaluation of various physical properties of the substance according to the present invention was based on the following method.
<Average degree of polymerization of cellulosic material>
ASTM Designation: D 1795-90 “Standard Test Method for Intrinsic Visibility of Cellulose”.
<Α-cellulose content of cellulosic material>
It is carried out according to JIS P8101-1976 (“dissolving pulp test method” 5.5 α cellulose).

<Shape of cellulose fiber (particle) (major axis, minor axis, major axis / minor axis ratio)>
Since the range of the size of cellulose fibers (particles) is wide, it is impossible to observe all with one kind of microscope. Therefore, an optical microscope and a scanning microscope (medium resolution SEM, high resolution SEM) are appropriately selected according to the size of the fibers (particles), and observed and measured.
When using an optical microscope, adjust the aqueous dispersion of cellulose fibers (particles) prepared at the time of “0.25% viscosity” measurement described later to an appropriate concentration, place it on a glass slide, and then cover Put on a glass and observe.
In addition, when using a medium resolution SEM (JSM-5510LV, manufactured by JEOL Ltd.), a sample aqueous dispersion is placed on a sample stage and air-dried, and then Pt—Pd is deposited by about 3 nm and observed.
In the case of using a high-resolution SEM (S-5000, manufactured by Hitachi Science Systems, Ltd.), a sample aqueous dispersion is placed on a sample stage and air-dried, and then Pt—Pd is evaporated by about 1.5 nm and observed.
The major axis, minor axis, and major axis / minor axis ratio of the cellulose fibers (particles) were measured by selecting 15 (pieces) or more from the photographed photographs. Some fibers were almost straight and curved like hair, but never round like lint. The minor axis (thickness) was varied among single fibers, but an average value was adopted. The high-resolution SEM was used for observing fibers 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) A sample and pure water are weighed so that an aqueous dispersion having a solid content concentration of 0.5% by mass is obtained, and the mixture is ace homogenizer (trademark, manufactured by Nippon Seiki Co., Ltd., AM-T type) at 15000 rpm for 15 minutes. scatter.
(2) Leave in an atmosphere at 25 ° C. for 3 hours.
(3) After putting the sample solution into the dynamic viscoelasticity measuring apparatus, the sample solution is allowed to stand for 5 minutes and then measured under the following conditions to determine a loss tangent (tan δ) at a frequency of 10 rad / s.
Equipment: ARES (100FRTN1 type)
(Trademark, manufactured by Rheometric Scientific, Inc.)
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”>
(1) Weigh the sample and pure water so that the cellulose concentration is 0.1% by mass, and disperse with an ace homogenizer (trademark, manufactured by Nippon Seiki Co., Ltd., AM-T type) at 15000 rpm for 15 minutes. To do.
(2) Put 20 g of the sample solution into a centrifuge tube and centrifuge for 5 minutes at 9800 m / s ² in a centrifuge.
(3) The upper liquid portion is removed and the mass (a) of the sediment component is measured.
(4) Next, the sedimentation component is absolutely dried, and the mass (b) of the solid content is measured.
(5) The content (c) of the “component that is stably suspended in water” is calculated using the following formula.
c = 5000 × (k1 + k2) [mass%]
However, k1 and k2 are calculated using the following formula and used.
k1 = 0.02−b + s2
k2 = k1 × w2 / w1
(Carboxymethylcellulose / sodium + hydrophilic substance) / cellulose = d / f [compounding ratio]
w1 = 19.98−a + b−0.02 × d / f
w2 = a−b
s2 = 0.02 × d × w2 / {f × (w1 + w2)}

When the content of “a component that is stably suspended in water” is very large, the weight of the sediment component becomes a small value, so that the measurement accuracy is lowered by the above method. In that case, the procedure after (3) is performed as follows.
(3 ′) Obtain the liquid portion of the upper layer and measure the weight (a ′).
(4 ′) Next, the upper layer component is completely dried, and the weight (b ′) of the solid content is measured.
(5 ′) The content (c) of “a component that is stably suspended in water” is calculated using the following formula.
c = 5000 × (k ₁ + k ₂ ) [mass%]
However, k1 and k2 are calculated using the following formula and used.
k1 = b′−s2 × w1 / w2
k2 = k1 × w2 / w1
(Carboxymethylcellulose / sodium + hydrophilic substance) / cellulose = d / f [compounding ratio]
w1 = a′−b ′
w2 = 19.98−a ′ + b′−0.02 × d / f
s2 = 0.02 × d × w2 / {f × (w1 + w2)}
If the boundary between the liquid portion of the upper layer and the sediment component is not clear in the operation (3) and separation is difficult, the operation is performed with the cellulose concentration lowered appropriately.

<The 0.25 mass% viscosity of a dry composition>
(1) Weigh out the sample and the dispersion medium so as to obtain an aqueous dispersion having a solid content concentration of 0.25% by mass, and prepare an “ion exchange water viscosity solution” and a “0.01% calcium chloride water viscosity solution”. To do.
(1a) Ion-exchanged water viscosity solution: A sample and ion-exchanged water are weighed and dispersed at 25 ° C. and 15000 rpm for 5 minutes using an ace homogenizer (trademark, manufactured by Nippon Seiki Co., Ltd., AM-T type).
(1b) 0.01% calcium chloride aqueous solution: A sample and 0.01% by mass calcium chloride water are weighed out and T.M. K. Disperse at 8000 rpm for 10 minutes at 60 ° C. using a homomixer (trademark, MARK-2 type manufactured by Tokushu Kika Kogyo Co., Ltd.).
(2) The above two kinds of viscosity solutions are allowed to stand in an atmosphere at 25 ° C. for 3 hours.
(3) Set in a rotational viscometer (manufactured by Tokimec Co., Ltd., B-type viscometer, BL-type) while still standing, and start rotating the rotor 30 seconds after the end of stirring, and then from the indicated value 30 seconds later Viscosity is calculated. The rotor speed is 60 rpm, and the rotor is appropriately changed depending on the viscosity.

<Determination of dispersibility of dry composition>
(1) The dispersibility index (%) is calculated from the “0.01% calcium chloride water viscosity” and the “ion-exchange water viscosity” at 0.25% by mass obtained in accordance with the following formula.
Dispersibility index (%) = (0.01% calcium chloride water viscosity / ion exchange water viscosity) × 100
(2) A sample having a dispersibility index of 50% or more is determined to be “dispersibility”.
<Measurement of particle size>
The particles were observed with a microscope or measured with a micrometer to determine the major and minor diameters. The number of repetitions at this time was 30.
<Specific gravity of particles>
The specific gravity was calculated according to JIS Z 8807-1976 (Solid specific gravity measuring method).
<PH>
Measured with a pH meter (“HM-50G type” manufactured by Toa DKK Corporation). However, the pH of the gel composition is measured using the liquid composition before gelation as a test sample.

<Preparation of 0.35 mass% aqueous dispersion and measurement of particle number>
First, the sample and water are weighed so that the solid content becomes an aqueous dispersion of 1% by mass, and dispersed at 8000 rpm for 10 minutes using “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.). . This 1% by mass sample aqueous dispersion: water is mixed at a ratio of 3.5: 6.5, and further dispersed for 5 minutes to prepare a 0.35% by mass sample aqueous solution. The temperature at this time is not particularly specified, but a temperature suitable for the dispersion of the sample is selected. Moreover, you may add the additive (calcium etc.) indispensable for expression of a function according to the property of the polysaccharide to be used.
The particle fixing action of the 0.35 mass% aqueous dispersion is a property of holding paper particles (a rectangle with a major axis of 5 mm, a minor axis of 3 mm, a thickness of 0.3 mm and a specific gravity of 0.9).
Fill each 100 mL sample bottle with 0.35 wt% sample aqueous dispersion. Next, 20 paper particles are added to each. After temperature regulation at 25 ° C. for 1 hour, the sample bottle is vigorously shaken up and down to mix. Further, after standing at 25 ° C. for 3 hours, visually count the number of particles floating on the liquid surface or the number of particles precipitated on the bottom surface, and substitute it into the expression of the immobilization index (%) described below. Find the immobilization index (%).

<Calculation of immobilization index in liquid and determination of stability>
The immobilization index (%) is obtained by the following formula.
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 settled on the bottom surface Fixation of liquid using only water-soluble polymers and polysaccharides with the same immobilization index When larger than the crystallization index, it is determined that the particle has an immobilizing action. That is, when the following immobilization indices X and Y are in a relationship of “immobilization index X> immobilization index Y”, it is determined to have stability.
Immobilization index X: Immobilization index when the dried composition (or thickening gelling agent) is made into a liquid Immobilization index Y: The dry composition (or thickening gel used when obtaining the immobilization index X) Immobilization index when the water-soluble polymer (or polysaccharide) contained in

<Measurement of particle size>
The particles were observed with a microscope or measured with a micrometer to determine the major and minor diameters. The number of repetitions at this time was 30.
<Average particle diameter of spherical particles>
From the major axis and minor axis of the particles used above, it is calculated as “(major axis + minor axis) / 2”. The number of repetitions at this time was 30.
<Specific gravity of particles>
The specific gravity was calculated according to JIS Z 8807-1976 (Solid specific gravity measuring method).

<PH>
The pH was measured with a pH meter (“HM-50G type” manufactured by Toa DKK Corporation).
<Determination of heat resistance of gel>
(1) Using a 1% by mass thickening gelling agent dispersion as a test sample, 20 paper particles (major axis 5 mm, minor axis 5 mm square, thickness 0.3 mm) were added and mixed uniformly. Then, it is poured and filled into a cylindrical glass container having an inner diameter of about 45 mm until the height becomes about 45 mm. As a method for dispersing the 1% thickening gelling agent, a suitable method is selected according to the properties of the thickening gelling agent.
(2) Paper particles (major axis 5 mm, minor axis 5 mm square, thickness 0.3 mm) are used as particles, and 20 of these are added per filled container.
(3) Heat at 120 ° C. for 30 minutes, and after completion of the heat treatment, visually check the completion of the gel at 80 ° C. and count the number of particles floating on the liquid surface and the number of particles settling on the bottom surface.
(4) Determination of heat resistance: Based on the number of particles counted in (3), an immobilization index is obtained using the following equation. When the immobilization index is 40% or more, it is determined that “there is heat resistance”.
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)

<Gel break strength>
(1) Using the above 1% by weight gelling agent dispersion as a test sample, a cylindrical glass container having an inner diameter of about 45 mm is poured and filled to a height of about 45 mm.
(2) After heating at 80 ° C. for 1 hour, cool at 25 ° C. for 3 hours.
(3) The gel is measured under the following conditions without taking it out of the container.
Apparatus: RHEO METER (NRM-2002J type) (manufactured by Fudo Kogyo Co., Ltd.)
Pushing jig: 10mmφ spherical jig Pushing speed: 20mm / min
Measurement temperature: 25 ° C

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to these at all. The dry compositions, sodium carboxymethyl cellulose, xanthan gum, dextrin, glucomannan and guar gum used in the examples are shown in the following (1) to (8).

(1) Preparation of dry composition A: Commercial bagasse pulp (average polymerization degree = 1320, α-cellulose content = 77%) is cut into a 6 × 16 mm square so that the solid content concentration becomes 77% by mass. Water was added to the. When this was passed once through a cutter mill (cutting head / horizontal blade gap: 2.03 mm, impeller rotation speed: 3600 rpm), taking care not to separate water and pulp chips as much as possible, the fiber length was 0.5 to It became 2.5 mm. This aqueous dispersion was diluted with water to 4% by mass and treated with a grindstone rotary grinder (grinder rotation speed: 1800 rpm). The number of treatments was 2, and the grinder clearance was changed from 60 to 40 μm.
Subsequently, the obtained aqueous dispersion was diluted with water to 2% by mass, and subjected to 8 passes with a high-pressure homogenizer (processing pressure 100 MPa), whereby a fine fibrous cellulose slurry A was obtained. The crystallinity of this fine fibrous cellulose slurry A was 74%. 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 0.38. The “component stably suspended in water” was 98% by mass.
Carboxymethylcellulose sodium: Dextrin: Fine fibrous cellulose: Rapeseed oil = 12.5: 39: 48: 0.5 (part by mass) Sodium carboxymethylcellulose (1 mass% aqueous solution viscosity: 3400 mPa · s) , Dextrin (DE: 28), fine fibrous cellulose slurry A. K. The mixture was stirred and mixed at 9000 rpm for 10 minutes with a homomixer (trademark, MARK-2 type, manufactured by Tokushu Kika Kogyo Co., Ltd.).
This dispersion is spread on a smooth aluminum plate with a thickness of about 3 mm, dried with a hot air dryer at 120 ° C. for 40 minutes, and the resulting film-like product is examined with a cutter mill (manufactured by Fuji Powder Co., Ltd.). An open 2 mm sieve was pulverized to such an extent that a scaly dry composition A was obtained.

  (2) Preparation of dry composition B: In the same manner as dry composition A, sodium carboxymethylcellulose: dextrin: fine fibrous cellulose: rapeseed oil = 7.5: 60: 32: 0.5 (parts by mass) The dry composition B was obtained. In addition, the same thing as the dry composition A was used for carboxymethylcellulose sodium, dextrin, fine fibrous cellulose slurry A, and rapeseed oil.

  (3) Preparation of dry composition C: In the same manner as dry composition A, xanthan gum: dextrin: fine fibrous cellulose: rapeseed oil = 24: 27.5: 48: 0.5 (parts by mass) To obtain a dry composition C. Xanthan gum (manufactured by Dainippon Pharmaceutical Co., Ltd.), dextrin used in the dry composition A, fine fibrous cellulose slurry A, and rapeseed oil were used.

(4) Preparation of dry composition D: Commercial wood pulp (average polymerization degree = 1820, α-cellulose content = 77 mass%) was cut into a 6 × 16 mm square and the solid content concentration was 80 mass%. Water was added so that This was passed once through a cutter mill (cutting head / horizontal blade gap: 2.03 mm, impeller rotation speed: 3600 rpm), taking care not to separate water and pulp chips as much as possible.
Next, the cutter mill-treated product and water were weighed out so that the cellulose concentration became 2% by mass, and stirred until there was no fiber entanglement. This aqueous dispersion was treated twice with a grindstone rotating grinder (grinder rotation speed: 1800 rpm) while changing the grinder clearance from 110 to 80 μm. Subsequently, 6 passes was performed with a high-pressure homogenizer (processing pressure: 95 MPa) to obtain a fine fibrous cellulose slurry D.
When observed with an optical microscope, fine fibrous cellulose having a major axis of 10 to 400 μm, a minor axis of 1 to 5 μm, and a major axis / minor axis ratio of 10 to 300 was observed. The loss tangent was 0.64, and the content of “component stably suspended in water” was 43% by mass. When observed with a high-resolution SEM, very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 10 to 150 nm, and a major axis / minor axis ratio of 30 to 300 was observed.
Using the above-mentioned fine fibrous cellulose slurry D, in the same manner as in the dry composition A, carboxymethylcellulose sodium: dextrin: fine fibrous cellulose: rapeseed oil = 12.5: 39: 48: 0.5 (mass Part) to obtain a dry composition D. In addition, the same thing as the dry composition A was used for carboxymethylcellulose sodium, dextrin, and rapeseed oil.

  (5) Preparation of dry composition X: In the same manner as dry composition A, carboxymethylcellulose sodium: dextrin: fine fibrous cellulose: rapeseed oil = 13: 19.5: 67: 0.5 (parts by mass) The dry composition X was obtained. In addition, the same thing as the dry composition A was used for carboxymethylcellulose sodium, dextrin, fine fibrous cellulose slurry A, and rapeseed oil.

(6) Preparation of dry composition Y: In the same manner as dry composition D, carboxymethylcellulose sodium: dextrin: fine fibrous cellulose: rapeseed oil = 13: 19.5: 67: 0.5 (parts by mass) The dry composition Y was obtained. In addition, the same thing as the dry composition D was used for carboxymethylcellulose sodium, dextrin, fine fibrous cellulose slurry D, and rapeseed oil.
(7) Xanthan gum (Dainippon Pharmaceutical Co., Ltd.)
(8) Glucomannan (Shimizu Chemical Co., Ltd., readily soluble type)
(9) Carboxymethylcellulose sodium (Daiichi Kogyo Seiyaku Co., Ltd.)
(10) Guar gum (Made by Unitech Foods)
The compositions of the dry compositions A to D, X, and Y are shown in Table 1.

[Example 1]
First, dispersibility was determined using the dry composition A as a sample.
(1) Weigh out the sample and dispersion medium so as to obtain an aqueous dispersion having a solid content concentration of 0.25% by mass, and prepare an “ion exchange water viscosity solution” and a “0.01% calcium chloride water viscosity solution”. did.
(1a) Ion-exchanged water viscosity solution: A sample and ion-exchanged water were weighed out and dispersed at 25 ° C. and 15000 rpm for 5 minutes using an ace homogenizer (trademark, manufactured by Nippon Seiki Co., Ltd., AM-T type).
(1b) 0.01% calcium chloride aqueous solution: A sample and 0.01% by mass calcium chloride water are weighed out and T.M. K. Using a homomixer (trademark, MARK-2 type, manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was dispersed at 8000 rpm for 10 minutes at 60 ° C.
(2) The two types of viscosity solutions were allowed to stand in an atmosphere at 25 ° C. for 3 hours.
(3) Set in a rotational viscometer (manufactured by Tokimec Co., Ltd., B-type viscometer, BL-type) while still standing, and start rotating the rotor 30 seconds after the end of stirring, and then from the indicated value 30 seconds later The viscosity was calculated. The rotor rotation speed was 60 rpm.
(4) The “0.01% calcium chloride water viscosity” at 0.25% by mass obtained above was 29 mPa · s.
(5) The “ion exchange water viscosity” at 0.25% by mass was 41 mPa · s.
(6) When the dispersibility index (%) was calculated according to the following formula, the dispersibility index was 71%, and the dry composition A was determined to be “dispersible”.
Dispersibility index (%) = (0.01% calcium chloride water viscosity / ion exchange water viscosity) × 100
Further, the dry composition A was used to determine the particle fixing effect.
(7) The sample and water are weighed out so that the solid content is an aqueous dispersion of 1% by mass, and “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used for 10 minutes at 8000 rpm. Distributed. This 1% by mass sample aqueous dispersion: water was mixed at a ratio of 3.5: 6.5 and further dispersed for 5 minutes to prepare a 0.35% by mass sample aqueous solution.
(8) A 0.35 mass% sample aqueous dispersion was filled in a 100 mL sample bottle, and 20 paper particles (a rectangle with a major axis of 5 mm, a minor axis of 3 mm, a thickness of 0.3 mm and a specific gravity of 0.9) were added. .
(9) After temperature regulation at 25 ° C. for 1 hour, the sample bottle is vigorously shaken up and down and mixed. Further, after standing at 25 ° C. for 3 hours, visually count the number of particles floating on the liquid surface or the number of particles precipitated on the bottom surface, and substitute it into the expression of the following immobilization index (%), When the immobilization index was determined, the immobilization index was 60%, and compared with Comparative Example 3, it was determined to have “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 precipitated on the bottom surface

[Example 2]
Using the dry composition B, the viscosity was measured in the same manner as in Example 1, and the dispersibility was determined.
The “0.01% calcium chloride water viscosity” at 0.25% by mass was 14 mPa · s. The “ion exchange water viscosity” at 0.25% by mass was 15 mPa · s.
When the dispersibility index (%) was calculated, the dispersibility index was 93%, and the dry composition B was determined to be “dispersible”.
Furthermore, using the dry composition B, the immobilization index measured by the same method as in Example 1 was 40%, and compared with Comparative Example 4, it was determined to have “stability”.

[Example 3]
Using the dry composition C, the viscosity was measured in the same manner as in Example 1, and the dispersibility was determined.
The “0.01% calcium chloride water viscosity” at 0.25% by mass was 54 mPa · s. The “ion exchange water viscosity” at 0.25% by mass was 102 mPa · s.
When the dispersibility index (%) was calculated, the dispersibility index was 53%, and the dry composition C was determined to be “dispersible”.
Furthermore, using the dry composition C, the immobilization index measured by the same method as in Example 1 was 70%, and compared with Comparative Example 5, it was determined to have “stability”.

[Example 4]
Using the above-mentioned dry composition D, the viscosity was measured by the same method as in Example 1, and the dispersibility was determined.
The “0.01% calcium chloride water viscosity” at 0.25% by mass was 39 mPa · s. The “ion exchange water viscosity” at 0.25% by mass was 69 mPa · s.
When the dispersibility index (%) was calculated, the dispersibility index was 57%, and the dry composition D was determined to be “dispersible”.
Furthermore, using the dried composition D, the immobilization index measured by the same method as in Example 1 was 70%, and compared with Comparative Example 3, it was determined to have “stability”.

[Example 5]
Dry composition A and xanthan gum were mixed at a mass ratio of 70:30 to prepare a thickening gelling agent a. The immobilization index of the thickening gelator a obtained by the same method as in Example 1 was 80%, and compared with Comparative Example 6, it was determined as “having stability”.

[Example 6]
The dry composition A and glucomannan were mixed at a mass ratio of 75:25 to prepare a thickening gelling agent b. A gel using the thickening gelling agent b was prepared by the following method, and the heat resistance was determined.
(1) 1% by mass thickening gelator b and water are mixed and dispersed at 10000 rpm for 5 minutes at 25 ° C. using an ace homogenizer (trademark, manufactured by Nippon Seiki Co., Ltd., AM-T type). I let you.
(2) Paper particles (major axis: 5 mm, minor axis: 5 mm square, thickness: 0.3 mm) were added to this 1% by weight thickening gelling agent aqueous dispersion and mixed uniformly. The mixture was poured and filled into a cylindrical glass container having an inner diameter of about 45 mm until the height was about 45 mm.
(3) Heated at 120 ° C. for 30 minutes, and after completion of the heat treatment, the completion of the gel was visually confirmed at 80 ° C., and the number of particles floating on the surface and the number of particles settling on the bottom surface were counted.
(4) Judgment of heat resistance: Based on the number of particles counted in (3), the immobilization index was determined using the following formula and found to be 80%. The immobilization index was 40% or more, and it was determined to be “heat resistant”.
Immobilization index (%) = [α− (β + γ)] / α × 100 (α: total number of particles, β: number of particles floating on the surface, γ: number of particles settling on the bottom surface)
Further, the gel breaking strength was measured by the following procedure and found to be 0.12N.
(5) Using the above 1% by weight thickening gelling agent dispersion as a test sample, a cylindrical glass container having an inner diameter of about 45 mm was poured and filled to a height of about 45 mm.
(6) After heating at 80 ° C. for 1 hour, it was cooled at 25 ° C. for 3 hours.
(7) The gel was measured under the following conditions without taking it out of the container.
Apparatus: RHEO METER (NRM-2002J type) (manufactured by Fudo Kogyo Co., Ltd.)
Pushing jig: 10mmφ spherical jig Pushing speed: 20mm / min
Measurement temperature: 25 ° C

[Example 7]
Drying composition A: Glucomannan: xanthan gum was mixed at a mass ratio of 50:40:10 to prepare a thickening gelling agent c. A gel was prepared in the same manner as in Example 6 using the thickening gelling agent c. When the immobilization index was determined, it was 60% and was judged to be “heat resistant”. When the gel breaking strength was measured, it was 0.75 N, which was significantly higher than that of the gel formed only from the dry composition A and glucomannan.

[Example 8]
Milk coffee was made using the dry composition A to confirm the precipitation-inhibiting effect. 0.01% by weight dry composition A, 0.03% by weight bacteriostatic agent (Mitsubishi Chemical Foods Co., Ltd., sucrose palmitate), 6% by weight granulated sugar (Daiichi Sugar Industry Co., Ltd.) A powder mixture was obtained. "TK homomixer" (manufactured by Tokushu Kika Kogyo Co., Ltd.), 48 mass% coffee extract (raw bean equivalent 8 times extract), 13 mass% milk and water at 80 ° C, 6500 rpm While mixing, the powder mixture was added to a total of 100% by mass. The mixture was further dispersed for 10 minutes, and sodium bicarbonate was added in an external ratio to adjust the pH to 6.8.
Next, it was homogenized at 15 MPa with a Menton Gorin type homogenizer (manufactured by APV) and filled into a 200 mL heat-resistant bottle. Furthermore, it sterilized for 40 minutes at 120 degreeC with the retort sterilizer (made by Hirayama Seisakusho).
A storage test was conducted at 5 ° C, 25 ° C and 60 ° C for one month. After the test, the heat-resistant bottle was inverted and the state of precipitation was confirmed. The precipitation was suppressed at all storage temperatures. The stability was good. The pH at this time was 6.5.

[Example 9]
Using a thickening gelling agent d mixed at a mass ratio of dry composition B: carboxymethyl cellulose / sodium = 20: 80, a fermented milk beverage was produced and evaluated.
A dispersion of 0.2% by weight thickening gelling agent d in water so that the total amount becomes 100% by weight, and 75% by weight of milk (manufactured by Minami Nihon Dairyo Kyodo Co., Ltd., milk fat content 3.5 % Non-fat milk solid content 8.3%) was poured into a stainless beaker and 3.3% by weight skimmed milk powder (manufactured by Snow Brand Milk Products Co., Ltd.) while stirring at 200 rpm at 25 ° C. using a propeller stirring blade. ) Was added and stirring was continued for 10 minutes.
The solution was homogenized at a processing pressure of 15 MPa using the Manton Gorin type homogenizer of Example 8, and further sterilized by stirring at 80 ° C. and 200 rpm for 30 minutes using a propeller stirring blade. Furthermore, it cooled to 30 degreeC in 20 minutes, stirring at 200 rpm in a clean bench. To this solution, a starter (manufactured by Danisco Carter Co., Ltd.) as a 0.01% by mass aqueous solution was added in an external ratio of 0.32% by mass, stirred with a spatula, and filled into a fermentation vessel. This was transferred to an incubator and fermented at 42 ° C. for 8 hours. After fermentation, the mixture was transferred to a refrigerator at 5 ° C. and passed for 3 days to obtain a stirring yogurt (non-fat milk solid content of 9.4% or more).
90% by mass of this stirring yogurt treated at 15 MPa using a Menton Gorin type homogenizer, 5% by mass of strawberry pulp and granulated sugar each, and cooled at 5 ° C. for 24 hours are fermented. It was a milk drink. The blending amount of the thickening gelling agent d in the fermented milk beverage was 0.2% by mass, and the pH was 4.5. Also, no abnormalities such as precipitation and separation were observed, and the stability was good.
When this fermented milk drink was sampled by 20 panelists, no panelists complained of a pasty feeling and both stability and texture were good.

[Example 10]
Using the thickening gelling agent e mixed at a mass ratio of dry composition A: guar gum = 70: 30, a grater was made and evaluated.
20 masses of 60 ° C. fructose glucose liquid sugar (manufactured by Oji Cornstarch Co., Ltd., “F-55”) while stirring with “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) in water at 60 ° C. %, 0.4% by mass of the above thickening gelling agent e and 5% by mass of granulated sugar (Daiichi Sugar Industry Co., Ltd.) are added and dispersed at 8000 rpm for 10 minutes. Soy sauce 30% by mass (Kikkoman Co., Ltd., salt concentration 16%), 5% by mass of salt (Salt Business Center), Asahi taste 1% by mass (Nippon Tobacco Inc.), apple vinegar 5 Add 100% by mass (100% by weight, manufactured by Mitsukan Co., Ltd., acidity 5.0%), 1% by weight grated onion, 1% by weight grated garlic, 2% by weight apple juice (manufactured by Ike Co., Ltd.) To be Engaged. Furthermore, 10% by mass of radish grated radish was added and stirred, and stirring was continued until 3 minutes had elapsed after the liquid temperature reached 80 ° C., and sterilization was performed. The salt concentration of the grater was 10% and pH 4.3.
This was filled in a 100 mL sample bottle, stored at 5 ° C. for 1 month, and the state of grated radish was confirmed. As a result, the grated radish was almost uniformly suspended, and the stability was good.

[Example 11]
Using the thickening gelling agent a of Example 5, a miso gel was made and evaluated. Water of 10 ° C. is put into a home mixer (manufactured by Sanyo Corporation, 11000 rpm) so that the total amount becomes 100% by mass, 1% by mass of the thickening gelling agent a is added, and dispersed for 4 minutes. 8% by mass of white miso (manufactured by Shinjo Miso Co., Ltd.) and 1% by mass of powder seasoning (manufactured by Ajinomoto Co., Inc.) previously dissolved in water were added and further dispersed for 1 minute.
This was filled in a 100 mL heat-resistant bottle, and 5 pieces of tofu cut into 8 mm squares were added per container. This was sterilized with the retort sterilizer of Example 7 at 120 ° C. for 30 minutes. When the position of the tofu was confirmed at 80 ° C. after sterilization, the tofu was uniform and the miso gel was heat resistant.

[Comparative Example 1]
Using the dry composition X, the viscosity was measured in the same manner as in Example 1, and the dispersibility was determined.
The “0.01% calcium chloride water viscosity” at 0.25% by mass was 18 mPa · s. The “ion exchange water viscosity” at 0.25% by mass was 101 mPa · s.
When the dispersibility index was calculated, the dispersibility index was 18%, and the dry composition X was determined to be “not dispersible”.

[Comparative Example 2]
Using the dry composition Y, the viscosity was measured in the same manner as in Example 1, and the dispersibility was determined.
The “0.01% calcium chloride water viscosity” at 0.25% by mass was 15 mPa · s. The “ion exchange water viscosity” at 0.25% by mass was 98 mPa · s.
When the dispersibility index was calculated, the dispersibility index was 15%, and the dry composition Y was determined to be “not dispersible”.

[Comparative Example 3]
Instead of the dry composition A of Example 1, an example in which only the water-soluble polymer as a constituent component was mixed at the same mass ratio (carboxyethylcellulose sodium: dextrin = 12.5: 39) was used. The immobilization index was measured in the same manner as in 1. The immobilization index was 0%.

[Comparative Example 4]
Instead of the dry composition B of Example 2, an example in which only the water-soluble polymer as a constituent component was mixed at the same mass ratio (carboxyethylcellulose sodium: dextrin = 7.5: 60) was used. The immobilization index was measured in the same manner as in 1. The immobilization index was 0%.

[Comparative Example 5]
Instead of the dry composition C of Example 3, only the water-soluble polymer as a constituent component was mixed at the same mass ratio (xanthan gum: dextrin = 24: 27.5) as in Example 1 The immobilization index was measured by the method. The immobilization index was 10%.

[Comparative Example 6]
Instead of the thickening gelling agent a of Example 5, the immobilization index was measured in the same manner as in Example 5 using only the constituent component polysaccharide (xanthan gum). The immobilization index was 0%.
[Comparative Example 7]
Instead of the thickening gelator b of Example 6, the immobilization index was measured in the same manner as in Example 5 using only polysaccharide (glucomannan). The immobilization index was 0%. In addition, glucomannan alone did not form a gel.
[Comparative Example 8]
The immobilization index was measured in the same manner as in Example 5 using only the polysaccharide (glucomannan: xanthan gum = 40: 10) instead of the thickening gelator c in Example 7. The immobilization index was 0%. Moreover, when only the said polysaccharide was used, although the gel formed, it was a rubber-like texture and was unsuitable as a foodstuff.

[Comparative Example 9]
Instead of the dry composition A of Example 8, a mixture of only water-soluble polymers as constituent components at the same mass ratio (carboxymethylcellulose sodium: dextrin = 12.5: 39) was used. Milk coffee was made and evaluated in the same manner as in No. 8.
Precipitation occurred at any storage temperature, and no precipitation inhibiting effect was observed. In particular, the product stored at 60 ° C. had a strong adhesion to the bottom surface, and even when the heat-resistant bottle was inverted 20 times or more, it did not disappear and the stability was poor.
[Comparative Example 10]
A fermented milk drink was produced and evaluated in the same manner as in Example 9, using only the polysaccharide (carboxymethylcellulose sodium) as a component instead of the thickening gelling agent d in Example 9. Although there was no separation, the milk component adhering to the bottom was fixed. Moreover, it was highly viscous and 16 out of 20 people complained of an unpleasant pasty feeling and the texture was poor.

[Comparative Example 11]
In place of the thickening gelling agent e in Example 10, only a polysaccharide (guar gum) as a constituent component was used, and a grated dripping was produced and evaluated in the same manner as in Example 10. There was only 55% of daikon radish from the bottom, and the stability was poor in the separated state.
[Comparative Example 12]
Instead of the thickening gelling agent a of Example 11, only a polysaccharide (xanthan gum) as a constituent component was used for trial manufacture in the same manner as in Example 11, but no gel was formed.
Table 2 shows the results of evaluation of the dry compositions and thickening gelling agents used in Examples 1 to 11 and Comparative Examples 1 to 12, and the liquid compositions and gel compositions prepared using the same.

The dry composition of the present invention is excellent in stability and dispersibility as compared with the prior art. Therefore, stability can be imparted while suppressing stickiness. Moreover, since it is excellent in dispersibility, even if it mixes with a tap water and a food raw material, it is highly practical in manufacture of a product.
Furthermore, by combining with a specific polysaccharide, it is possible to provide a novel thickening gelling agent and a liquid or gel composition containing the same.
These properties can be used not only in the food field but also in pharmaceuticals, cosmetics, and industrial applications.

Claims (10)

  A dry composition comprising 1 to 49% by mass of crystalline fine fibrous cellulose and 51 to 99% by mass of a water-soluble polymer using plant cell walls as raw materials.   The dry composition according to claim 1, wherein the water-soluble polymer is carboxymethylcellulose sodium and dextrin.   2. The dry composition according to claim 1, wherein the water-soluble polymer is xanthan gum and dextrin.   The dry composition according to any one of claims 1 to 3, glucomannan, galactomannan, alginic acids, xanthan gum, tamarind seed gum, pectin, carrageenan, gellan gum, agar, sodium carboxymethylcellulose, soybean water-soluble polysaccharide, At least one polysaccharide selected from the group consisting of Karaya gum, psyllium seed gum, pullulan, gum arabic, tragacanth gum, gaddy gum, arabinogalactan and curdlan, and dry composition: polysaccharide = 1: 99 to 99: A thickening gelling agent characterized by containing at a mass ratio of 1.   The thickening gelling agent according to claim 4, wherein the polysaccharide is selected from the group consisting of glucomannan, galactomannan and alginic acids. The thickening gelling agent according to claim 4, wherein the polysaccharide contains xanthan gum and at least one selected from the group consisting of glucomannan, galactomannan and alginic acids.   A liquid composition comprising the dry composition according to claim 1.   A gel composition comprising the dry composition according to claim 1.   A liquid composition comprising the thickening gelling agent according to claim 4.   A gel composition comprising the thickening gelling agent according to any one of claims 4 to 6.