JP2008048604A - Stabilizers containing water-dispersible cellulose and polysaccharides - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stabilizer which comprises water-dispersible cellulose of minute fibrous cellulose and polysaccharide so as to have particle-fixing function, provide a good-appearance article and reduce load on a production process. <P>SOLUTION: The stabilizer comprises water-dispersible cellulose comprising water-dispersible component of minute fibrous cellulose comprising plant cell walls as raw material, having <1 specific loss tangent, and a specific polysaccharide, so as to have particle-fixing function, provide a good appearance article and reduce load on the production process. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a stabilizer containing water-dispersible cellulose, which is fine fibrous cellulose, and at least one polysaccharide, and having a particle fixing action.

  Conventionally, polysaccharides such as galactomannan, xanthan gum, and pectin have been used as thickening stabilizers for thickening products such as foods and cosmetics. In order to immobilize particles using these polysaccharides, it is necessary to impart a very high viscosity. Such excessive consistency is a problem because it imposes a load on the manufacturing process, such as impairing the commercial value and making stirring and pumping difficult.

Patent Documents 1 to 3 and the like are known as thickeners containing fine fibrous cellulose and polysaccharides. The effects shown in these are “mamako prevention”, “intestinal regulation” and the like, and the particle immobilization action is not described.
In Patent Documents 4 and 5, there is a disclosure relating to a composition in which cellulose nanofibrils obtained from cells having a primary wall of about 80% or more and other additives are blended. This is to improve the redispersibility of the dried product and to supplement the functions of cellulose nanofibrils, not to fix the particles.
Patent Document 6 has a description of sesame sauce and acidic milk drinks containing water-dispersible cellulose and polysaccharides. However, it can stabilize suspension of small particles such as sesame paste and milk protein that cannot be visually confirmed. There is a function different from the immobilization of the “particles in which each particle can be visually discerned” according to the present invention.
Japanese Patent No. 1731182 JP 60-260517 A Japanese Patent No. 1850006 Special table 2001-520180 gazette Japanese Patent No. 3247391 JP 2004-411119 A

  An object of this invention is to provide the stabilizer which provides a particle fixed effect | action to the particle | grains in a liquid composition, and can manufacture a good-looking product.

  The present inventor has solved the problem and made the present invention by containing water-dispersible cellulose, which is fine fibrous cellulose made from plant cell walls, and a specific polysaccharide. That is, the present invention is as follows.

(1) Fine fibrous cellulose made from plant cell walls as a raw material, and stably suspended in water (major axis: 0.5 to 30 μm, minor axis: 2 to 600 nm, major axis / minor axis ratio: 20 to 400) in an amount of 10% by mass or more, and a loss tangent when the aqueous dispersion is 0.5% by mass is less than 1, water dispersible cellulose, galactomannan, glucomannan, From sodium alginate, xanthan gum, tamarind seed gum, pectin, carrageenan, gellan gum, agar, sodium carboxymethyl cellulose, soybean water-soluble polysaccharide, karaya gum, psyllium seed gum, pullulan, gum arabic, tragacanth gum, gaddy gum, arabinogalactan, curdlan A composition comprising at least one selected polysaccharide comprising water Sexual Cellulose: polysaccharide = 1: 9 to 9: stabilizers, characterized in that it contains at a mass ratio.

  (2) 50 to 95% by mass of the water-dispersible cellulose according to (1) containing 10% by mass or more of a component that is stably suspended in water, and 5 to 50 of a water-soluble polymer and / or a hydrophilic substance. A composition comprising a water-dispersible dry composition comprising at least mass% and at least one polysaccharide selected from the polysaccharides according to claim 1, wherein the water-dispersible dry composition: A stabilizer characterized by containing saccharides in a mass ratio of 1: 9 to 9: 1.

  (3) A water-dispersible dry composition comprising 50 to 95% by mass of the water-dispersible cellulose described in (1), 1 to 49% by mass of a water-soluble polymer, and 1 to 49% by mass of a hydrophilic substance, and galacto The stabilizer according to (2), comprising a polysaccharide selected from mannan, xanthan gum, tamarind seed gum, and pectin.

  (4) A liquid composition formulated by adding the stabilizer according to any one of (1) to (3).

  (5) A liquid food composition having a pH of 3 to 8 or a salt concentration of 0.001 to 20%, which is formulated by adding the stabilizer according to any one of (1) to (3).

  INDUSTRIAL APPLICABILITY The present invention can provide a stabilizer capable of providing a particle fixing action and producing a good-looking product by containing water-dispersible cellulose, which is fine fibrous cellulose, and a polysaccharide.

Hereinafter, the present invention will be specifically described focusing on its preferred form. The water-dispersible cellulose of the present invention is made from plant cell walls. Specifically, materials that can be stably obtained at low cost and can be used industrially are preferable, such as wood (conifers, hardwoods), cotton linters, kenaf, Manila hemp (Abaca), sisal hemp Pulp mainly composed of natural cellulose such as jute, survivorgrass, esparto grass, bagasse, rice straw, straw, straw and bamboo is used. Cotton, papyrus grass, beet, ridges, honey, and ganpi can also be used, but reasons such as difficulty in securing stable raw materials, high content of components other than cellulose, and difficulty in handling May not be preferable. When regenerated cellulose is used as a raw material, sufficient performance is not exhibited, so regenerated cellulose is not included as a raw material of the present invention.
Specific examples of preferable raw materials are wood pulp, cotton linter pulp, bagasse pulp, wheat straw pulp, rice straw pulp, bamboo pulp and the like. Particularly preferred are cellulosic substances originating from the cell walls of gramineous plants, specifically bagasse pulp, wheat straw pulp, rice straw pulp and bamboo pulp.

The crystallinity of the fine fibrous cellulose used in the present invention is not particularly defined, but the crystallinity as measured by the X-ray diffraction method (Segal method) is preferably greater than 50%. 55% or more is more preferable. The water-dispersible dry composition used in the present invention contains components other than cellulose, but these components are amorphous and are counted as amorphous.

  Most of the cellulose used in the present invention, that is, 90% or more, is “fine fibrous”. In this specification, “fine fibrous” means a length (major axis) of 5 nm to 5 mm, a width (minor axis) of 1 nm to 200 μm, and a length as observed and measured with an optical microscope and an electron microscope. It means that the ratio of the width to the width (major axis / minor axis) is 5 to 10,000. Among them, the preferred form of “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 length to width (major axis / minor axis) of 5 to 5. 400.

  The water-dispersible cellulose or water-dispersible dry composition of the present invention contains a component that is stably suspended in water. Specifically, it is a component having the property of being stably suspended in water without settling even when it is centrifuged at 1000 G for 5 minutes in the form of a 0.1% by weight aqueous dispersion. The length (major axis) observed and measured with a high-resolution scanning electron microscope (SEM) is 0.5 to 30 μm, the width (minor axis) is 2 to 600 nm, and the ratio of length to width (major axis) / Minor axis ratio) is composed of fibrous cellulose having a ratio of 20 to 400. Preferably, the width is 100 nm or less, more preferably 50 nm.

The water-dispersed cellulose or water-dispersible dry composition of the present invention contains 10% by mass or more of this “component that is stably suspended in water”. When the content of this component is less than 10% by mass, the above-described function is not sufficiently exhibited. The larger the content, the better, but it is preferably 30% by mass or more, more preferably 50% or more. Unless otherwise specified, the content of this component represents the abundance ratio in the total cellulose, and is measured and calculated so that it is not included even if a water-soluble component is included. .
The water-dispersible cellulose or water-dispersible dry composition of the present invention has a loss tangent (tan δ) of less than 1 measured in a 0.5% by weight aqueous dispersion at a strain of 10% and a frequency of 10 rad / s. And preferably less than 0.6. If it is less than 0.6, the performance is further improved. When the loss tangent is 1 or more, the particle fixing action described later is inferior.

  In order to make the loss tangent of the water-dispersible cellulose or water-dispersible dry composition of the present invention less than 1, it is necessary to take out microfibrils derived from plant cell walls without cutting them short. However, with the current technology, it is not possible to perform only “miniaturization” without “short fiber” at all. (In this case, “short fiber” means that the fiber is cut short, or the state of the shortened fiber. Also, “miniaturization” means that the fiber is thinned by giving an action such as tearing, or In other words, in order to make the loss tangent less than 1, it is important to advance the “miniaturization” while minimizing the “short fiber” of the cellulose fiber. Although the preferable method for that is shown below, it does not limit to these methods at all.

The cellulosic substance originating from the plant cell wall selected as a raw material in order to advance the “miniaturization” while minimizing the “short fiber” of the cellulose fiber has an average degree of polymerization of 400 to 12000, and α The cellulose content (%) is preferably 60 to 100% by mass, more preferably the α-cellulose content (%) is 60 to 85% by mass.
Further, a high-pressure homogenizer is preferable as an apparatus used for advancing “miniaturization” while minimizing “shortening” of cellulose fibers. Specific examples of the high-pressure homogenizer include Emulflex (AVESTIN, Inc.), Optimizer System (Sugino Machine Co., Ltd.), Nanomizer System (Nanomizer Co., Ltd.), Microfluidizer (MFIC Corp.), Valve Homogenizer ( Sanwa Machinery Co., Ltd., Invensys APV, Niro Soavi, Izumi Food Machinery Co., Ltd.). The processing pressure of the high-pressure homogenizer is preferably 30 MPa or more, more preferably 60 to 414 MPa.

  Polysaccharides of the present invention include galactomannan, glucomannan, sodium alginate, 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 galactomannan, xanthan gum, tamarind seed gum and pectin. Further, it is more preferable if the type of galactomannan is guar gum, locust bean gum or tara gum.

The galactomannan used in the present invention is a polysaccharide having a structure composed of a main chain in which β-D-mannose is β-1,4 bonded and a side chain in which α-D-galactose is α-1,6 bonded. It is. Examples of galactomannans include guar gum, locust bean gum, tara gum, etc. The ratio of mannose to glucose is about 2: 1 for guar gum, about 4: 1 for locust bean gum, and about 3: 1 for tara gum.
The glucomannan used in the present invention is a polysaccharide having a structure in which D-glucose and D-mannose are linked by β-1,4, and the ratio of glucose to mannose is about 2: 3. If 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.

  The sodium alginate used in the present invention is a water-soluble polysaccharide in which alginic acid is neutralized with sodium. Alginic acid is a 1,4-bond block copolymer consisting of β-D-mannuronic acid (abbreviated as M) and α-L-guluronic acid (abbreviated as G). A block composed of M (MMMGM), a block composed of G (GGGGG), and a block in which both residues are alternately mixed (MGGG) , And consists of three segments.

The xanthan gum used in the present invention has a structure in which the main chain has a β-1,4-bonded D-glucose, and is composed of D-mannose, D-glucuronic acid, and D-mannose on the main chain anhydroglucose. The side chain is attached. 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 tamarind seed gum used in the present invention is xyloglucan having a main chain of glucose and xylose in the side chain.

  The pectin used in the present invention has α-D-galacturonic acid linked to α-1,4 in the main chain 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.

The carrageenan used in the present invention 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 used in the present invention is one 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.
The agar used in the present invention comprises β-D-galactose and α-L-galactose β-1,4 bonds, α-1,3 bonds alternately having a repeating structure, and ionic many other than agarose. It is a polysaccharide consisting of agaropectin which is a saccharide.

The sodium carboxymethylcellulose used in the present invention 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 used in the present invention is composed of sugars such as galactose, arabinose, galacturonic acid, rhamnose, xylose, glucose, etc. Yes.
Karaya gum used in the present invention is a partially acetylated branched polysaccharide containing about 40% uronic acid and not 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.

The psyllium seed gum used in the present invention has a highly branched structure with xylan as the main chain, and the side chain is composed 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.
The pullulan used in the present invention has a linear structure in which maltotriose repeats α-1,6-glycosidic bonds.
Although the molecular structure of gum arabic used in the present invention has not been clarified, its constituent sugars are 36% D-galactose, 31% L-arabinose, 13% L-rhamnose, 18% D-glucuronic acid, Protein 2% is reported.

The tragacanth gum used in the present invention is obtained from the sap of legume tragacanth and is said to contain 70% tragacantic acid and 10% arabinogalactan.
The gaddy gum used in the present invention is composed of D-glucuronic acid, L-arabinose, D-galactose, D-mannose and D-xylose, and the D-galactose residue constitutes the main chain.
The arabinogalactan used in the present invention has D-galactose as the main chain, and the ratio of the side chain to L-arabinose 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.
The curdlan used in the present invention is a linear glucan in which glucose is β-1,3-glucoside-bonded.

The particles of the present invention are particles having a specific gravity of 0.1 to 3.5 and a size that allows each particle to be visually discerned. The particle having a size that can be visually discriminated specifically 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 particle shape is not particularly limited.
The particle immobilization action of the present invention is expressed based on a particle immobilization index. When the particle immobilization index of an aqueous dispersion or liquid composition using the stabilizer of the present invention is larger than the particle immobilization index of an aqueous dispersion or liquid composition using only a polysaccharide, the particle immobilization action is achieved. It is determined that it has. The particle immobilization index mentioned here is the ratio (%) of the immobilized particles in all particles, and is represented by “particle immobilization index (%) = [{α− (β + γ)} / α] × 100”. The
(Α: total number of particles, β: number of particles floating on the liquid surface, γ: number of particles precipitated on the bottom surface)

In addition to stabilizers, the stabilizers of the present invention include starches, fats and oils, proteins, peptides, amino acids, salts, salts such as various phosphates, surfactants, emulsifiers, acidulants, sweeteners, dextrins. , Water-soluble saccharides, sugar alcohols, preservatives, shelf life improvers, antibacterial agents, foaming agents, fragrances, dyes, pH adjusters, antifoaming agents, minerals, dietary fiber, seasonings, acids, alkalis, alcohols, etc. These components may be appropriately blended.

  The water-dispersible dry composition of the present invention is a dried product comprising 50 to 95% by mass of water-dispersible cellulose and 5 to 50% by mass of a water-soluble polymer and / or a hydrophilic substance. Preferably, the water-dispersible cellulose: water-soluble polymer: hydrophilic substance is in the range of 50 to 95: 1 to 49: 1 to 49 mass%, more preferably 60 to 75: 5 to 20:15 to 25 mass%. It is a dried product composed of the above-mentioned range, and exhibits a granular shape, a granular shape, a powder shape, a scale shape, a small piece shape, and a sheet shape. This composition is characterized in that when it is put into water and given mechanical shearing force, the particles are disintegrated and fine fibrous cellulose is dispersed in water. When the water-dispersible cellulose is less than 50% by mass, the cellulose ratio is lowered and the effect is not exhibited. When it is 95% by mass or more, the blending ratio of other components is relatively lowered, so that sufficient dispersibility in water cannot be ensured.

The water-soluble polymer used in the present invention has an action of preventing keratinization between celluloses at the time of drying. Specifically, gum arabic, arabinogalactan, alginic acid and salts thereof, curdlan, Gutty gum, carrageenan, caraya gum, agar, xanthan gum, guar gum, enzymatic degradation guar gum, quince seed gum, gellan gum, gelatin, tamarind seed gum, indigestible dextrin, tragacanth gum, farsellan, pullulan, pectin, locanto bean gum, water soluble 1 type, or 2 or more types of substances selected from the basic soybean polysaccharide, sodium carboxymethyl cellulose, methyl cellulose, sodium polyacrylate and the like are used.
Of these, sodium carboxymethylcellulose is preferable. As this carboxymethylcellulose sodium, the substitution degree of the carboxymethyl group is 0.5 to 1.5, preferably 0.5 to 1.0, more preferably 0.6 to 0.8. The viscosity of the 1% by mass aqueous solution is about 5 to 9000 mPa · s, preferably about 1000 to 8000 mPa · s, and more preferably about 2000 to 6000 mPa · s.

  The hydrophilic substance used in the present invention is a substance that is highly soluble in cold water, hardly causes viscosity, and is solid at room temperature, dextrins, water-soluble saccharides (glucose, fructose, sucrose, lactose, isomerization) From sugar, xylose, trehalose, coupling sugar, palatinose, sorbose, reduced starch saccharified starch, maltose, lactulose, oligosaccharide, fructooligosaccharide, galactooligosaccharide, etc., sugar alcohols (xylitol, maltitol, mannitol, sorbitol, etc.) One or more selected substances. As described above, the water-soluble polymer has an effect of preventing the keratinization of cellulose, but depending on the substance, the water permeability to the inside of the dry composition is inferior, so it is necessary to provide a strong mechanical shear force in water for a long time. May occur. The hydrophilic substance mainly has a function of enhancing the water conductivity, and specifically promotes water disintegration of the dry composition. Since dextrins are particularly strong as this action, it is preferable to use dextrins.

  The dextrins used in the present invention are partial degradation products generated by hydrolyzing starch with acid, enzyme, and heat, and glucose residues are mainly α-1,4 bonds and α-1,6. It consists of a bond, and a DE (dextrose equivalent) of about 2 to 42, preferably about 20 to 42 is used. Branched dextrin from which glucose and low-molecular oligosaccharides have been removed can also be used.

In addition to water-dispersible cellulose, water-soluble polymer, and hydrophilic substance, the water-dispersible dry composition of the present invention includes starches, fats and oils, proteins, salt, various phosphates and other salts, emulsifiers, and acidulants. Ingredients such as sweeteners, fragrances, pigments, pH adjusters, antifoaming agents, foaming agents, preservatives, shelf life improvers, surfactants, antibacterial agents, and disintegrants may be appropriately blended.
As described above, when the water-dispersible dry composition of the present invention is introduced into water and given a mechanical shearing force, the structural unit (particles) is disintegrated and fine fibrous cellulose is dispersed in water. It becomes like this. At this time, the “mechanical shearing force” means that a 0.5 mass% aqueous dispersion is dispersed with a rotary homogenizer at a maximum of 15 000 rpm for 15 minutes, and the temperature is 80 ° C. or less. Means that.

The aqueous dispersion thus obtained has a state before drying, that is, “a component that is stably suspended in water” in an amount of 10% by mass or more based on the total cellulose content (the measurement method will be described later). As described above, this “component that is stably suspended in water” has a length (major axis) of 0.5 to 30 μm and a width (minor axis) observed and measured by a high-resolution scanning electron microscope (SEM). ) Is 2 to 600 nm, and the ratio of the length to the width (major axis / minor axis ratio) is 20 to 400, preferably made of fibrous cellulose having a width (minor axis) of 100 nm or less, more preferably 50 nm. The loss tangent at 0.5% by mass of the aqueous dispersion measured by the method described later is less than 1.
The mass ratio of the water-dispersible cellulose and the polysaccharide constituting the stabilizer of the present invention is water-dispersible cellulose: polysaccharide = 1: 9 to 9: 1 as a solid content, preferably 2: 8 to 8: 1. : 2, more preferably 3: 7 to 7: 3. Similarly, the mass ratio of the water-dispersible dry composition to the polysaccharide is, as a solid content, water-dispersible dry composition: polysaccharide = 1: 9 to 9: 1, preferably 2: 8 to 8: 2. More preferably, it is 3: 7-7: 3.

  The liquid composition of the present invention takes a liquid or paste form at room temperature, and includes liquid food compositions, liquid cosmetic compositions, liquid pharmaceutical compositions, liquid industrial compositions, and the like. The amount of the stabilizer of the present invention to be blended in these liquid compositions is not particularly limited, but is usually about 0.001 to 2% by mass, preferably about 0.1 to 1% by mass. .

  Examples of liquid food compositions include “tea, coffee, black tea, Japanese tea, oolong tea, barley tea, etc., green tea, cocoa, juice, juice, soy milk, soy milk, etc.”, “raw milk, processed milk, fermented food Milk beverages containing dairy ingredients such as milk beverages and lactic acid bacteria beverages, “fermented milk”, “Zenzai”, “various beverages including nutrition-enriched beverages such as calcium-fortified beverages and dietary fiber-containing beverages”, “coffee whitener, Dairy products such as whipping cream, custard cream, soft cream, etc., soups, stews, seasonings such as sauces, sauces, dressings, etc. ”,“ Fruit processed products represented by fruit sauce, fruit preparation, jam ”,“ Food food such as tube liquid food ”,“ Liquid or pasty health food ” And such "liquid or pasty pet food acids" and the like, retort food, frozen food, as food such as microwave, even with different processing techniques or in the form at the time of use preparations are included in the present invention. Since the liquid food composition is usually supplied at a pH of 3 to 8 and a salt concentration of 0.001 to 20%, it is required to exhibit an effect under such conditions.

  Examples of pharmaceutical compositions include “oral medicines such as syrups, vitamins, and nourishing tonics”, “nasal medicines such as hormones”, “infusions / tubes such as infusions, antitumor drugs, and chemotherapeutics” `` Pharmaceuticals '', `` Food meals such as tube liquid foods classified into pharmaceuticals '', `` Ointments such as skin drugs '', `` Medicated cosmetics, vitamin-containing health agents, hair preparations, medicated toothpastes, bath preparations, insecticides '' Quasi-drugs such as herbicides, insect repellents, odor control agents, mouth fresheners, "" artificial cartilage, bioadhesives, biomaterials such as artificial organs ", drug carriers / DNA carriers, patch agents, coating agents, etc. Can be given. 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 foundation, funny, lipstick, lip balm, cheek red, sunscreen cosmetics, eyelash cosmetics such as eyebrows and mascara, and nail polishes such as nail polish and light removal liquid " , "Shampoos, hair rinses, hair tonics, 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 hand cleaners Cleaning agents, bath cosmetics, shavings Cosmetics, fragrances, toothpaste, ointments, plasters and the like. Examples of liquid industrial compositions include pigments, paints, inks, deodorants / fragrances, antibacterial / antifungal agents, adhesives, coating agents, surfactants, hygiene materials, culture materials, chromatographic column packing, etc. Experimental materials, pesticides, paper, detergents, liquid soaps.

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 performed according to JIS P 8101-1976 (“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 prescribed in JIS K 0131-1996 (“General Rules for X-ray Diffraction Analysis”) and is defined by the following equation: .
Crystallinity (%) = {(Ic−Ia) / Ic} × 100
Here, Ic is the diffraction intensity at the diffraction angle 2θ = 22.5 degrees in the X-ray diffraction diagram, and Ia is the baseline intensity (minimum value intensity) around the diffraction angle 2θ = 18.5 degrees.

<Shape of cellulose fiber (particle) (major axis, minor axis, major axis / minor axis ratio)>
Since the range of the size of cellulose fibers (particles) is wide, it is impossible to observe all with one kind of microscope. Therefore, an optical microscope and a scanning microscope (medium resolution SEM, high resolution SEM) are appropriately selected according to the size of the fibers (particles), and observed and measured.
When using an optical microscope, the sample and pure water are weighed out so as to obtain an aqueous dispersion having a solid content concentration of 0.25% by mass, and “Excel Auto Homogenizer” (manufactured by Nippon Seiki Co., Ltd.) is used. The one dispersed for a minute is adjusted to an appropriate concentration, placed on a slide glass, and further covered with a cover glass and observed.
In addition, when using a medium resolution SEM (manufactured by JEOL Ltd., “JSM-5510LV”), a sample aqueous dispersion is placed on a sample stage and air-dried, and then Pt—Pd is deposited by about 3 nm and observed.

When using a high-resolution SEM (manufactured by Hitachi Science Systems, Inc., “S-5000”), place the sample aqueous dispersion on the sample stage, air dry, and then deposit Pt—Pd by about 1.5 nm for observation. .
The major axis, minor axis, and major axis / minor axis ratio of the cellulose fibers (particles) were measured by selecting 15 (pieces) or more from the photographed photographs. Some fibers were almost straight and curved like hair, but never round like lint. The minor axis (thickness) was varied among single fibers, but an average value was adopted. The high-resolution SEM was used when observing a fiber having a minor axis of several nm to 200 nm, but one fiber was too long to fit in one field of view. Therefore, photography was repeated while moving the field of view, and then the pictures were synthesized and analyzed.

<Content of “component that is stably suspended in water”>
It calculates | requires from the following (1)-(5) and (3 ')-(5').
(1) The sample and pure water are weighed out so that the cellulose concentration is 0.1% by mass and dispersed with an ace homogenizer (manufactured by Nippon Seiki Co., Ltd., AM-T type) at 15000 rpm for 15 minutes.
(2) Put 20 g of sample solution into a centrifuge tube and centrifuge at 1000 G for 5 minutes in a centrifuge.
(3) The upper liquid portion is removed and the mass (a) of the sediment component is measured.
(4) Next, the sedimentation component is absolutely dried, and the mass (b) of the solid content is measured.
(5) The content (c) of the “component that is stably suspended in water” is calculated using the following formula.

c = 5000 × (k1 + k2) [mass%]
However, k1 and k2 are calculated using the following formula and used. (Where k1: amount of “fine fibrous cellulose” contained in the upper liquid portion, k2: amount of “fine fibrous cellulose” contained in the precipitation component, and w1: contained in the upper liquid portion. (W2: amount of water contained in the precipitation component, s2: amount of “water-soluble polymer + hydrophilic substance” contained in the precipitation component.)
k1 = 0.02−b + s2
k2 = k1 × w2 / w1
(Water-soluble polymer + hydrophilic substance) / cellulose = d / f [Blending ratio]
w1 = 19.98−a + b−0.02 × d / f
w2 = a−b
s2 = 0.02 × d × w2 / {f × (w1 + w2)}
When the content of the “component that is stably suspended in water” is very large, the mass 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 ′) The upper liquid portion is obtained and the mass (a ′) is measured.
(4 ′) Next, the upper layer component is completely dried, and the mass (b ′) of the solid content is measured.
(5 ′) The content (c) of “a component that is stably suspended in water” is calculated using the following formula.
c = 5000 × (k1 + k2) [mass%]
However, k1 and k2 are calculated using the following formula and used. (Where k1: amount of “fine fibrous cellulose” contained in the upper liquid portion, k2: amount of “fine fibrous cellulose” contained in the precipitation component, and w1: contained in the upper liquid portion. (W2: amount of water contained in the precipitation component, s2: amount of “water-soluble polymer + hydrophilic substance” contained in the precipitation component.)
k1 = b′−s2 × w1 / w2
k2 = k1 × w2 / w1
(Water-soluble polymer + hydrophilic substance) / cellulose = d / f [Blending ratio]
w1 = a′−b ′
w2 = 19.98−a ′ + b′−0.02 × d / f
s2 = 0.02 × d × w2 / {f × (w1 + w2)}
If the boundary between the liquid portion of the upper layer and the sediment component is not clear in the operation (3) and separation is difficult, the operation is performed with the cellulose concentration lowered appropriately.

<Loss tangent (= loss elastic modulus / storage elastic modulus)>
It calculates | requires in the procedure of the following (1)-(3).
(1) The sample and pure water are weighed so as to obtain an aqueous dispersion having a solid content concentration of 0.5% by mass, and dispersed with “Excel Auto Homogenizer” (manufactured by Nippon Seiki Co., Ltd.) at 15000 rpm for 15 minutes.
(2) Leave in an atmosphere at 25 ° C. for 3 hours.
(3) After putting the sample liquid into the dynamic viscoelasticity measuring apparatus, the sample is allowed to stand for 5 minutes, and then measured under the following conditions to determine a loss tangent (tan δ) at a frequency of 10 rad / s.
Apparatus: “ARES” (Rheometric Scientific, Inc., 100FRTN1 type)
Geometry: Double Wall Couette
Temperature: 25 ° C
Distortion: 10% (fixed)
Frequency: 1 → 100 rad / s (Raise over about 170 seconds)

<Preparation of 0.35% mass concentration aqueous dispersion and particle number measurement>
First, a sample and water were weighed so that an aqueous dispersion having a solid content of 1% by mass was dispersed using a “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 8000 rpm for 10 minutes. 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. In this example, 100 mg of calcium chloride was added per 1 g of stabilizer when pectin was used.

The particle fixing action of the 0.35% by mass aqueous dispersion is the action of fixing any of the particles (1) to (4) described below, and also has a particle fixing index (%). It is expressed as
(1) Spherical particles a: polypropylene particles (major axis 2.4 mm, minor axis 2.4 mm, average particle diameter 2.4 mm, specific gravity 0.9)
(2) Spherical particles b: particles made of polyacetal resin (major axis 2.4 mm, minor axis 2.4 mm, average particle diameter 2.4 mm, specific gravity 1.4)
(3) Plate-like particles c: paper-made particles (long axis 5 mm, short axis 3 mm rectangle, thickness 0.3 mm, specific gravity 0.9)
(4) Plate-like particles d: polyethylene terephthalate particles (long diameter 5 mm, short diameter 3 mm rectangle, thickness 0.3 mm, specific gravity 1.4)
Fill each 100 mL sample bottle with 0.35 wt% stabilizer aqueous dispersion and the same wt% polysaccharide aqueous dispersion. Next, any one of the particles (1) to (4) is selected, and 20 particles are added to each of the 0.35 mass% stabilizer aqueous dispersion and the same mass% polysaccharide aqueous dispersion. 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 formula of the particle immobilization index (%) described later. Determine the particle immobilization index (%).

<Fruit sauce, soft yogurt, fermented milk beverage, non-oil dressing, corn soup, grated soup, massage agent, consommé soup particle count>
These liquid compositions are prepared according to the method described below, and 20 particles per filled container are added in an external split. After a predetermined time has passed, the number of particles floating on the liquid surface or the number of particles precipitated on the bottom surface is counted visually, and the result is substituted into the formula for the particle immobilization index (%) described below to obtain the particle immobilization index ( %). However, when the added particles are small, 50 particles instead of 20 particles may be added.

<Particle immobilization index, particle immobilization action>
The particle immobilization index (%) is obtained by the following formula.
Particle 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 The particle immobilization index of the aqueous dispersion or liquid composition using the stabilizer of the present invention is the same concentration When it is larger than the particle immobilization index of the prepared aqueous dispersion or liquid composition using only the polysaccharide, it is determined that it has a particle immobilization action. That is, when the following particle immobilization indices X and Y are in a relationship of “particle immobilization index X> particle immobilization index Y”, it is determined that the particles have immobilization action.
Particle immobilization index X: Particle immobilization index when the stabilizer of the present invention is used as an aqueous dispersion or liquid composition Particle immobilization index Y: Included in the stabilizer used when obtaining the particle immobilization index X Particle immobilization index when polysaccharide is used as aqueous dispersion or liquid composition

<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).

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to these at all. The water dispersible cellulose, water dispersible dry composition, guar gum, pectin, glucomannan, xanthan gum, tamarind seed gum, karaya gum, and water-soluble soybean polysaccharide used in the examples are shown in the following (1) to (10). .

(1) Preparation of water-dispersible dry composition A: Commercially available wood pulp (average polymerization degree = 1720, α-cellulose content = 78 mass%) is cut into a 6 × 16 mm square and has a solid content concentration of 80 Water was added so that it might become mass%. This was passed once through a cutter mill (cutting head / horizontal blade gap: 2.03 mm, impeller rotation speed: 3600 rpm), taking care not to separate water and pulp chips as much as possible.
The cutter mill-treated product and water were weighed out so that the cellulose concentration was 1.5% by mass, and stirred until there was no fiber entanglement. This aqueous dispersion was treated with a grindstone rotary grinder (grinder rotation speed: 1800 rpm). The number of treatments was 2, and the grinder clearance was changed from 110 to 80 μm.
Next, the obtained aqueous dispersion was directly subjected to 18 passes with a high-pressure homogenizer (treatment pressure: 55 MPa) to obtain a water-dispersible cellulose A slurry. When observed with an optical microscope, fine fibrous cellulose having a major axis of 10 to 400 μm, a minor axis of 1 to 5 μm, and a major axis / minor axis ratio of 10 to 300 was observed. The loss tangent was 0.64. The content of “a component that is stably suspended in water” was 15% by mass. When observed with a high-resolution SEM, very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 10 to 150 nm, and a major axis / minor axis ratio of 30 to 300 was observed.

Water-dispersible cellulose A: carboxymethylcellulose sodium: dextrin = 70:18:12 (parts by weight) Water-dispersible cellulose A slurry with carboxymethylcellulose sodium (1% by weight aqueous solution viscosity: about 3400 mPa · s) And dextrin (DE: about 23) were added, and 15 kg was stirred and mixed at 8000 rpm for 30 minutes with a stirring homogenizer (“TK AUTO MIXER” manufactured by Tokushu Kika Kogyo Co., Ltd.). Cellulose A ′ slurry was obtained.
Next, this mixed solution was cast into an aluminum plate shape with a thickness of 2 mm using an applicator, and dried at 120 ° C. for 45 minutes using a hot air dryer to obtain a film. This was pulverized with a cutter mill (manufactured by Fuji Powder Co., Ltd.) so that the sieve having an opening of 1 mm was almost completely passed through to obtain a water-dispersible dry composition A.
The degree of crystallinity of the water-dispersible dry composition A was 68% or more, the loss tangent was 0.64, and the content of “component stably suspended in water” was 20% by mass. When observed with a high-resolution SEM, very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 15 to 130 nm, and a major axis / minor axis ratio of 30 to 300 was observed.

(2) Adjustment of water-dispersible cellulose B: Commercially available straw pulp (average polymerization degree = 930, α-cellulose content = 68% by mass) is cut into a 6 × 12 mm square to be 4% by mass. Water was added and stirred for 5 minutes with a home mixer. This was dispersed for 1 hour with a high-speed rotation type homogenizer (Yamato Scientific, “ULTRA-DISPERSER”).
This aqueous dispersion was treated with a grindstone rotary grinder (grinder rotation speed: 1800 rpm). The number of treatments was 2, and the grinder clearance was changed from 60 to 40 μm.
Next, the obtained aqueous dispersion was diluted with water to 2% by mass, and subjected to 8 passes with a high-pressure homogenizer (treatment pressure: 175 MPa) to obtain a water-dispersible cellulose B slurry. The crystallinity was 74%. When observed with an optical microscope, fine fibrous cellulose having a major axis of 10 to 700 μm, a minor axis of 1 to 30 μm, and a major axis / minor axis ratio of 10 to 150 was observed. The loss tangent was 0.43. The content of “a component that is stably suspended in water” was 89% by mass. When observed with a high-resolution SEM, very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 6 to 300 nm, and a major axis / minor axis ratio of 30 to 350 was observed.

(3) Preparation of water-dispersible dry composition C: Commercial bagasse pulp (average polymerization degree = 1320, α-cellulose content = 77%) was cut into a 6 × 16 mm square and the solid content concentration was 77% by mass. Water was added so that This was passed once through a cutter mill (cutting head / horizontal blade gap: 2.03 mm, impeller rotation speed: 3600 rpm), taking care not to separate water and pulp chips as much as possible. Cutter mill processed product, carboxymethylcellulose sodium (1 mass% aqueous solution viscosity: about 3400 mPa · s) and water are weighed out so that the cellulose concentration is 2 mass% and the concentration of carboxymethylcellulose sodium is 0.118 mass%. The mixture was stirred until the fibers were tangled.
The obtained aqueous dispersion was directly subjected to 9 passes with a high-pressure homogenizer (treatment pressure 90 MPa) to obtain a water-dispersible cellulose C slurry. When observed with an optical microscope and medium resolution SEM, fine fibrous cellulose having a major axis of 10 to 500 μm, a minor axis of 1 to 25 μm, and a major axis / minor axis ratio of 5 to 190 was observed. The loss tangent was 0.32. The “component stably suspended in water” was 99% by mass. When the “component that is stably suspended in water” was observed with a high-resolution SEM, a very fine fibrous cellulose having a major axis of 1 to 20 μm, a minor axis of 10 to 400 nm, and a major axis / minor axis ratio of 20 to 300 was obtained. Observed.

Water dispersible cellulose C: carboxymethylcellulose sodium: dextrin: rapeseed oil = 68: 12: 19.7: 0.3 (parts by weight) Water dispersible cellulose C slurry with carboxymethylcellulose sodium (1 mass) % Aqueous solution viscosity: about 3400 mPa · s) and dextrin (DE: about 28) were added, and 15 kg was stirred at 8000 rpm with a stirring type homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd., “TK AUTO HOMO MIXER”). After stirring and mixing for a minute, 20 MPa and one pass treatment were performed with the above-described high-pressure homogenizer to obtain a water-dispersible cellulose C ′ slurry.
The water-dispersible cellulose C ′ slurry is dried with a drum dryer, scraped off with a scraper, and the obtained product is pulverized with a cutter mill (manufactured by Fuji Powdal Co., Ltd.) to almost pass through a 2 mm sieve. Thus, a water dispersible dry composition C was obtained. The crystallinity of the water-dispersible cellulose composition C was 57% or more, the loss tangent was 0.52, and the “component stably suspended in water” was 100% by mass. When the “component that is stably suspended in water” was observed with a high-resolution SEM, a very fine fibrous cellulose having a major axis of 1 to 15 μm, a minor axis of 10 to 330 nm, and a major axis / minor axis ratio of 20 to 250 was obtained. Observed.

(4) Guar gum (Made by Unitech Foods)
(5) Pectin (CP Kelco, LM pectin)
(6) Glucomannan (Shimizu Chemical Co., Ltd.)
(7) Xanthan gum (Dainippon Pharmaceutical Co., Ltd.)
(8) Tamarind seed gum (manufactured by Dainippon Pharmaceutical Co., Ltd.)
(9) Karaya gum (manufactured by Sanei Pharmaceutical Trading Co., Ltd.)
(10) Water-soluble soybean polysaccharide (Fuji Oil Co., Ltd.)

[Example 1]
A stabilizer containing a water-dispersible dry composition A: guar gum in a mass ratio of 6: 4 is prepared. The stabilizer and water were weighed out so that the solid content became an aqueous dispersion having a mass of 1% by mass, and dispersed using TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 8000 rpm for 10 minutes. 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 aqueous stabilizer solution. Filled.
20 “spherical particles a” were added to one sample bottle containing 0.35 mass% sample aqueous dispersion, and the temperature was adjusted at 25 ° C. for 1 hour, and then the sample bottle was vigorously shaken up and down and mixed. . Further, after standing at 25 ° C. for 3 hours, the number of particles floating on the liquid surface or the number of particles precipitated on the bottom surface was counted by visual observation to obtain a particle immobilization index (%). The particle immobilization index when “spherical particle a” was added was X (a1).
Similarly, X (b1) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, X (c1) was used as the particle immobilization index when “plate-like particle c” was added instead of spherical particle a.
Similarly, X (d1) is the particle immobilization index when “plate-like particles d” are added instead of the spherical particles a.
These results are shown in Table 1.

[Example 2]
A water-dispersible cellulose B: a stabilizer containing guar gum in a mass ratio of 6: 4, 0.35% by mass aqueous dispersion was used using a water-dispersible cellulose B slurry (solid content 2% by mass). Prepared in the same manner as in Example 1. The particle immobilization index when 20 “spherical particles a” were added thereto was X (a2).
Similarly, X (b2) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, instead of the spherical particles a, the particle immobilization index when “plate-like particles c” were added was X (c2).
Similarly, X (d2) was used as the particle immobilization index when “plate-like particle d” was added instead of spherical particle a.
These results are shown in Table 2.

[Example 3]
Water-dispersible dry composition C: A 0.35 mass% aqueous dispersion of a stabilizer containing guar gum in a mass ratio of 8: 2 was prepared in the same manner as in Example 1. The particle immobilization index when 20 “spherical particles a” were added was defined as X (a3).
Similarly, X (b3) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, X (c3) was used as the particle immobilization index when “plate-like particle c” was added instead of spherical particle a.
Similarly, X (d3) was used as the particle immobilization index when “plate-like particle d” was added instead of spherical particle a.
These results are shown in Table 3.

[Example 4]
Water dispersible dry composition C: A 0.35 mass% aqueous dispersion of a thickener containing 6: 4 mass ratio of guar gum was prepared in the same manner as in Example 1. The particle immobilization index when 20 “spherical particles a” were added was defined as X (a4).
Similarly, X (b4) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, X (c4) was used as the particle immobilization index when “plate-like particles c” were added instead of the spherical particles a.
Similarly, X (d4) was used as the particle immobilization index when “plate-like particles d” were added instead of the spherical particles a.
These results are shown in Table 4.

[Example 5]
Water-dispersible dry composition C: A 0.35 mass% aqueous dispersion of a stabilizer containing guar gum in a mass ratio of 4: 6 was prepared in the same manner as in Example 1. The particle immobilization index when 20 “spherical particles a” were added was defined as X (a5).
Similarly, X (b5) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, X (c5) was used as the particle immobilization index when “plate-like particle c” was added instead of spherical particle a.
Similarly, X (d5) was used as the particle immobilization index when “plate-like particle d” was added instead of spherical particle a.
These results are shown in Table 5.

[Example 6]
Water-dispersible dry composition C: Stabilizer containing pectin at a mass ratio of 8: 2, 0.35 mass% aqueous dispersion, and stabilizer so that the solid content becomes 1 mass% aqueous dispersion Water was weighed out and dispersed at 85 ° C. and 8000 rpm for 10 minutes using “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.). 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 stabilizer aqueous solution, and 100 mg per 1 g stabilizer. Of calcium chloride was added. The particle immobilization index when 20 “spherical particles a” were added was defined as X (a6).
Similarly, X (b6) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, instead of the spherical particles a, the particle immobilization index when “plate-like particles c” were added was X (c6).
Similarly, X (d6) was used as the particle immobilization index when “plate-like particle d” was added instead of spherical particle a.
These results are shown in Table 6.

[Example 7]
Water dispersible dry composition C: A 0.35 mass% aqueous dispersion of a stabilizer containing pectin in a mass ratio of 6: 4 was prepared in the same manner as in Example 6. The particle immobilization index when 20 “spherical particles a” were added was defined as X (a7).
Similarly, X (b7) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, X (c7) was used as the particle immobilization index when “plate-like particles c” were added instead of the spherical particles a.
Similarly, X (d7) was used as the particle immobilization index when “plate-like particle d” was added instead of spherical particle a.
These results are shown in Table 7.

[Example 8]
A water-dispersible dry composition C: A stabilizer containing a glucomannan in a mass ratio of 6: 4 was prepared in the same manner as in Example 1, except that a 0.35% by mass aqueous dispersion was prepared. The particle immobilization index when 20 “spherical particles a” were added was defined as X (a8).
Similarly, X (b8) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, X (c8) was used as the particle immobilization index when “plate-like particle c” was added instead of spherical particle a.
Similarly, X (d8) was used as the particle immobilization index when “plate-like particles d” were added instead of the spherical particles a.
These results are shown in Table 8.

[Example 9]
Fruit sauce A was prepared and evaluated by the following procedure using a stabilizer (hereinafter referred to as stabilizer a) in which water-dispersible dry composition C and guar gum were powder-mixed at a mass ratio of 6: 4.
In a beaker, 14.32% by mass of water and 50% by mass of fructose-glucose liquid sugar (“F-55” manufactured by Oji Cornstarch Co., Ltd.) were heated to 60 ° C., and “TK homomixer” (special machine) A mixture of 0.68% by mass of the stabilizer a and 5% by mass of granulated sugar (manufactured by Daiichi Sugar Industry Co., Ltd.) was added with stirring at 8000 rpm. Dispersed for minutes.
Further, the dispersion apparatus was replaced with a propeller stirring blade, 30% by mass of strawberry puree (thawed frozen strawberry and thawed) was added and stirred at 400 rpm. Stirring was continued until 2 minutes after the liquid temperature reached 80 ° C., and sterilized to fill the container. This was designated as fruit sauce A ′.
To this fruit sauce A ′, 20 pieces of blueberry particles (thawed frozen blueberry and sterilized by heating at 80 ° C., spherical product having a major axis of 17 mm and a minor axis of 1.4 mm) are added to the fruit sauce A ′ in an external ratio. Source A. After cooling the fruit sauce A at 5 ° C. for 1 hour, the container was shaken vigorously up and down and stored at 5 ° C. for 30 days. The blueberry particle immobilization index X (a12) was 100%. The pH of the fruit sauce A was 3.5.
These results are shown in Table 9.

[Example 10]
Using the fruit sauce A ′ of Example 9, soft yogurt B was prepared and evaluated by the following procedure.
In a clean bench, 85% by mass of the following yogurt for stirring and 15% by mass of the fruit sauce A ′ prepared in Example 9 were mixed at 5 ° C. Furthermore, 20 blueberry particles (thawed frozen blueberry and sterilized by heating at 80 ° C., spherical product having a major axis of 17 mm and a minor axis of 1.4 mm) are added in an external ratio, and then a propeller stirring blade is used. Then, the mixture was stirred at 5 ° C. and 400 rpm for 1 minute, filled into a cup, and this was designated as soft yogurt B. The plate was stored at 5 ° C. for 7 days, and the blueberry particle immobilization index X (b13) was 80%. At this time, the content of the stabilizer a in the soft yogurt B was 0.1% by mass, and the pH was 4.2.
These results are shown in Table 10.
Moreover, the manufacturing method of the stirring yogurt used here is as follows.
21.7% by mass of water and 75% by mass of milk (manufactured by Southern Japan Dairy Kyodo Co., Ltd., milk fat content 3.5% or more, non-fat milk solid content 8.3%) are poured into a stainless steel beaker and stirred with a propeller While stirring at 200 rpm at 25 ° C. using a blade, 3.3% by mass of skim milk powder (manufactured by Snow Brand Milk Products Co., Ltd.) was added, and stirring was continued for 10 minutes.
The solution was homogenized at a processing pressure of 15 MPa using a high-pressure homogenizer, and further stirred for 30 minutes at 80 ° C. and 200 rpm using a propeller stirring blade to sterilize the solution. Furthermore, it cooled to 30 degreeC in 20 minutes, stirring at 200 rpm in a clean bench. A starter (manufactured by Danisco Carter, “MSK-Mix AB N 1-45 Visbybac DIP”) as an aqueous solution of 0.01% by mass was added to this solution in an external ratio of 0.32% by mass, stirred with a spatula, and fermented. The container was filled. This was transferred to an incubator and fermented at 42 ° C. for 12 hours. After fermentation, the mixture was transferred to a refrigerator at 5 ° C. and passed for 3 days to obtain a stirring yogurt (non-fat milk solid content of 9.4% or more).

[Example 11]
14.32% by mass of water and 40% by mass of fructose-glucose liquid sugar (“F-55” manufactured by Oji Cornstarch Co., Ltd.) were added and heated to 60 ° C., and “TK homomixer” (special machine industry stock) While stirring at a company), a powder mixture of 0.68% by mass of the stabilizer a and 5% by mass of granulated sugar (Daiichi Sugar Industry Co., Ltd.) is added and dispersed at 8000 rpm for 10 minutes. It was.
Further, the dispersion apparatus was replaced with a propeller stirring blade, and 40% by mass of strawberry puree (thawed and thawed frozen strawberry) heated to 80 ° C. and sterilized was added and stirred at 400 rpm. Stirring was continued until 2 minutes after the liquid temperature reached 80 ° C., and sterilization was performed.
Using this fruit sauce C and the stirred yogurt of Example 10, fermented milk drink D was prepared and evaluated by the following procedure.
In a clean bench, 30% by mass of fruit sauce C, 50% by mass of the stirred yogurt of Example 8 and 20% by mass of water were mixed for 2 minutes at 400 rpm using a propeller stirring blade.
This solution was homogenized at a processing pressure of 15 MPa using a high-pressure homogenizer and filled into a heat-resistant container. 20 blueberry particles (thawed frozen blueberry and sterilized by heating at 80 ° C., spherical product having a major axis of 18 mm and a minor axis of 1.4 mm) per heat-resistant container were added in an external ratio. After cooling at 5 ° C. for 1 hour, the heat-resistant container was vigorously shaken up and down to obtain a fermented milk drink D. Blueberry particle fixation index X (a14) of fermented milk drink D after standing at 5 ° C. for another 23 hours was 90%. At this time, the content of the stabilizer a in the fermented milk beverage D was 0.2% by mass, and the pH was 4.0.
These results are shown in Table 11.

[Example 12]
A non-oil dressing E was prepared and evaluated by the following procedure using a stabilizer (hereinafter referred to as stabilizer b) in which water-dispersible dry composition C and xanthan gum were powder-mixed at a mass ratio of 5: 5.
While stirring 50.95% by mass of water with a propeller stirring blade, 20% by mass of a 1% by mass thickener b aqueous dispersion is added. 5% by weight granulated sugar (Daiichi Sugar Industry Co., Ltd.), 3% by weight salt, 0.9% by weight Consomme granule (by Ike Corporation), 0.1% by weight sodium glutamate (Nippon Tobacco Inc.) Company) and stirred at 80 ° C. and 400 rpm for 4 minutes. Furthermore, 19% by weight apple vinegar (manufactured by Mitsukan Co., Ltd.), 1% by weight lemon juice (Pokka Corporation, 100% fruit juice) and 0.05% by weight garlic juice are added and stirred for another 2 minutes. Filled. In addition to this, 50 coarsely ground pepper particles (major axis 1.8 mm, minor axis 1.1 mm), 50 dry Italian parsley particles (major axis 4.1 mm, minor axis 1.9 mm), 50 coarse particles per filled container. Bitter dust particles (major axis 2.0 mm, minor axis 1.8 mm) were added in an external ratio, cooled at 25 ° C. for 1 hour, and shaken vigorously up and down to obtain non-oil dressing E. The content of the stabilizer b in the non-oil dressing E is 0.2% by mass, the pH is 3.3, and the salt concentration is 3% by mass or more.
The non-oil dressing E was allowed to stand at 25 ° C. for 2 weeks, and the following pellet particle immobilization index X (b15), parsley particle immobilization index X (c16), and pepper particle immobilization index X (c17) were obtained.
Pepper particle immobilization index X (b15): 72%,
Parsley particle immobilization index X (c16): 96%,
Red pepper particle immobilization index X (d17): 90%.
These results are shown in Table 12.

[Example 13]
The stabilizer a used in Example 9 was blended, and corn soup F was prepared and evaluated according to the following procedure.
While stirring 88.6% by mass of water with “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), 0.4% by mass of stabilizer a was added and dispersed at 80 ° C. and 7000 rpm for 5 minutes. Furthermore, commercially available dried soup (Pokka Corporation Co., Ltd.) not containing 11% by mass of polysaccharide was added, dispersed for 5 minutes, filled in a heat-resistant container, and 20 corn particles (major axis 10 mm, minor axis per heat-resistant container). 8 mm, thickness 5 mm) was added in an external ratio. Sterilized at 85 ° C. for 10 minutes, cooled at 25 ° C. for 1 hour, and shaken vigorously up and down to obtain corn soup F. Corn soup F had a pH of 6.8 and a salt concentration of 0.73% by mass. The corn particle immobilization index X (b18) after standing at 25 ° C. for 7 days was 95%.
These results are shown in Table 13.

[Example 14]
Using a stabilizer in which water-dispersible dry composition C and xanthan gum were powder-mixed at a mass ratio of 7: 3 (hereinafter referred to as “stabilizer c”), grated weeping G was prepared and evaluated.
While stirring 43.82% by mass of water with “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), 0.18% by mass of stabilizer c is added and dispersed at 80 ° C. and 10,000 rpm for 10 minutes. The dispersing device was replaced with a propeller stirring blade, and 10% by weight granulated sugar (Daiichi Sugar Co., Ltd.), 5% by weight salt, 35% by weight soy sauce (by Kikkoman Corporation, salt concentration 16%), 1% by weight % Garlic juice, 5% by weight apple vinegar (manufactured by Mitsukan Co., Ltd.) was added, and the mixture was further dispersed for 10 minutes and filled in a heat-resistant bottle. Add 50 radish grated particles (major axis 4.1mm, minor axis 1.1mm) per heat-resistant bottle, sterilize by heating at 80 ° C for 10 minutes, cool at 25 ° C for 1 hour, shake vigorously up and down, This was called Grated Weeping G. The pH of grated weeping G was 4.2, and the salt concentration was 10.6% by mass.
The daikon grated particle immobilization index X (c19) after the grater G was left at 25 ° C. for 21 days was 100%.
These results are shown in Table 14.

[Example 15]
Scrub massage agent H was prepared and evaluated using a stabilizer (hereinafter referred to as stabilizer d) in which water-dispersible dry composition A: guar gum was mixed at a mass ratio of 6: 4.
While stirring 87.6% by mass of purified water (Japanese Pharmacopoeia) with “TK Homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), 0.4% by mass of stabilizer d was added and 15% at 10,000 rpm. Dispersed for minutes. The dispersing apparatus was changed to a propeller stirring blade, 8% by mass glycerin (Japanese Pharmacopoeia) and 4% by mass disinfecting ethanol (Japanese Pharmacopoeia) were added and stirred at 300 rpm for 2 minutes. To this, 50 spherical cellulose particles (major axis 0.75 mm, minor axis 0.75 mm, average particle diameter 0.75 mm) were added as a scrub, filled in a sample bottle, and allowed to stand at 25 ° C. for 3 hours. The massage agent H was shaken vigorously up and down.
After further standing at 25 ° C. for 1 day, the spherical cellulose particle immobilization index X (b20) was determined to be 52%.
These results are shown in Table 15.
[Example 16]
Using a stabilizer in which water-dispersible dry composition C and tamarind seed gum were powder-mixed at a mass ratio of 8: 2 (hereinafter referred to as “stabilizer e”), grated P was prepared in the same manner as in Example 14. And evaluated.
In place of the stabilizer c of Example 14, 0.38% by mass of the stabilizer e was added to adjust the grater P. However, the water used for the adjustment was 43.62% by mass.
The pH of grated weeping P was 4.1, and the salt concentration was 10.6% by mass.
The radish grated particle fixation index X (c30) of grated weeping P was 70%.
These results are shown in Table 16.
[Example 17]
Consomme soup Q was prepared and evaluated using a stabilizer in which water-dispersible dry composition C and Karaya gum were powder-mixed at a mass ratio of 7: 3 (hereinafter referred to as stabilizer f).
While stirring 98% by mass of water with “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), 0.3% by mass of stabilizer f was added and dispersed at 80 ° C. and 10,000 rpm for 10 minutes. The dispersion apparatus was replaced with a propeller stirring blade, 1.5% by mass of consomme granules (manufactured by Ike Co., Ltd.) and 0.2% by mass of sodium chloride were added thereto, and the mixture was further dispersed for 5 minutes and filled into a sample bottle. 20 pieces of ground pepper (long diameter 2.0 mm, short diameter 1.8 mm) per sample bottle were added in an external ratio, cooled at 25 ° C. for 1 hour, and shaken vigorously up and down to obtain consomme soup Q.
Consomme soup Q had a pH of 6.8 and a salt concentration of 1% by mass.
After allowing the consomme soup Q to stand at 25 ° C. for 24 hours, the pellet particle immobilization index X (b31) was 80%.
These results are shown in Table 17.
[Example 18]
Soft yogurt R was adjusted and evaluated using a stabilizer (hereinafter referred to as stabilizer g) in which water-dispersible dry composition C and water-soluble soybean polysaccharide were powder-mixed at a mass ratio of 6: 4.
While stirring 21.5% by mass of water at 80 ° C. with “TK homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), 0.2% by mass of stabilizer g was added and dispersed at 8000 rpm for 10 minutes. Then, it cooled to 25 degreeC. Further, 75% by weight of milk (manufactured by Minami Nihon Dairy Kyodo Co., Ltd., milk fat content 3.5% or more, non-fat milk solid content 8.3%) is poured into a stainless steel beaker, using a propeller stirring blade at 25 ° C. While stirring at 200 rpm, 3.3% by mass of skim milk powder (manufactured by Snow Brand Milk Products Co., Ltd.) was added and stirring was continued for 10 minutes.
The solution was homogenized at a processing pressure of 15 MPa using a high-pressure homogenizer, and further stirred for 30 minutes at 80 ° C. and 200 rpm using a propeller stirring blade to sterilize the solution. The mixture was further cooled to 30 ° C. in 20 minutes while stirring at 200 rpm. To this solution, a starter (manufactured by Kyodo Dairies Co., Ltd.) in a 0.01% by mass aqueous solution was added in an external ratio of 0.2% by mass, stirred with a spatula, and filled into a fermentation vessel. This was transferred to an incubator and fermented at 42 ° C. for 12 hours. After fermentation, the mixture was transferred to a refrigerator at 5 ° C. and passed for 3 days to obtain a stirring yogurt (non-fat milk solid content of 9.4% or more).
The stirring yoghurt was transferred to a beaker and stirred for 5 minutes at 5 ° C. and 200 rpm using a propeller stirring blade to break the curd and fill the container 100 g at a time. Twenty yellow peaches (5 mm square cubes) per container were added in an external ratio to obtain soft yogurt R. The pH of soft yogurt R was 3.8, and the yellow peach particle immobilization index X (b32) after standing at 5 ° C. for 24 hours was 90%.
These results are shown in Table 18.

[Comparative Example 1]
Instead of the stabilizer described in Example 1, guar gum was used, and 20 “spherical particles a” were added to a 0.35 mass% aqueous dispersion prepared in the same manner as in Example 1. The particle immobilization index at that time was defined as Y (a9).
Similarly, Y (b9) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, Y (c9) was used as the particle immobilization index when “plate-like particle c” was added instead of spherical particle a.
Similarly, Y (d9) was used as the particle immobilization index when “plate-like particles d” were added instead of the spherical particles a.
These results are shown in Tables 1-5.

[Comparative Example 2]
Instead of the stabilizer described in Examples 6 and 7, 20 particles of “spherical particles a” were added to a 0.35 mass% aqueous dispersion prepared using pectin in the same manner as in Examples 6 and 7. ”Was added as Y (a10).
Similarly, Y (b10) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, Y (c10) was used as the particle immobilization index when “plate-like particles c” were added instead of the spherical particles a.
Similarly, Y (d10) was used as the particle immobilization index when “plate-like particle d” was added instead of spherical particle a.
These results are shown in Tables 6-7.

[Comparative Example 3]
In place of the stabilizer described in Example 8, glucomannan was used, and 20 “spherical particles a” were added to 0.35% by mass aqueous dispersion prepared in the same manner as in Example 8. The particle immobilization index was Y (a11).
Similarly, Y (b11) was used as the particle immobilization index when “spherical particle b” was added instead of spherical particle a.
Similarly, instead of the spherical particles a, the particle immobilization index when “plate-like particles c” were added was Y (c11).
Similarly, Y (d11) was used as the particle immobilization index when “plate-like particles d” were added instead of the spherical particles a.
These results are shown in Table 8.

[Comparative Example 4]
Fruit sauce I ′ was prepared using guar gum instead of stabilizer a, which was used when preparing fruit sauce A ′ of Example 9. To this fruit sauce I ′, 20 blueberry particles of Example 9 were added per filled container to obtain a fruit sauce I. As for the blueberry particles of Fruit Sauce I, 90% was floating on the liquid surface, and the particle immobilization index Y (a21) was 10%. The pH was 3.5.
These results are shown in Table 9.

[Comparative Example 5]
Instead of the fruit sauce A ′ of Example 10, the fruit sauce I ′ of Comparative Example 4 was used. That is, soft yogurt J was prepared and evaluated using guar gum instead of stabilizer a. As for the blueberry particles of soft yogurt J, 50% floated on the liquid surface, and the particle immobilization index Y (b22) was 50%. The pH was 4.2.
These results are shown in Table 10.

[Comparative Example 6]
Fermented milk drink K was prepared and evaluated using guar gum instead of stabilizer a in Example 11. As for the blueberry particle | grains of fermented milk drink K, 90% was floating on the liquid level, and the particle | grain fixed parameter | index Y (a23) was 10%. The pH was 4.0.
These results are shown in Table 11.

[Comparative Example 7]
Non-oil dressing L was prepared and evaluated using xanthan gum instead of stabilizer b of Example 12. The non-oil dressing L has a pH of 3.3 and a salt concentration of 3% by mass or more.
The powder particle immobilization index Y (b24), parsley particle immobilization index Y (c25), and pepper particle immobilization index Y (c26) of the non-oil dressing L were determined as follows.
Pepper particle immobilization index Y (b24): 6% (94% was precipitated on the bottom surface)
Parsley particle immobilization index Y (c25): 10% (90% was floating on the liquid surface)
Red pepper particle immobilization index Y (d26): 12% (88% was deposited on the bottom)
These results are shown in Table 12.

[Comparative Example 8]
Corn soup M was prepared and evaluated using guar gum instead of stabilizer a of Example 13. Corn particles of corn soup M were all precipitated on the bottom surface, and the immobilization index Y (b27) was 0%. The pH was 6.8 and the salt concentration was 0.73% by mass.
These results are shown in Table 13.

[Comparative Example 9]
Grape N is prepared and evaluated using xanthan gum in place of stabilizer c of Example 14. Grated daikon N radish grated particle immobilization index Y (c28) was 70%, pH 4.2, and salt concentration 10.6% by mass. The grater N had three-layer separation, and the appearance was poor.
These results are shown in Table 14.

[Comparative Example 10]
Massage O was prepared and evaluated using guar gum instead of stabilizer d of Example 15. All the spherical cellulose particles of the massage agent O were precipitated on the bottom surface, and the immobilization index Y (b29) was 0%.
These results are shown in Table 15.
[Comparative Example 11]
In place of the stabilizer e of Example 16, tamarind seed gum was used, and the grater S was adjusted and evaluated in the same manner as in Example 16.
The pH of grated weeping S was 4.1, and the salt concentration was 10.6% by mass.
The grated dripping S caused separation and poor appearance, and the radish grated particle immobilization index Y (c33) was 0%.
These results are shown in Table 16.
[Comparative Example 12]
Consomme soup T was prepared and evaluated using karaya gum instead of the stabilizer f of Example 17.
Consomme soup T had a pH of 6.8 and a salt concentration of 1% by mass.
After allowing the consomme soup T to stand at 25 ° C. for 24 hours, the pellet particle immobilization index Y (b34) was 20%. (80% was deposited on the bottom.)
These results are shown in Table 17.
[Comparative Example 13]
Soft yogurt U was prepared and evaluated using water-soluble soybean polysaccharide instead of the stabilizer g of Example 18.
The pH of soft yogurt U was 3.8, and the yellow peach particle immobilization index Y (b35) after standing at 5 ° C. for 24 hours was 20%.
These results are shown in Table 18.

  The water-dispersible cellulose, which is the fine fibrous cellulose of the present invention, and a stabilizer containing at least one type of polysaccharide have a particle fixing action and can provide a good-looking product. In addition, the load on the manufacturing process can be reduced. This property can be used not only in the food field but also in applications such as pharmaceuticals and cosmetics.

Claims (5)

A fine fibrous cellulose made from plant cell walls as a raw material, and stably suspended in water (major axis: 0.5 to 30 μm, minor axis: 2 to 600 nm, major axis / minor axis ratio: 20 to 400) Water dispersible cellulose characterized by having a loss tangent of less than 1 in the case of 0.5 mass% aqueous dispersion, and galactomannan, glucomannan, sodium alginate, Selected from xanthan gum, tamarind seed gum, pectin, carrageenan, gellan gum, agar, sodium carboxymethylcellulose, soybean water-soluble polysaccharide, karaya gum, psyllium seed gum, pullulan, gum arabic, tragacanth gum, gaddy gum, arabinogalactan, curdlan A composition comprising at least one polysaccharide comprising a water dispersible cell. Loin: Polysaccharides = 1: 9 to 9: stabilizers, characterized in that it contains at a mass ratio. The water-dispersible cellulose according to claim 1 containing 10% by mass or more of a component that is stably suspended in water, and 50 to 95% by mass of a water-soluble polymer and / or a hydrophilic substance. A water-dispersible dry composition characterized by the above and a composition containing at least one polysaccharide selected from the polysaccharides according to claim 1, wherein the water-dispersible dry composition: polysaccharide = 1: A stabilizer characterized by containing in a mass ratio of 9 to 9: 1. A water-dispersible dry composition comprising 50 to 95% by mass of the water-dispersible cellulose according to claim 1, 1 to 49% by mass of a water-soluble polymer, and 1 to 49% by mass of a hydrophilic substance, galactomannan and xanthan gum The stabilizer according to claim 2, characterized in that it comprises a polysaccharide selected from, tamarind seed gum and pectin. The liquid composition mix | blended by adding the stabilizer in any one of Claims 1-3. The liquid food composition which is mix | blended by adding the stabilizer in any one of Claims 1-3 which is pH 3-8 or salt concentration 0.001-20%.