JPH10251446A - Water-dispersible composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-dispersible composite which is excellent in easiness of dispersion and dispersion stability and is useful as a food additive, etc., by compounding water-insoluble or water-swellable carboxymethylcellulose or its alkali salt having specified content of carboxymethyl ether bond and crystallinity with a water-soluble gum and/or a hydrophilic substance. SOLUTION: This compsn. comprises 50-99 pts. water-insoluble or water- swellable carboxymethylcellulose or its alkali metal salt having a degree of carboxymethyl ether group substitution per anhydrous glucose unit of 0.01 or higher but lower than 0.4 and a crystallinity of cellulose I type of 60% or higher but lower than 88% with 1-50 pts. water-soluble gum and/or hydrophilic substance. When carboxymethylcellulose or its alkali metal salt having the above properties has an average particle size of 40μm or smaller the dispersion stability in water is improved and a sense of incongruent feeling when such a compsn. is added to a food can be decreased.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-insoluble or water-swellable carboxymethylcellulose or a water-dispersible complex comprising a combination of an alkali metal salt thereof and a saccharide, and is used for food, medicine, cosmetics, and plastics. It is used in various fields such as industrial materials such as agents, dyeing, paints, civil engineering, and construction. For example, paste, food additives,
Excipients, compounding materials for rubber and plastics, additives for paints, abrasives, water retention agents, shape retention agents, dispersion stabilizers, emulsion stabilizers, ice crystal inhibitors, heat stabilizers, foam stabilizers, viscosity modifiers It can be used in the fields of muddy water conditioner, sludge preventer, etc.

[0002]

2. Description of the Related Art Conventionally, as a water-dispersible composite mainly composed of cellulose, for example, Japanese Patent Publication No. 40-1217
No. 4 discloses that an interfering agent is added to a cellulose crystallite aggregate to obtain an aqueous colloidal dispersion. In addition, Japanese Patent Publication 56-3
No. 1094 and Japanese Patent Publication No. 57-14771 describe an aqueous composite in which a dispersant and a disintegrant are combined with microcrystalline cellulose. It is disclosed that a complex is obtained by mixing and grinding cellulose, a water-soluble polymer, a saccharide and the like in the presence of water, followed by drying and grinding. In addition, Japanese Patent Application Laid-Open
No. 268129 describes a complex comprising fine cellulose and water-soluble gums and / or a hydrophilic substance, and having a colloid fraction of 65% or more when redispersed in water.

On the other hand, as a patent relating to a cellulose derivative having a carboxymethylated surface, a cellulose raw material such as pulp, linter, or cotton is subjected to acid hydrolysis to wash and remove non-crystalline regions, followed by grinding, purification, and the like. Japanese Patent Publication No. 45-19438 discloses a sizing agent for fibers made from microcrystalline cellulose which is a finely powdered cellulose obtained by drying.
No. 2881.

The sizing agent disclosed in Japanese Patent Publication No. 45-19438 is capable of forming a high-concentration and low-viscosity dispersion in an aqueous alkaline solution, and capable of uniformly sizing the inside of a fiber bundle and quickly desizing with an alkaline solution. It is characterized by being able to.

In Japanese Patent Publication No. 3-2881, in the carboxymethyl etherification of microcrystalline cellulose, the weight ratio of water / aliphatic alcohol and the molar ratio of water / glucose are limited, and solid sodium hydroxide is further added. A method is disclosed for selectively carboxymethyl etherifying a cellulose surface by use. Further, the detailed description clearly shows that the cellulose derivative produced by the method imparts dispersion / suspension stability and a smooth texture as a food additive.

In the above two prior applications, the starting material uses microcrystalline cellulose obtained by removing an amorphous region by acid hydrolysis, and the derivative obtained by carboxymethyl etherifying the surface is the same. Is determined.

Further, a method for producing an alkali metal salt of carboxymethyl cellulose ether which is insoluble in water (JP-A-60-1985)
No. 177001) has also been filed.

Further, carboxymethylcellulose (CM
A number of patents relating to the complex containing C) have been filed, but since they are used as water-soluble polymers, it can be determined that the degree of carboxymethylation is 0.4 or more.

[0009]

The composite containing cellulose as a main component described in JP-A-7-268129 forms a stable, colloid-free dispersion having a smooth structure in which cellulose is uniformly dispersed. Therefore, when redispersed, the ratio of particles of 10 μm or more is 40% or less,
When the ratio of the particles having a length of 10 μm or more is more than 5%, the aspect ratio of the particles having a length of 10 μm or more must be 3.0 or less, and the colloid fraction must be 65% or more. Therefore, only a very limited amount of cellulose is used.

[0010] Further, fine cellulose forms strong hydrogen bonds between cellulose surfaces as it dries, and forms strong aggregates which are not redispersed in water. It forms a dense and very strong irreversible aggregate because it is easy and has a large specific surface area.

[0011] Therefore, when producing a dried composite containing fine cellulose as a main component as described above, the amounts of water-soluble gums and hydrophilic substances added to prevent hydrogen bonding during drying are large. When this complex was dispersed in water, the viscosity of the water-soluble gums was remarkable, and application to a low-viscosity liquid product was difficult.

[0012]

Means for Solving the Problems and Action As a means for solving the above-mentioned problems, a study was conducted on a complex containing water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof as a main component. As a result, a new effect has been found, and the present application has been made.

That is, the degree of carboxymethyl ether group substitution per anhydroglucose unit is 0.01 to 0.4.
Water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof and a water-soluble gum and / or a hydrophilic substance having a degree of crystallinity of cellulose I of less than 60% and less than 88%. It is a water-dispersible complex characterized by containing.

The composite of the present invention comprises a water-insoluble or water-swellable carboxymethylcellulose, which is a cellulose derivative having a lightly carboxymethyletherified moiety, or an alkali metal salt thereof, as a main component. Compared to cellulose used as a body,
It has a high affinity for water and shows a form in which the etherified portion is dissolved or swelled in water. That is, particles having an effect as if carboxymethylcellulose or an alkali metal salt thereof were immobilized on the cellulose particles can be obtained. Therefore, when the composite is redispersed in water, it is not affected by the particle size, particle size distribution, aspect ratio, and colloid fraction of cellulose as the main component of the composite as described in JP-A-7-268129. However, smoothness and roughness were remarkably improved.

[0015] Further, when producing a complex containing fine water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof as a main component, a part of the hydroxyl groups present on the cellulose surface is replaced by carboxymethyl groups. Therefore, the hydrogen bond generated during drying is suppressed. Therefore, compared with the composite containing fine cellulose as a main component, the minimum amount of addition and blending of the water-soluble gums and / or hydrophilic substances as other components of the composite is reduced. As a result, the degree of freedom in blending and designing various materials using the composite of the present invention is expanded. That is, the composite of the present invention improves physical properties such as water retention and shape retention, and the viscosity can be separately controlled by another thickening component.

In particular, by making the average particle size 40 μm or less, not only the dispersion stability in water is improved, but also
The feeling of foreign substances when added to food can be reduced.

Further, a sizing agent, a food additive, an excipient, a compounding material for rubber and plastics, a coating additive, an abrasive, a water retention agent, a water retention agent characterized by containing the complex of the present invention as a constituent component. Excipients, dispersion stabilizers, emulsion stabilizers, ice crystal inhibitors,
Heat stabilizers, foam stabilizers, viscosity modifiers, muddy water regulators, and sludge preventers are industrially useful.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The cellulose and lignocellulose used as the starting material in the present invention include those exemplified below. Examples of cellulose include wood pulp, purified linter, natural cellulose such as cellulose produced by microorganisms such as acetic acid bacteria, and regenerated cellulose obtained by dissolving cellulose in a solvent such as a copper ammonia solution or a morpholine derivative and spinning again. . Lignocellulose is a complex composed of three components of cellulose, hemicellulose and lignin, and examples thereof include wood flour, coconut husk powder, and walnut husk powder.

Further, depending on the application, fine cellulose obtained by depolymerizing various kinds of waste paper, waste paper deinked pulp and the above-mentioned cellulose-based material by acid hydrolysis, alkali hydrolysis, enzymatic decomposition, explosion treatment, etc., or mechanically treated. Fine cellulose or the like is used. These raw materials are appropriately selected depending on the intended use of the composite containing water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof as a main component. In producing water-insoluble or water-swellable carboxymethyl cellulose or its alkali metal salt, which is the main component of the composite,
A carboxymethyl group having a total of 0.01 or more and less than 0.4, preferably 0.03 or more and 0.37 or less per anhydroglucose unit applied by a known carboxymethylcellulose production method, and cellulose I Has a crystallinity of 60% or more and less than 88%, particularly preferably 6% or less.
It must be between 5% and 80%.

In the present invention, when the amount of carboxymethyl ether bond is less than 0.01 per anhydroglucose unit, a swelling phase of carboxymethylcellulose is not sufficiently formed on the particle surface, and the characteristics of the present invention such as water dispersion stability, texture and the like. Is not sufficiently expressed. On the other hand, when the ratio is 0.4 or more, the portion dissolved in water increases, and it is difficult to maintain the shape as particles. For this reason, the water insolubility and water swelling characteristic of the present invention cannot be exhibited.

Further, those having a degree of crystallinity of less than 60% make it difficult to maintain the form of fibers or particles,
The features of the present invention do not appear. On the other hand, if the degree of crystallization is 88% or more, sufficient hydrophilicity and water swelling property cannot be obtained because the degree of carboxymethylation is low.

In particular, the use of water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof having an average particle size of 40 μm or less can improve the texture in food additives and paint additives, and improve the smoothness of the coating film. Important in terms of retention. In addition, the smaller the average particle size, the higher the water dispersion stability in water.

The water-soluble gums, which are other components of the composite, are water-soluble gums having high water swellability and good compatibility with cellulose in water, and include locust bean gum, guar gum, tamarind gum, and quince gum. Seed gum, karaya gum, gum arabic, tragacanth gum, gum ghatti, arabinogalactan, agar, carrageenan, alginic acid and its salts, furceleran, pectin, quince, xanthan gum, curdlan, pullulan, dextran, gellan gum, gelatin, sodium cellulose glycolate And the like. These can be used alone or in combination of two or more. Among them, sodium cellulose glycolate has both a swelling property and a hydrophilic property, so that it can be used as a gum alone. However, it is necessary to add a large amount of other water-soluble gums when used alone, and when used in a large amount, the viscosity of the entire system is significantly increased. It is preferably used in combination with a toxic substance.

Hydrophilic substances are substances having high solubility in cold water and having almost no viscosity, and include starch hydrolysates, dextrins, glucose, fructose, xylose, sucrose, lactose, maltose, isomerized sugar, Coupling sugar, palatinose, neosugar, mannitol, reduced starch saccharified candy, maltose, lactulose, polydextrose, fructooligosaccharides, monosaccharides such as galactooligosaccharides, water-soluble saccharides including oligosaccharides, xylitol, maltitol, mannitol, sorbitol And sugar alcohols such as Soroboth. These can be used alone or in combination of two or more.

The water-soluble gums allow water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof to be rapidly dispersed in water, and water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof. It further enhances dispersion stability and functions as a protective colloid.

The hydrophilic substance promotes dispersion of water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof in water, and the effect is further enhanced by combining with a water-soluble gum.

In order to make the dispersibility or dispersion stability of the water-dispersible composite remarkable, it is necessary that the water-soluble gum and / or the hydrophilic substance in the composite composition be 1 to 50 parts. .

When the water-soluble gum or the hydrophilic substance is used alone, if it is less than 1 part, the dispersibility of the dry powder of water-insoluble or water-swellable carboxymethylcellulose or its alkali metal salt in water is reduced. However, when it exceeds 50 parts, the viscosity increases due to the water-soluble gums.
This is not preferable because it reduces the texture. Further, if the amount of the water-soluble gum or hydrophilic substance is excessive, the amount of the water-insoluble component of the obtained water-dispersible composite is decreased, which is not preferable.

When a water-soluble gum and a hydrophilic substance are used in combination, the properties of the water-insoluble or water-swellable carboxymethylcellulose or the alkali metal salt thereof, and the properties of the water-soluble gum and the hydrophilic substance are used. The mixing ratio can be appropriately selected depending on the kind, and the total of the water-soluble gum and the hydrophilic substance needs to be 1 to 50 parts.

That is, the affinity of water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof for water and the stickiness, granulating properties, coating properties of water-soluble gums, and dispersibility and disintegration properties of hydrophilic substances. The physical properties, particularly the dispersibility and the viscosity, of the resulting composite vary greatly depending on the balance of the above, but the balance can be adjusted by controlling the amounts and proportions of the water-soluble gums and the hydrophilic substance. Therefore, since the properties differ depending on the type of the water-soluble gum and the hydrophilic substance to be used, the numerical values of the water-soluble gum and the hydrophilic substance cannot be individually limited. When the amount is less than 1 part in total, the effect of promoting the dispersion of the obtained composite in water is not recognized, and when it exceeds 50 parts, the water-insoluble component of the obtained water-dispersible composite is reduced. Undesirably leads to

As a method for forming a complex, water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof is mixed with a water-soluble gum and / or a hydrophilic substance to form a slurry, which is then dried and dried. Some methods are followed by grinding.

In the case of mixing with water-soluble gums and / or hydrophilic substances, care must be taken in particular that the water-soluble gums are sufficiently dissolved and uniformly mixed. For this purpose, it is necessary to sufficiently stir and mix in the presence of at least 75% of the total weight of water when mixing the water-soluble components. At this time, it is also possible to disperse the water-soluble component in a small amount of water in advance and then add and mix.

Heat treatment is an effective method for accelerating dissolution. Further, a heat treatment may be performed to further promote the composite. In particular, when using xanthan gum or carrageenan, it is necessary to once heat-treat a slurry mixed with water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof before drying at 60 ° C or more.

In the case of drying, known drying methods such as a vacuum freeze dryer, a spray dryer, a flash dryer, a fluid phase dryer, a tray dryer and the like can be used. In the case of pulverization, a known pulverizer such as an impact mill such as a sample mill, a hammer mill, a pin mill, and a knife mill, and a jet mill can be used. After the pulverizing step, a classification step may be provided.

[0035]

The embodiments of the present invention will be described below with reference to examples, but the present invention is not limited by these examples. In addition, all "parts" indicating the blending amount indicate "parts by weight".

Example 1 After shredding a commercial DP pulp,
The acid-insoluble residue obtained by hydrolyzing in N-hydrochloric acid at 95 ° C. for 120 minutes was filtered, washed, dehydrated, dried, and pulverized with a sample mill to obtain fine cellulose. 100 parts of the fine cellulose is put into a mixture of 435 parts of isopropanol (IPA), 65 parts of water and 9.9 parts of NaOH,
Stirred for hours. To this slurry system was added 23.0 parts of a 50% monochloroacetic acid IPA solution, and the mixture was heated to 70 ° C. and reacted for 1.5 hours. The resulting reaction product was washed with 80% methanol, and then replaced with methanol and dried to obtain water-insoluble sodium carboxymethylcellulose having a crystallinity of cellulose I of 74.2% and a DS of 0.18. The average particle size of this sodium carboxymethyl cellulose is 2
4.6 μm, the aspect ratio was 4.1. Next, a water-insoluble sodium carboxymethylcellulose having a crystallinity of cellulose I of 74.2% and a DS of 0.18 was used.
A dispersion having a total solid content of 5.0% was prepared by mixing xanthan gum and glucose with a solid content ratio of 90/2/8, respectively. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

[Example 2] The water-insoluble sodium carboxymethylcellulose of Example 1 (crystallinity of cellulose type I = 74.2%, DS 0.18), xanthan gum and maltodextrin were mixed at a solid content ratio. 80
A dispersion having a total solid content of 5.0% was prepared. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

[Example 3] The water-insoluble sodium carboxymethylcellulose of Example 1 (crystallinity of cellulose type I = 74.2%, DS 0.18), xanthan gum and starch hydrolyzate were mixed at solid contents. 80/3 in ratio
A dispersion having a total solid content of 6.0% was prepared. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Example 4 The water-insoluble sodium carboxymethylcellulose of Example 1 (crystallinity of cellulose type I = 74.2%, DS 0.18), λ-carrageenan,
The sorbitol was formulated at a solids ratio of 82/9 /
A dispersion having a total solid content of 8.0%, which was designated as 9, was prepared.
This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Example 5 Water-insoluble carboxymethylcellulose (DS 0.18) obtained by converting the water-insoluble sodium carboxymethylcellulose of Example 1 (cellulose type I crystallinity = 74.2%, DS 0.18) into an acid form, Commercially available sodium cellulose glycolate (crystallinity of cellulose type I =
A dispersion having a total solid content of 5.0% was prepared by mixing 32.5% and DS 0.63) with a solid content ratio of 93/7, respectively. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Example 6 After shredding a commercial DP pulp, 1
The acid-insoluble residue obtained by hydrolysis in N-hydrochloric acid at 95 ° C for 120 minutes was filtered, washed and dehydrated to obtain undried fine cellulose. 250 parts of the undried fine cellulose was placed in a mixture of 600 parts of isopropanol (IPA), 50 parts of water and 9.9 parts of NaOH, and stirred at 30 ° C. for 1 hour. To this slurry system was added 23.0 parts of a 50% monochloroacetic acid IPA solution, and the mixture was heated to 70 ° C. and reacted for 2.5 hours. The obtained reaction product was washed with 80% methanol, then replaced with methanol and dried, and the crystallinity of cellulose type I was 78.
1%, water-insoluble sodium carboxymethylcellulose with a DS of 0.08 was obtained. Next, the composition of cellulose I-type crystallinity = 78.1%, DS 0.08, water-insoluble sodium carboxymethylcellulose, xanthan gum, and glucose were respectively 80/3/17 in solid content ratio.
A dispersion having a total solid content of 5.0% was prepared. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Example 7 After cutting a commercial linter, 1N
-An acid-insoluble residue obtained by hydrolysis in hydrochloric acid at 95 ° C for 120 minutes was filtered, washed, dehydrated, dried, and pulverized with a sample mill to obtain fine cellulose. 100 parts of the fine cellulose is put in a mixture of 435 parts of isopropanol (IPA), 65 parts of water and 20.0 parts of NaOH,
Stirred for hours. 50% monochloroacetic acid
41.5 parts of an IPA solution was added, the temperature was raised to 70 ° C., and the reaction was performed for 2.0 hours. The obtained reaction product was washed with 80% methanol, then replaced with methanol and dried, and cellulose I was dried.
A water-insoluble sodium carboxymethylcellulose having a crystallinity of the mold = 67.3% and a DS of 0.31 was obtained. next,
Crystallinity of cellulose type I = 67.3%, DS 0.31
Of water-insoluble sodium carboxymethylcellulose, xanthan gum, guar gum, and starch hydrolyzate were adjusted to a solid content ratio of 88/2/1/9 to prepare a dispersion having a total solid content of 5.0%. . This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Example 8 After shredding a commercial DP pulp,
The acid-insoluble residue obtained by hydrolysis in N-hydrochloric acid at 95 ° C for 120 minutes was filtered, washed and dehydrated to obtain undried fine cellulose. 250 parts of the undried fine cellulose were mixed with 600 parts of isopropanol (IPA), 50 parts of water and 20.0 parts of NaOH.
The mixture was stirred at 30 ° C. for 1 hour. To this slurry system, 41.0 parts of a 50% monochloroacetic acid IPA solution was added, and the mixture was heated to 70 ° C. and reacted for 2.5 hours. The obtained reaction product was washed with 80% methanol, and then replaced with methanol and dried.
A water-insoluble sodium carboxymethyl cellulose with 4.9%, DS 0.17 was obtained. Next, the crystallinity of cellulose type I = 74.9%, water-insoluble sodium carboxymethylcellulose having a DS of 0.17, the fine cellulose of Example 1, xanthan gum, and maltodextrin were mixed at a solid content ratio. A dispersion having a total solid content of 5.0%, which was 70/10/3/17, was prepared. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Example 9 The water-insoluble sodium carboxymethylcellulose of Example 7 (crystallinity of cellulose type I = 67.3%, DS 0.31) and sorbite were mixed at a solid content ratio of 75/25, respectively. A dispersion having a total solid content of 5.0% was prepared. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Comparative Example 1 The fine cellulose of Example 1 (crystallinity of cellulose type I = 89.1%) was used as it was.

Comparative Example 2 Fine cellulose (crystallinity of cellulose I type = 89.1%) of Example 1 and commercially available sodium cellulose glycolate (crystallinity of cellulose I type = 32.5%) , DS0.63) with a total solid content of 5.0%, each having a solid content ratio of 90/10.
Was prepared. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Comparative Example 3 The composition of the fine cellulose of Example 6 (crystallinity of cellulose type I = 88.7%), xanthan gum and glucose was 7 in terms of solid content ratio.
A dispersion having a total solid content of 5.0%, which was 5/5/20, was prepared. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite.

Comparative Example 4 100 parts of the fine cellulose of Example 1 (crystallinity of cellulose type I = 89.1%), 522 parts of isopropanol (IPA), 78 parts of water, and NaOH 6
The mixture was added to 8.4 parts of the mixture and stirred at 30 ° C. for 1.0 hour. To this slurry system was added 35.0 parts of a 50% monochloroacetic acid IPA solution, and the mixture was heated to 70 ° C. and reacted for 1.5 hours. The obtained reaction product was washed with 80% methanol, and then replaced with methanol and dried to obtain sodium carboxymethylcellulose having a cellulose type I crystallinity of 31.2% and a DS of 0.31. Next, the total solid content of the sodium carboxymethylcellulose having a crystallinity of cellulose type I = 31.2% and DS 0.31, a xanthan gum and a starch hydrolyzate each having a solid content ratio of 88/2/10 was determined. A dispersion having a partial concentration of 5.0% was prepared. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite. However, since this complex was completely dissolved in water, the water dispersibility and texture test of the test items could not be measured.

[Comparative Example 5] After shredding a commercial DP pulp,
The acid-insoluble residue obtained by hydrolysis in N-hydrochloric acid at 95 ° C. for 120 minutes was filtered and washed, and a cellulose dispersion having a solid content of 10% was prepared. The cellulose dispersion was supplied with a medium stirring wet grinding apparatus (Apex Mill, AM-1 type, Kotobuki Giken Kogyo Co., Ltd.) using zirconia beads having a diameter of 1 mm as a medium, the rotation speed of the stirring blade was 1800 rpm, and the cellulose dispersion was supplied. 1 under the condition of 0.4 liter / min
Pulverization treatment was performed by passing twice to obtain paste-like cellulose. The colloidal fraction of this cellulose was 74%, the particle size was 4.6 μm, and the crystallinity of cellulose type I was 88.3%. A dispersion having a total solid content of 5.0% was prepared by mixing the cellulose, xanthan gum, and glucose at a solid content ratio of 75/5/20, respectively. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite. When this complex is dispersed in water, the colloid fraction is 96%, and the particle size is 4.8 μm.
m, the ratio of particles having a size of 10 μm or more was 3.1%.

[Comparative Example 6] Cellulose (cellulose I) obtained by filtering and washing an acid-insoluble residue obtained by hydrolyzing the commercial DP pulp described in Comparative Example 5 with an acid.
(A crystallinity of the mold = 88.3%), and a dispersion liquid having a total solid content of 5.0%, in which the composition ratio of xanthan gum and glucose was 90/2/8 in terms of the solid content ratio, respectively. This was heated at 80 ° C. for 60 minutes with stirring, and then dried by spray drying to obtain a dry powder of the water-dispersible composite. When this complex is dispersed in water, the colloid fraction is 78% and the particle size is 20.
The ratio of particles having a particle size of 1 μm, 10 μm or more was 78.4%.

[Test Method] 1) DS Measurement (Methanol Nitrate Method) About 2.0 g of a sample was precisely weighed and placed in a 300 ml Erlenmeyer Erlenmeyer flask. 100 ml of methanol nitrate (a solution obtained by adding 100 ml of special grade concentrated nitric acid to 1 liter of anhydrous methanol) is added, and shaken for 3 hours to give sodium carboxymethylcellulose (N
a-CMC) was converted to carboxymethylcellulose (H-CMC). 1.5-2.0 g of the absolutely dried H-CMC was precisely weighed,
Placed in a 00 ml Erlenmeyer Erlenmeyer flask. H-CMC was wet with 15 ml of 80% methanol, 100 ml of 0.1N-NaOH was added, and the mixture was shaken at room temperature for 3 hours. Phenol as an indicator
Excess NaOH was back titrated with 0.1N H ₂ SO ₄ using phthalein. DS was calculated by the following equation.

[0052]

(Equation 1)

2) Measurement of Crystallinity The crystallinity of cellulose type I was determined by measuring the X-ray diffraction of the sample. For the measurement of X-ray diffraction, an appropriate amount of a sample was placed on a glass cell, and an X-ray diffraction measuring device (RAD-2C system, manufactured by Rigaku Denki Co., Ltd.) was used. The calculation of the crystallinity of cellulose type I was performed by the method of Segal et al. (L. Segal, JJ Greenly e.
tal, Text. Res. J., 29, 786, 1959), and the 2θ of the diffractogram obtained from the X-ray diffraction measurement performed using the method of Kamide et al. (K. Kamide et al, Polymer J., 17, 909, 1985). = 4 ° ~
Using the diffraction intensity at 32 ° as a baseline, the diffraction intensity was calculated from the diffraction intensity of the 002 plane and the diffraction intensity of the amorphous portion at 2θ = 18.5 ° by the following equation. χc = (I002c−Ia) / I002c × 100 χc: Crystallinity (%) of cellulose type I I002c: 2θ = 22.6 °, diffraction intensity of 002 plane Ia: 2θ = 18.5 °, diffraction intensity of amorphous portion

3) Average particle size Laser diffraction scattering particle size distribution analyzer (Microtrack Model-
9220-SRA, manufactured by Nikkiso Co., Ltd.), and the value of D50 was taken as the average particle size.

4) Water dispersibility test The turbidity of the 0.15% aqueous dispersion was measured every minute for 120 minutes. The turbidity of the same sample was measured three times in the same manner, and the average value was defined as the turbidity at that time. Thereafter, the water dispersibility at the elapse of 120 minutes was evaluated as follows by a relative value with the turbidity immediately after the start of the measurement as 100. −-relative value 90 or more, −-relative value 70 or more, Δ-relative value 50 or more, × -relative value 30 or more, XX-relative value less than 30

5) Texture test For 20 skilled panelists, a 5% by weight aqueous dispersion of the composite was prepared by dispersing each dried composite in water, and each was tasted in an independent panel. The test method was used. The contents were 1) whether or not they felt smooth, and 2) whether or not they felt rough. The smoothness was evaluated by the feeling of melting at the moment of putting into the mouth, and the roughness was evaluated by the feeling of foreign substances remaining on the tongue as the rear mouth.

[0057]

[Table 1]

[0058]

The water-dispersible composite of the present invention is a dry product which is convenient for transportation and storage, and gives a smooth and non-textured dispersion when dispersed in water.

Further, the water-dispersible composite of the present invention can be used for food,
Suspension stabilizers, emulsion stabilizers, thickening stabilizers, abrasives in pharmaceuticals, cosmetics, paints, ceramics, resins, industrial products, etc.
It is effective in fields requiring uniform dispersibility and long-term stability such as cloudy agents. For example, to give examples in the food field, cocoa drinks, juice drinks, matcha drinks, taste drinks such as powdered milk drink, milk cocoa, milk coffee, lactic acid drinks, milk drinks such as soy milk,
Ice cream, soft ice cream, ice confectionery such as sorbet, pudding, jelly, jam, gel foods such as mizuyokan, milkshake, coffee, whitener, hop cream, mayonnaise, dressings, sauce, soup, kneading, flower Pastes, canned cans, spreads, tube liquid foods, filling and toppings for bread and cakes, bean paste, honzant, fishery products, bread and cakes, Japanese sweets, noodles, pasta, frozen dough, powdered fats and oils,
In powder flavors, powder soups, powder spices, cream powders, etc., suspension stabilizers, emulsion stabilizers, thickening stabilizers,
It can be used as foam stabilizer, cloudy agent, composition imparting agent, fluidity improver, shape-retaining agent, anti-separation agent, dough modifier, powdered base material, and also replaces dietary fiber base material and fats and oils in the above general foods There is a usage such as a low-calorie base material.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hiroaki Namba 2-8-1, Iida-cho, Iwakuni-shi, Yamaguchi Japan Japan Paper Manufacturing Co., Ltd.

Claims (4)

[Claims] 1. The degree of carboxymethyl ether group substitution per anhydroglucose unit is from 0.01 to less than 0.4, and the crystallinity of cellulose type I is from 60% to 88%.
Water-insoluble or water-swellable carboxymethylcellulose or an alkali metal salt thereof in an amount of from 50 to 99 parts and a water-soluble gum and / or from 1 to 50 parts of a hydrophilic substance as components. Complex. 2. The degree of substitution of carboxymethyl ether groups per anhydroglucose unit is 0.01 or more and less than 0.4, and the crystallinity of cellulose type I is 60% or more and 88% or more.
Water-insoluble or water-swellable carboxymethyl cellulose or an alkali metal salt thereof having an average particle size of less than 40
The water-dispersible composite according to claim 1, which has a size of not more than μm. 3. The water-dispersible complex according to claim 1, wherein the water-soluble gum is one or more selected from sodium cellulose glycolate, guar gum, karaya gum, carrageenan, xanthan gum, and pectin. . 4. The water-dispersible complex according to claim 1, wherein the hydrophilic substance is a starch hydrolyzate, a water-soluble saccharide, or a sugar alcohol.