JP7028494B1 - Xanthan gum and foods using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide xanthan gum capable of imparting high viscosity even when added to water and saline in a powder state, and a food product using the same. SOLUTION: The xanthan gum according to the present invention is a xanthan gum having an average particle size of 25 to 150 μm obtained by heat-treating a powdery or granular raw material xanthan gum and having a concentration of 0.4% by mass. The viscosity (μ (w) and μ (s)) at 20 ° C. after 60 minutes is calculated by adding to ion-exchanged water at 20 ° C. or 3.0% by mass sodium chloride aqueous solution to disperse the mixture, and the following formula (1). ) And the formula (2). μ (s) / μ (w) ≧ 0.25 (1) μ (w) ≧ 400 mPa · s (2) (Here, μ (w) is the viscosity in the case of ion-exchanged water, and μ (s). ) Is the viscosity in the case of 3.0% by mass sodium chloride aqueous solution.) [Selection diagram] None.

Description

Patent Law Article 30 Paragraph 2 Applicable Reiwa Announced in the sales promotion pamphlet "Inagel Ultra Xanthan TOP" on September 9, 2

The present invention relates to xanthan gum and foods using the same.

Xanthan gum is a thickening polysaccharide having excellent acid resistance, salt resistance, heat resistance, and enzyme resistance. Therefore, it is used as a thickener for various foods such as low pH foods such as dressings, retort foods, salted fish, and tsukudani. When producing foods containing salt, xanthan gum may be added to saline solution at room temperature. It is known that the xanthan gum powder has a remarkably slow dissolution rate when it is directly added to a saline solution to dissolve it.

Conventionally, high-viscosity xanthan gum and salt-soluble xanthan gum that can be dissolved in water to impart high viscosity have been proposed (see, for example, Patent Documents 1 to 6). However, the conventional high-viscosity xanthan gum has extremely low viscosity when it is tried to be dissolved in a saline solution at room temperature in a powder state. There is no problem when the xanthan gum is dissolved in water in advance and then the salt is dissolved, but the case where the powder is directly dissolved in the salt water becomes a problem. When dissolving xanthan gum in saline solution, it is necessary to go through a step of dissolving it by stirring for a long time after adding it, or a step of heating and dissolving it.

Such a step cannot be used for manufacturing a product that cannot be diluted with water, or a product that does not undergo a heating step or an emulsification step (using an emulsifier). For example, salted fish, separate type dressing, etc. In manufacturing at a factory, leaving it for a long time after putting it in is not preferable from the viewpoint of workability and microbial contamination. The use of an emulsifier has problems such as limited products and an increase in processes.
On the other hand, there is also a salt solution easily soluble xanthan gum produced by homogenizing an aqueous solution of xanthan gum. This xanthan gum has a problem that the viscosity is lower than that of normal xanthan gum due to the homogenizer treatment and the dispersion stability is inferior.

Patent Document 1 describes a highly viscous xanthan gum that has been heat-treated in a powder state. It is stated that the viscosity of the aqueous solution is increased, but there is no description about the solubility in saline solution. Although the improvement in liquidity is disclosed, it does not mention foods containing salt or indications other than foods. Usually, the highly viscous xanthan gum produced through heat treatment has poor solubility in a saline solution, and the viscosity decreases when salt is added to the highly viscous xanthan gum solution. Furthermore, the particle size of xanthan gum has not been investigated.

Patent Document 2 describes a highly viscous xanthan gum that has been heat-treated in a powder state. Similar to Patent Document 1, it is a highly viscous xanthan gum that does not easily become a stepchild, but there is no description regarding its solubility in saline solution. Furthermore, the particle size of xanthan gum has not been investigated.

Patent Document 3 describes modified xanthan gum obtained by heat-treating xanthan gum having an acetyl group content of 1% or less. It describes the increase in reactivity with galactomannan and glucomannan, viscosity increase, emulsification / dispersion stability, water retention, and improvement of texture, but does not describe dissolution in saline solution. Furthermore, the particle size of xanthan gum has not been investigated.

Patent Document 4 describes that it has been found that the highly viscous xanthan gum that has been heat-treated with moisture has salt resistance. In the examples, the salt tolerance of xanthan gum is evaluated by the viscosity when the sodium chloride solution is added to the dispersion solution of xanthan gum. That is, it was evaluated by adding a saline solution to the dissolved xanthan gum, not by directly adding the xanthan gum powder to the saline solution. Furthermore, the particle size of xanthan gum has not been investigated.

Patent Document 5 describes foods containing heat-treated high-viscosity xanthan gum. According to the examples, in order to dissolve the highly viscous xanthan gum in a product containing salt, a heat treatment or a homogenizer treatment is performed. Highly viscous xanthan gum that requires such treatment cannot be applied to foods containing heat-denaturing substances.

For example, in Example 1, xanthan gum is forcibly dissolved by heat treatment at 180 ° C. In Example 2, a homomixer (emulsifier) is used to forcibly dissolve the xanthan gum molecule. In Example 3, heat treatment at 80 ° C. for 10 minutes, in Example 4, heating and homogenization, and in Example 5, heat treatment at 120 ° C. for 25 minutes. Example 6 is thawed with hot water, and Examples 7 to 9 are heat-treated. Further, in the viscosity test at the salt concentration shown in Reference Example 2, an aqueous solution of xanthan gum dissolved in advance at a concentration of 1% is used. It is not disclosed that powdered xanthan gum is directly dissolved in a salt-containing product at room temperature.

Patent Document 6 describes a high-salt food using modified xanthan gum and a method for producing the same. In Patent Document 6, in order to enhance the solubility of xanthan gum in a saline solution, an aqueous solution of xanthan gum is physically treated (pressure homogenizer). The molecule of xanthan gum is denatured by the physical treatment, and the viscosity value in the aqueous solution (salt 0%) becomes lower than that of the conventional product.

Patent Document 7 describes a solution-affinity polysaccharide having an improved affinity for a 5 wt% aqueous saline solution. This solution-affinitive polysaccharide has a viscosity after 10 minutes when it is dissolved in a 5% by weight aqueous solution of salt at 20 ° C. by 1.0% by weight, and 10 when it is dissolved in water at 20 ° C. by 1.0% by weight. It is a solution-affinitive polysaccharide (xanthan gum) characterized by having a viscosity of 50% or more after minutes. Further, a highly viscous xanthan gum obtained by heat-treating this xanthan gum is described.

Japanese Unexamined Patent Publication No. 10-33125 Japanese Unexamined Patent Publication No. 11-116603 Japanese Unexamined Patent Publication No. 2006-21867 Japanese Patent No. 4201391 Japanese Unexamined Patent Publication No. 11-308971 Japanese Unexamined Patent Publication No. 58-47449 Japanese Unexamined Patent Publication No. 2012-139161

Therefore, an object of the present invention is to provide xanthan gum that can impart high viscosity even when added to water and saline in a powder state, and a food product using the same.

As a result of diligent studies to solve the above problems, the present inventors have found that xanthan gum having predetermined conditions for viscosity when dissolved in ion-exchanged water at 20 ° C. or a 3.0% by mass sodium chloride aqueous solution. , Water and saline have been found to be able to impart high viscosity when added in a powder state, leading to the present invention.

That is, the xanthan gum according to the present invention is a xanthan gum having an average particle size of 25 to 150 μm obtained by heat-treating a powdery or granular raw material xanthan gum, and has a concentration of 0.4% by mass of 20. The viscosity (μ (w) and μ (s)) at 20 ° C. after 60 minutes by adding to ion-exchanged water at ° C. or 3.0% by mass sodium chloride aqueous solution is the following formula (1) and It is characterized by satisfying the formula (2).
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 400 mPa ・ s (2)
(Here, μ (w) is the viscosity in the case of ion-exchanged water, and μ (s) is the viscosity in the case of a 3.0% by mass sodium chloride aqueous solution.)

Further, the food product of the present invention is characterized by containing the above-mentioned xanthan gum.

According to the present invention, it is possible to provide xanthan gum that can impart high viscosity even when added to water and saline in a powder state, and a food product using the same.

It is a graph which shows the storage elastic modulus (G') of xanthan gum. It is a graph which shows the loss tangent (tan δ) of xanthan gum.

The xanthan gum of the present invention is a xanthan gum having an average particle size of 25 to 150 μm obtained by heat-treating a powdered or granular raw material xanthan gum, and has ions at a concentration of 0.4% by mass at 20 ° C. The viscosities (μ (w) and μ (s)) at 20 ° C. after 60 minutes after addition to exchanged water or 3.0% by mass sodium chloride aqueous solution are determined by the following formulas (1) and (2). ) Satisfies.
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 400 mPa ・ s (2)
(Here, μ (w) is the viscosity in the case of ion-exchanged water, and μ (s) is the viscosity in the case of a 3.0% by mass sodium chloride aqueous solution.)

The viscosities μ (w) and μ (s) are specifically obtained by the following methods. When the viscosity is μ (w), xanthan gum is added to ion-exchanged water at 20 ° C. with stirring so as to have a concentration of 0.4% by mass, and the mixture is stirred for 10 minutes. A laboratory agitator can be used for agitation. Stir at 300 rpm for 10 minutes and leave for 49 minutes. Then, the mixture is stirred for 1 minute under the same conditions, and the viscosity is measured to give μ (w). Further, the viscosity is measured by the same method except that the ion-exchanged water is changed to a 3.0% by mass sodium chloride aqueous solution, and the viscosity is determined to be μ (s).

The stirring in the present invention is intended to be a weak stirring as if it was stirred by hand. When a stirrer is used, stirring and mixing to the extent that the swollen particles are not destroyed, so-called low-speed stirring, corresponds to the stirring in the present invention. Since the salt-soluble xanthan gum does not develop viscosity by such stirring, a solubilizer such as a homogenizer or a high-speed stirrer has been used to dissolve the molecules.
The xanthan gum of the present invention develops viscosity even when it is stirred at a low speed, that is, at a level of stirring by hand using a spartel, muddler, whisk, etc., and when stirring by hand, in addition to the case of using a stirrer. It can have a remarkable effect.

The present inventors have found that the viscosity ratio (μ (s) / μ (w)) represented by the above formula (1) is an index of the saline solubility of xanthan gum. When this viscosity ratio is 0.25 or more, the solubility in saline solution is good. μ (s) / μ (w) is preferably 0.30 or more, and more preferably 0.35 or more.
Further, the viscosity μ (w) of 400 mPa · s or more means that the xanthan gum has good solubility in water. The viscosity μ (w) is preferably 600 mPa · s or more, and more preferably 800 mPa · s or more. The viscosity μ (s) is preferably 220 mPa · s or more, and more preferably 400 mPa · s or more.

The xanthan gum of the present invention can be produced by subjecting powdered or granular raw material xanthan gum to an appropriate heat treatment. Generally, a large amount of mucilage is produced by inoculating the microorganism xanthomonas campestris with glucose or starch as a carbon source and purely culturing at about 30 ° C. Then, when alcohol is added, a mucilage which is a polysaccharide is precipitated, and the separated polysaccharide is further purified, dried and pulverized to obtain xanthan gum. The xanthan gum that has been dried and pulverized in this way is the raw material xanthan gum in the present invention. This raw material xanthan gum is also included in the raw material xanthan gum in the present invention because there is no change in physical properties even if the raw material xanthan gum is further pulverized to adjust the particle size or granulated into granules.

The drying step before pulverization for obtaining this raw material xanthan gum is heating performed to evaporate alcohol and water, and the product temperature does not rise due to heating. Even if the product temperature rises, it is only for a very short time, and it is not heated to the extent that it affects the viscosity. The method for obtaining this raw material xanthan gum has been described in various literatures, is known, and is a method used as a usual method.

On the other hand, a raw material xanthan gum that has been dissolved or swollen in water and then re-dried by vacuum freeze-drying or vacuum drying as described in Patent Document 7 does not fall under the raw material xanthan gum in the present invention. When the xanthan gum molecules dissolved in water are dried by vacuum freeze-drying or vacuum drying, the xanthan gum molecules are dried in a spread state unlike the usual drying method. Therefore, the molecule has a longer distance between molecules than the raw material xanthan gum, and has a molecular structure different from that of the raw material xanthan gum.

Further, the xanthan gum dried by the vacuum freeze-drying method or the vacuum drying method has a lower viscosity when dissolved in water than the raw material xanthan gum, and the viscosity does not easily increase even after heat treatment. In general, the reason is that when a polysaccharide is processed by dissolving the powder and powdering it again, the polysaccharide molecule is reduced in molecular weight by a heating or freezing step and the viscosity is lowered. This is because the raw material xanthan gum is dissolved in water and then powdered again by vacuum freeze-drying or the like to reduce the molecular weight of the raw material xanthan gum, and the viscosity when dissolved in water is lower than that of the raw material xanthan gum.

The average particle size of commercially available powdered xanthan gum is usually about 160 to 200 μm, but it can be heat-treated after being pulverized to about 25 to 150 μm. Alternatively, the heat-treated product may be pulverized to 25 to 150 μm. The heat treatment can be performed by storing powdery or granular xanthan gum in a heat-resistant container made of stainless steel or the like and heating it in a blower dryer at a predetermined temperature (for example, 50 to 250 ° C.) for a predetermined time. When granular xanthan gum is used, it is preferable that the particle size of the single particles constituting the granules is 25 to 150 μm.

The heating temperature is selected in the range of 50 to 250 ° C. Heating above 250 ° C. is not performed because it causes adverse effects such as severe browning of the powder. Since the degree of heat treatment mainly depends on the heat temperature, the degree of heat treatment in the present invention is smaller than that of the highly viscous xanthan gum described in Patent Documents 1 to 5. The heating time is in the range of 1 minute to 7 days and is selected according to the heating temperature. However, the higher the heating temperature, the shorter the heating time needs to be. For example, when the heating temperature is 70 ° C. or lower, the heating time can be 24 hours or more. On the other hand, when heating at a relatively high temperature of about 150 ° C., the heating time is about 5 minutes or less.
The above-mentioned heating conditions are an example, and the conditions may differ depending on the raw material, the container, and the heating device used.

The particle size of the xanthan gum of the present invention after the heat treatment is preferably in the range of 25 to 150 μm. The particle size refers to the average particle size obtained by using a particle size distribution meter. The present inventors have found that by defining the particle size of xanthan gum to 25 to 150 μm, the solubility in a saline solution becomes higher while maintaining the viscosity of the aqueous solution. The particle size of xanthan gum is more preferably 35 to 120 μm, and most preferably 45 to 100 μm. This is because if the average particle size is too small, the secondary aggregation of single particles becomes intense, the apparent dissolution rate slows down, and the viscosity decreases due to the reduction in molecular weight. Also, if the average particle size is too large, the dissolution in the saline solution will be delayed.

The xanthan gum is preferably pulverized to adjust the particle size. The pulverization may be performed either before the heat treatment or after the heat treatment. Examples of the crusher include a hammer mill, a ball mill, a pin mill, an air flow type crusher, a refrigerating crusher, a roller mill, a stone mill type crusher, and the like, and any kind of crusher can be used. The average particle size of the pulverized product after pulverization is determined using a microscope, a particle size distribution measuring device, or the like.

It has been found by the present inventors that the particle size is related to the solubility of heat-treated high-viscosity xanthan gum in saline solution. Since the specific surface area of general particles increases as the particle size is reduced, the dissolution rate increases as long as there is no aggregation during dissolution. However, in the case of heat-treated high-viscosity xanthan gum, it dissolves in water and exhibits structural viscosity, resulting in a state close to that of gel. The structure is physically broken by pulverization to reduce the molecular weight, and the viscosity is lower than that before pulverization. The viscosity does not increase when the dissolution rate is increased by fine grinding. In the conventional high-viscosity xanthan gum whose purpose is to increase the viscosity, the idea of finely pulverizing cannot occur.

Since the xanthan gum of the present invention is excellent in saline solubility, heat resistance, acid resistance, and enzyme resistance, it can be used in conventional applications to improve its properties. It is suitable not only for foods that require heat treatment at 120 ° C. or higher, but also for foods that are manufactured without undergoing heating or emulsification steps. For example, the xanthan gum of the present invention is used for sauces, dressings, sauces, pickles, boiled foods, instant foods, retort pouch foods, beverages, desserts, flour products, nursing foods, etc. to thicken and improve dispersion stability. Effects such as taste improvement, glossing, and emulsification can be obtained.

Separation-type dressings containing solids in which fats and oils and seasonings are separated may contain 2% by mass or more of salt. When directly dissolved in such foods without heating or homogenizing, the effect of the xanthan gum of the present invention is particularly exhibited, and the effect of preventing the precipitation of solids and delaying the separation of oils is obtained. Be done. In addition, some long-term care foods contain a large amount of milk components, calcium, and minerals, and there is also a type in which water and milk are added to adjust the errand. Even in such a long-term care food, the xanthan gum of the present invention can be rapidly dissolved at the time of use adjustment to develop viscosity and impart an appropriate thickening.

The amount of xanthan gum added in the present invention can be appropriately selected depending on the food. For example, in the case of desserts, a sufficient effect can be obtained if it is 0.03% by mass or more. The amount of addition to which the desired effect is sufficiently obtained is 0.1% by mass or more in the case of sauces, tsukudani, retort foods and wheat flour products, and 0.05% by mass or more in the case of the remaining foods. be. The xanthan gum of the present invention can be quickly imparted with viscosity after being added to a target food product. In the case of food that can be warmed, there is little change in viscosity even if it is cooled.

The xanthan gum of the present invention can be used not only for food applications as described above, but also for pharmaceuticals, quasi-drugs, cosmetics, chemical products, and civil engineering such as oil drilling. The xanthan gum of the present invention is produced through heat treatment and pulverization, and is not chemically treated, so that it is highly safe. Therefore, it is expected to be effective not only in the listed fields but also in various fields.

Regarding the heating of xanthan gum, it is known that it becomes insoluble in water and becomes a super absorbent polymer by excessive heating (Japanese Patent Laid-Open No. 2003-192703). It is said that the reason is that it has an apparently cross-linked structure. It apparently has a crosslinked structure and is polymerized, and swells to the state just before the xanthan gum particles are completely dissolved. As a result, the viscosity increases. The highly viscous xanthan gums shown in Patent Documents 1 to 5 and 7 also have increased viscosity for the same reason. Similar to starch and the like, the aggregate of swollen particles immediately before dissolution is more viscous due to friction between adjacent particles than the state in which the molecules are completely dissolved and melted.

However, in saline, the negatively charged ionic groups in xanthan gum cannot be ionized. Since the repulsion in the particles is suppressed and the swelling does not proceed, the particles having a crosslinked structure do not develop viscosity in particular. In order to develop viscosity in saline solution, it is necessary to perform a predetermined treatment to dissolve the xanthan gum particles. For example, heat treatment of a salt dispersion for solving a crosslinked structure with heat energy, homogenizer treatment of a salt dispersion for breaking xanthan gum particles, and the like are performed.

After such treatment, it was difficult to obtain sufficient viscosity in saline solution using xanthan gum having a crosslinked structure. Further, even in the heat-treated xanthan gum solution dissolved in water, the ionization of the negatively charged ionic group is weakened when salt is added. As a result, the repulsion in the xanthan gum particles is suppressed, the swelling becomes insufficient, and the viscosity tends to decrease.

The crosslinked structure of xanthan gum can be weakened by heat treatment under appropriate conditions. The present invention has found such a weakened xanthan gum having a crosslinked structure and identified it by its physical properties. In the xanthan gum of the present invention, the particles sufficiently swell in water to develop viscosity. Since the xanthan gum of the present invention has weak cross-linking, it can sufficiently swell due to the repulsion of negative ion groups even if the degree of ionization of negative ion groups is small in saline solution. In this way, sufficient viscosity is developed.

Hereinafter, examples of the present invention will be specifically described, but these are not limited to the present invention.
<Preparation of raw material xanthan gum>
Xanthan gum 1-1 (Inagel V-10, manufactured by Ina Food Industry Co., Ltd.) was pulverized by an airflow crusher to prepare pulverized samples (1-2 to 1-8) having a predetermined average particle size. Further, xanthan gum 2-1 (Inagel V-10T, manufactured by Ina Food Industry Co., Ltd.) was also pulverized in the same manner to prepare pulverized samples (2-2-2-8) having a predetermined average particle size. The particle size was adjusted by changing the number of pulverizations and the air pressure.

The crushed sample and the uncrushed sample are used as raw material xanthan gum. The average particle size (volume average particle size) of the raw material xanthan gum was measured using a particle size distribution meter (Microtrac MT3000, manufactured by Nikkiso Co., Ltd.). The results are summarized below.
Raw material xanthan gum 1-1: Average particle size 180 μm
Raw material xanthan gum 1-2: Average particle size 145 μm
Raw material xanthan gum 1-3: Average particle size 117 μm
Raw material xanthan gum 1-4: average particle size 96 μm
Raw material xanthan gum 1-5: Average particle size 65 μm
Raw material xanthan gum 1-6: Average particle size 49 μm
Raw material xanthan gum 1-7: Average particle size 36 μm
Raw material xanthan gum 1-8: Average particle size 25 μm
Raw material xanthan gum 2-1: Average particle size 196 μm
Raw material xanthan gum 2-2: Average particle size 149 μm
Raw material xanthan gum 2-3: Average particle size 115 μm
Raw material xanthan gum 2-4: Average particle size 99 μm
Raw material xanthan gum 2-5: Average particle size 75 μm
Raw material xanthan gum 2-6: Average particle size 46 μm
Raw material xanthan gum 2-7: Average particle size 36 μm
Raw material xanthan gum 2-8: Average particle size 28 μm

The raw material xanthan gum is heat-treated under various conditions, and the following viscosities (μ (w), μ (s)) of the treated xanthan gum are measured. Solubility in saline is evaluated by μ (w) and viscosity ratio (μ (s) / μ (w)).
μ (w): Xanthan gum was added to ion-exchanged water at 20 ° C. at a concentration of 0.4% by weight to disperse it, and the viscosity at 20 ° C. after 60 minutes had elapsed. It was added to 498.0 g of ion-exchanged water with stirring, and the mixture was stirred for 10 minutes. For stirring, a laboratory stirrer (product name: tornado, model number: SM-103, stirring blade: propeller type 3-blade φ50 mm, manufacturer: manufactured by AS ONE) was used, and the mixture was stirred at 300 rpm for 10 minutes. Then, the mixture was left to stand for 49 minutes, stirred for 1 minute under the same conditions to make the viscosity uniform, and then the viscosity was measured to give μ (w).
μ (s): Xanthan gum is added to a 3.0% sodium chloride aqueous solution at 20 ° C. at a concentration of 0.4% by weight and dispersed, and the viscosity at 20 ° C. after 60 minutes has elapsed. Specifically, xanthan gum 2 .0 g was added to 498.0 g of a 3.0 wt% sodium chloride aqueous solution at 20 ° C. with stirring, and the mixture was stirred for 10 minutes. For stirring, a laboratory stirrer (product name: tornado, model number: SM-103, stirring blade: propeller type 3-blade φ50 mm, manufacturer: manufactured by AS ONE) was used, and the mixture was stirred at 300 rpm for 10 minutes. Then, the mixture was left to stand for 49 minutes, stirred for 1 minute under the same conditions to make the viscosity uniform, and then the viscosity was measured to give μ (s).
The dissolution conditions in this example are examples of low-speed stirring, and are not limited to these conditions.

When both the following formulas (1) and (2) are satisfied, it is assumed that the solubility in water and saline solution is excellent. Since it is easily soluble in saline solution, it is used as an example. A comparative example is one that does not satisfy either the formula (1) or the formula (2).
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 400 mPa ・ s (2)

The equipment and conditions used for measuring the viscosity are as follows.
・ B-type viscometer BROOKFIELD (LVDV-1 PRIME)
Measurement temperature: 20 ° C
Rotor: The optimum rotor (No. 1 to 3) was used according to the viscosity.
Rotor: Rotation speed 30 rpm, measure viscosity after 1 minute

<Preliminary test>
The xanthan gum of the present invention is obtained by a specific method of heat-treating a powdery or granular raw material xanthan gum. Effect with xanthan gum produced by the method described in Patent Document 7 (drying only) (hereinafter referred to as "FD xanthan gum") and further heat-treated to make it highly viscous xanthan gum (hereinafter referred to as "FD highly viscous xanthan gum"). In order to explain the difference between the above, the viscosity of the xanthan gum, the FD xanthan gum, and the FD highly viscous xanthan gum of the present invention was measured and the difference in physical properties was investigated.

The xanthan gum of the present invention was produced by the following method. Specifically, 2 kg of xanthan gum (Inagel V-10, manufactured by Ina Food Industry Co., Ltd.) was pulverized with an air flow crusher to prepare a raw material xanthan gum having an average particle diameter of 94 μm. 1000 g of this sample was housed in a stainless steel container and heat-treated at 100 ° C. for 1 hour with a blower dryer to obtain xanthan gum (invention product) of the present invention.

FD xanthan gum was prepared according to the method described in Patent Document 7. Specifically, 30 g of xanthan gum (Inagel V-10, manufactured by Ina Food Industry Co., Ltd.) was dissolved in 1000 g of purified water. This was dried (60 ° C.) in a vacuum freeze-dryer (TAKARA FREEZE-DRYER (model: TF10-85ATNNN, Takara TEM)) to prepare FD xanthan gum having a moisture value of 9.5%.

Further, each part of the FD xanthan gum was continuously subjected to the predetermined heat treatment, and then pulverized with a table crusher to an average particle diameter of 95 μm to obtain FD highly viscous xanthan gums (i) to (vii). The predetermined heat treatments (i) to (vii) are shown below.
(i) 72 hours at 65 ° C.
(ii) 72 hours at 85 ° C
(iii) 1 hour at 100 ° C.
(iv) 3 hours at 120 ° C
(v) 6 hours at 80 ° C
(vi) 2 hours at 90 ° C
(vii) 30 minutes at 110 ° C However, (iii), (iv), and (vii) were beyond the heating range of the vacuum lyophilizer, so they were taken out of the vacuum lyophilizer and blown dryer (Hot air). Heat treatment was performed with rapid drying oven, soyokaz (manufactured by ISUZU).

The above-mentioned viscosities (μ (w), μ (s)) of the obtained xanthan gum were measured. Furthermore, the solubility in saline solution was evaluated by μ (w) and the viscosity ratio (μ (s) / μ (w)).
The results are summarized in the table below.

From Table 1 above, the xanthan gum of the present invention satisfied the above conditions (1) and (2), but the FD xanthan gum and the FD highly viscous xanthan gum produced by the method described in Patent Document 7 were μ ( The value of w) did not satisfy the condition of (2), and the viscosity was low.

As described in Patent Document 7, the FD xanthan gum and the FD highly viscous xanthan gum are obtained by dissolving the raw material xanthan gum in water and then pulverizing it again by vacuum freeze-drying. Generally, when a polysaccharide is processed by dissolving the powder and powdering it again, the polysaccharide molecule is reduced in molecular weight by a heating or freezing step, and the viscosity is lowered. Therefore, the viscosity when dissolved in water is lower than that of the raw material xanthan gum.

Further, as described in paragraph 0016 of Patent Document 7, the density of the single particle powder of the FD xanthan gum powder is lower than that of the raw material xanthan gum. Therefore, when heat-treated, it becomes difficult to form an apparent crosslinked structure. On the other hand, since the xanthan gum of the present invention has a higher density of single particle powder than the FD xanthan gum, it has a crosslinked structure appropriately weakened by heat treatment under appropriate conditions, and exhibits the effect of the present invention.

The xanthan gum of the present invention and the highly viscous xanthan gum shown in Experimental Example 4 (paragraph 0042) of Patent Document 7 have a larger difference in viscosity value depending on the dissolution concentration than ordinary xanthan gum. Specifically, when the viscosities of ordinary xanthan gum are compared by dissolving them in ion-exchanged water at different concentrations (0.4% and 1.0%), ordinary xanthan gum has a viscosity value of 0.4% and 1.0%. The difference is small, whereas the difference is large in the case of highly viscous xanthan gum. The table below shows the viscosity of 0.4% and the viscosity of 1.0% when dissolved in ion-exchanged water (viscosity measurement 60 lapses after dissolution, measurement at 20 ° C.).

The highly viscous xanthan gum shown in Experimental Example 4 (paragraph 0042) of Patent Document 7 is an aggregate of swollen particles immediately before dissolution, which is completely dissolved when dissolved in water. In short, the high viscosity in Patent Document 7 is due to friction between adjacent particles. Even if it shows high viscosity in the high concentration range of 1.0% concentration, the number of adjacent particles decreases in the low concentration range. As a result, friction between the particles does not occur and the viscosity is extremely lowered. It can be seen that the high-viscosity xanthan gum of Patent Document 7 has an extremely low viscosity at 0.4% concentration as compared with the viscosity at 1.0% concentration.

In FD drying and vacuum drying, xanthan gum is dissolved in water and then evacuated to perform drying. Since such a drying method is not blast drying, the drying efficiency is poor. In particular, when a substance containing a large amount of water such as an aqueous solution is dried, the time required to complete the drying becomes very long, which is inferior in reality. Highly viscous ones are difficult to dry. Therefore, even if it is commercialized, it is very expensive and has no industrial advantage.

As described above, the xanthan gum of the present invention obtained by a specific method of heat-treating a powdery or granular raw material xanthan gum has an excellent effect on the xanthan gum described in Patent Document 7. That is, the xanthan gum described in Patent Document 7 is a solution-affinitive polysaccharide obtained by dissolving the raw material xanthan gum in water and then drying it by vacuum drying or vacuum freeze drying. Therefore, it is not the raw material xanthan gum in the form of powder or granules of the present invention, nor is it obtained by heat-treating the raw material xanthan gum of the present invention, and the effects of the present invention cannot be obtained.

The xanthan gum of the present invention and the highly viscous xanthan gum shown in Patent Documents 1 to 5 and 7 have different viscosity values depending on the elapsed time after being dissolved in a solvent. Specifically, the xanthan gum of the present invention dissolves in a short time as long as the stepchild (lump) is not possible to stabilize the viscosity value, whereas the highly viscous xanthan gum shown in the patent document takes a long time to dissolve and the viscosity is stable. It takes time to do it. These differences are due to the differences in the crosslinked structure. That is, since the xanthan gum of the present invention has a weak crosslinked structure, it swells quickly and its viscosity stabilizes in a short time. On the other hand, the highly viscous xanthan gum in the patent document has a strong crosslinked structure, so that it takes a long time to swell and it takes a long time for the viscosity to stabilize. The table below shows the viscosity values of the xanthan gum of the present invention and the xanthan gum of the patent document for each elapsed time.

The xanthan gum of the present invention develops a viscosity faster than that of the xanthan gum of Patent Document 7, and can be used without any problem in a product prepared at the time of use. High viscosity was also shown for the final product (viscosity after 24 hours).
Since the xanthan gum of Patent Document 7 has a long distance between molecules and a reduced number of contacts, cross-linking due to heating is unlikely to occur. However, unlike the present invention, the cross-linking itself is not weakened, and each cross-linking is in a strong state. Therefore, the viscosity in the saline solution is not as high as that of the xanthan gum of the present invention.

<Experimental Example 1: Preparation of xanthan gum>
Each raw material xanthan gum (1000 g) was heat-treated at 80 ° C. for 6 hours. Specifically, each raw material xanthan gum was housed in a container and installed in a blower dryer for heat treatment. The subsequent heat treatment was carried out in the same manner except that the temperature and time were changed. The viscosity μ (w) and μ (s) of the treated xanthan gum were measured, and the viscosity ratio (μ (s) / μ (w)) was determined. The results obtained are summarized in the table below.

The xanthan gum obtained by heat treatment at 80 ° C. for 6 hours satisfies the following formulas (1) and (2), and it can be seen that it has excellent solubility in water and saline solution.
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 400 mPa ・ s (2)

Each raw material xanthan gum (1000 g) was heat-treated at 90 ° C. for 2 hours. The viscosity μ (w) and μ (s) of the treated xanthan gum were measured, and the viscosity ratio (μ (s) / μ (w)) was determined. The results obtained are summarized in the table below.

The xanthan gum obtained by heat treatment at 90 ° C. for 2 hours satisfies the following formulas (1) and (2), and it can be seen that it has excellent solubility in water and saline solution.
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 400 mPa ・ s (2)

Each raw material xanthan gum (1000 g) was heat-treated at 110 ° C. for 30 minutes. The viscosity μ (w) and μ (s) of the treated xanthan gum were measured, and the viscosity ratio (μ (s) / μ (w)) was determined. The results obtained are summarized in the table below.

The xanthan gum obtained by heat treatment at 110 ° C. for 30 minutes satisfies the following formulas (1) and (2), and it can be seen that it has excellent solubility in water and saline solution.
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 400 mPa ・ s (2)

Each raw material xanthan gum (1000 g) was heat-treated at 80 ° C. for 20 hours. The viscosity μ (w) and μ (s) of the treated xanthan gum were measured, and the viscosity ratio (μ (s) / μ (w)) was determined. The results obtained are summarized in the table below.

The xanthan gum obtained by heat treatment at 80 ° C. for 20 hours did not satisfy the following formula (1), and it was shown that the solubility in saline solution was inferior.
μ (s) / μ (w) ≧ 0.25 (1)

Each raw material xanthan gum (1000 g) was heat-treated at 120 ° C. for 2 hours. The viscosity μ (w) and μ (s) of the treated xanthan gum were measured, and the viscosity ratio (μ (s) / μ (w)) was determined. The results obtained are summarized in the table below.

The xanthan gum obtained by heat treatment at 120 ° C. for 2 hours did not satisfy the following formula (1), and it was shown that the solubility in saline solution was inferior.
μ (s) / μ (w) ≧ 0.25 (1)

It was confirmed that an appropriate combination was present in the temperature and time of the heat treatment for obtaining xanthan gum having excellent saline solubility (Examples 1 to 48). When the temperature is low, long-time heating is required, and when the heating temperature is high, a short time is sufficient. For example, in the case of 80 ° C., it is preferably about 4 to 8 hours, and in the case of 90 ° C., it is preferably about 1.5 to 4 hours. When the temperature is higher than 110 ° C., it is preferably within 40 minutes.
Xanthan gum adjusted to an average particle size of 25 to 150 μm has a higher viscosity (μ (w)) and viscosity ratio (μ (s) / μ (w)), and has better solubility in saline solution. It was confirmed that.

The viscosity of the xanthan gum of the present invention can also be confirmed using a dynamic viscoelastic device.
The xanthan gum of Example 5 was dissolved in a sodium chloride aqueous solution (3.0% by mass) at 20 ° C. at a concentration of 0.3% by mass, and the dynamic viscoelasticity and strain dependence were examined. The storage elastic modulus (G') and the loss elastic modulus (G ") were obtained, and the loss tangent (tan δ (G" / G')) was calculated. A viscoelasticity measuring device (Discovery HR-3 TA Instrument Japan Co., Ltd.) was used for the measurement of dynamic viscoelasticity. Similarly, the raw material xanthan gum (conventional product (Comparative Example 1)) and the xanthan gum described in JP-A-11-116603 (Comparative Example 7) also have a storage elastic modulus (G') and loss tangent (tanδ (G)). "/ G')) was requested.

FIG. 1 shows the storage elastic modulus (G') of each xanthan gum, and FIG. 2 shows the loss tangent (tan δ (G "/ G')) of each xanthan gum. G', which is an index (high viscosity) of a solid, is As shown in FIG. 1, Example 5> Conventional product (Comparative Example 1)> Comparative Example 7. Tan δ, which is an index of liquid (low viscosity), is Comparative Example 7> Comparative Example 1> Implementation. Example 5 is shown in FIG. 2. Since the xanthan gum of the example has the largest storage elastic modulus (G') and the smallest loss tangent (tan δ), it is a comparative example or a conventional xanthan gum. It can be seen that higher viscosity can be imparted to the saline solution.

<Experimental example 2: Effect of order of processing steps>
The xanthan gum (average particle diameter 180 μm) of Example 1 was adjusted to have an average particle diameter of 65 μm using an air flow crusher, and was used as Example 49. The xanthan gum of Example 49 was produced in the same manner as in Example 5 except that the order of pulverization and heat treatment for adjusting the average particle size was changed.
For the xanthan gum of Example 49, the viscosities μ (w) and μ (s) were measured in the same manner, and the viscosity ratio (μ (s) / μ (w)) was determined. The results are summarized in the table below together with the results of Example 5.

The xanthan gum of Example 49 has the same characteristics as that of Example 5. From these results, it was confirmed that the order of pulverization and heat treatment for adjusting the average particle size did not affect the properties of the obtained xanthan gum.

<Experimental Example 3: Comparison with salt-soluble xanthan gum>
A 3% solution of the raw material xanthan gum 1-3 was prepared (10 kg) and subjected to homogenizer treatment with a pressure homogenizer (Gorlin, manufactured by APV). Further, freeze-drying was performed at 40 ° C. to form a powder. The average particle size of the obtained xanthan gum was 120 μm (homogenizer-treated product 1). This xanthan gum was also prepared by heat-treating it at 80 ° C. for 6 hours. (Homogenizer treated product 2). For these, the viscosities μ (w) and μ (s) were measured in the same manner as described above, and the viscosity ratio (μ (s) / μ (w)) was determined. The results are summarized in the table below together with the results of Example 3.

When the xanthan gum solution is homogenized and then pulverized, the viscosity (μ (w)) when dissolved in water is 210 mPa · s (<400 mPa · s), and the viscosity when dissolved in saline solution (μ (s)). )) Is 180 mPa · s (Comparative Example 35). Due to this, the viscosity ratio (μ (s) / μ (w)) is a large value of 0.59 or more. In the xanthan gum of Comparative Example 35, μ (w) remained at 220 mPa · s even after heat treatment, and the viscosity did not increase (Comparative Example 36).
From these results, it can be seen that the xanthan gum of the present invention cannot be obtained when the xanthan gum solution is homogenized.

<Experimental example 4: Effect of heating time>
Using 1000 g each of the raw material xanthan gum 1-5, the treatment at 90 ° C. was performed for different times to prepare xanthan gum. The viscosities μ (w) and μ (s) of the obtained xanthan gum were measured in the same manner, and the viscosity ratio (μ (s) / μ (w)) was determined. The viscosity of untreated xanthan gum (raw material xanthan gum 1-5, Comparative Example 37) was measured in the same manner. The results are summarized in the table below.

When the heating temperature is 90 ° C., the xanthan gum obtained by the treatment for 90 to 240 minutes satisfies the following formulas (1) and (2) and has excellent solubility in water and saline solution. (Examples 50 to 54).
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 400 mPa ・ s (2)

<Experimental Example 5: Change of salt concentration>
The xanthan gum obtained in Example 45 was dissolved in saline solutions having different concentrations. The viscosity (μ (s)) represented below was measured together with the above-mentioned viscosity (μ (w)), and the viscosity ratio (μ (s) / μ (w)) was determined. The results are summarized in the table below.
μ (s): Xanthan gum is added to a sodium chloride aqueous solution at each concentration of 20 ° C. at a concentration of 0.4% by weight and dispersed, and the viscosity at 20 ° C. after 60 minutes has elapsed.

In each case, the following mathematical formulas (1) and (2) are satisfied.
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 400 mPa ・ s (2)
It was confirmed that the xanthan gum of the present invention can be well dissolved and imparted viscosity to a saline solution having a salt concentration of 1 to 5% by mass. In a general food containing salt, the salt concentration is usually about 0.3 to 5% by mass, so that a desired effect can be obtained when the xanthan gum of the present invention is applied.

<Experimental example 6: Dressing without heating>
Ingredients were formulated with the formulations (parts by mass) shown in Table 11 below to produce dressings (300 g each). The viscosity of the obtained dressing was measured at 20 ° C. The viscosity of the dressing is usually required to be 70 mPa · s or more.
In addition, each dressing was packed in a jar and the jar was manually shaken for 30 seconds to stir. The oil separation status after standing for one month was visually confirmed and evaluated according to the following criteria. The results are summarized in the table below.
◎: No separation 〇: Slight but no problem △: Separation ×: Severe separation

The dressing using the xanthan gum of the example has a sufficient viscosity of 120 mPa · s or more at 20 ° C., and separation does not occur even if it is left for one month after stirring. On the other hand, when the xanthan gum of the comparative example was used, the viscosity at 20 ° C. was 60 mPa · s at the maximum, and it was surely separated when left for one month after stirring.
It has been shown that the xanthan gum of the examples can impart a stable and high viscosity to foods such as dressings produced without heating.

<Experimental example 7: salted fish>
Xanthan gums of Example 5, Comparative Example 1, Comparative Example 7, and Comparative Example 35 were added to commercially available salted fish, and the viscosities were compared. The amount of xanthan gum added was 0.1% by mass. The viscosity of the liquid portion from which the solid content had been removed was measured at 20 ° C. The results are summarized in the table below. If it is 70 mPa · s or more, it can be considered that the viscosity is imparted.

Since the xanthan gum of the present invention is easily soluble in saline solution, it was possible to impart viscosity to salted fish even with a small amount of addition.

<Experimental example 8: Soy sauce thickening>
Xanthan gums of Example 14, Comparative Example 2, Comparative Example 16 and Comparative Example 35 were added to a commercially available soy sauce soup stock (salt concentration 5%), and the viscosities were compared. The amount of xanthan gum added was 0.2% by mass. The viscosity at 20 ° C. is measured and the results are summarized in the table below. If it is 60 mPa · s or more, it can be considered that the viscosity is imparted.

Since the xanthan gum of the present invention is easily soluble in saline solution, it was possible to impart viscosity to the soy sauce broth even with a small amount of addition.

<Experimental Example 9: Salt-supplemented beverage (salt concentration 0.3%)>
Xanthan gum of Example 2, Comparative Example 1, Comparative Example 20 and Comparative Example 35 was added to a commercially available isotonic beverage (salt concentration 0.3%) to produce a thickened beverage for people with swallowing disorders. The amount of xanthan gum added was 0.2% by mass. The viscosity at 10 ° C. is measured and the results are summarized in the table below. If it is 300 mPa · s or more, it can be considered that an appropriate viscosity has been imparted as a beverage for a person with a swallowing disorder.

Since the xanthan gum of the present invention is easily soluble in saline solution, it was possible to impart appropriate viscosity to the isotonic beverage for people with swallowing disorders even with a small amount of addition.

<Experimental Example 10: Isotonic beverage containing errand-adjusted vitamins (final salt concentration 0.3%)>
Xanthan gum of Example 2, Comparative Example 1, Comparative Example 20, and Comparative Example 35 is added to a commercially available vitamin-containing isotonic beverage powder (final salt concentration 0.3%), and is used for thickened beverages for people with swallowing disorders. The powder was prepared. The amount of xanthan gum added was 0.2% by mass (when water was added). A specified amount of water (10 ° C.) was added thereto and dissolved to produce a beverage. The viscosity after 10 minutes is measured and the results are summarized in the table below. If it is 300 mPa · s or more, it can be considered that an appropriate viscosity has been imparted as a beverage for a person with a swallowing disorder.

Since the xanthan gum of the present invention is easily soluble in saline solution, it was possible to impart appropriate viscosity to an isotonic beverage containing a vitamin-containing preparation for use even with a small amount of addition for a person with a swallowing disorder.

<Experimental Example 11>
Xanthan gum of Example 16, Comparative Example 2, Comparative Example 34, and Comparative Example 35 was added and dissolved in milk at 10 ° C. at a concentration of 0.2% by mass, respectively. The viscosity after 10 minutes is measured and the results are summarized in the table below. If it is 100 mPa · s or more, it can be considered that an appropriate viscosity has been imparted to a person with a swallowing disorder for drinking.

Since the xanthan gum of the present invention increases the viscosity of milk even when added in a small amount, even a nursing food containing a large amount of milk component can be appropriately thickened for drinking by a person with a swallowing disorder. It has been shown that the xanthan gum of the present invention can impart the desired viscosity to calcium-rich foods such as milk. From this result, it is presumed that the xanthan gum of the present invention can similarly impart viscosity to foods for use-time adjustment type calcium supplementation, mineral and vitamin supplementation for people with swallowing disorders.

<Experimental example 12: Massage gel>
The xanthan gum of the present invention was added to salt to produce a massage gel used for tightening the skin. 5 g each of the xanthan gums of Example 24, Comparative Example 1, Comparative Example 10 and Comparative Example 35 were added to 500 g of salt and mixed. 100 g of water was added thereto, and the mixture was stirred and kneaded. Visually observe the cohesive state of the obtained kneaded product, and the results are summarized in the table below.

The massage gel using the xanthan gum of the present invention was well-organized and easy to use. It was shown that the xanthan gum of the present invention can retain its shape by imparting sufficient viscosity not only in a saline solution of about 0.3 to 5% by mass but also in the presence of a larger amount of salt.

<Experimental example 13: Assuming retort food>
In order to fill the retort pouch with food, it is necessary to keep the seasoning liquid viscous and the ingredients do not settle. In addition, most of the foods filled in the retort pouch contain salt such as curry, Chinese bowl, oyakodon, and beef bowl.

Xanthan gum of Example or Comparative Example was added to the ingredient liquid assuming a retort food, and the sedimentation condition of the ingredient was examined. Assuming the ingredients, sections of potatoes and carrots of appropriate size (about 1 cm square) were prepared, and the ingredients were prepared by adding the seasoning solution to the assumed saline solution (concentration: 3% by mass). Xanthan gum of Example 22, Comparative Example 1, Comparative Example 8 and Comparative Example 35 was added thereto at a concentration of 0.5% by mass and placed. After 3 hours, the sedimentation condition of the ingredients was visually observed. If the ingredients in the liquid were in a state where they were floating and did not sink, or were in a state where they hardly settled, "no sedimentation" was given, and in other cases, "with sedimentation" was given. The results are summarized in the table below.

The ingredient liquid assuming a retort food using the xanthan gum of the present invention was stable without sedimentation of the ingredients. The xanthan gum of the present invention can impart sufficient viscosity even in the presence of salt. It was confirmed that the ingredients can be uniformly filled in a container such as a pouch, so that it is suitably used in the production of retort foods.

Claims (2)

Xanthan gum having an average particle size of 25 to 150 μm, which has been heat-treated with respect to the powdered or granular raw material xanthan gum, is ion-exchanged water at 20 ° C. or 3.0% by mass chloride at a concentration of 0.4% by mass. The viscosities (μ (w) and μ (s)) at 20 ° C. measured at a rotation speed of 30 rpm using a B-type viscosity meter after 60 minutes have passed since they were added to an aqueous sodium solution and dispersed are shown in the following formula (1) and Xanthan gum characterized by satisfying the formula (2).
μ (s) / μ (w) ≧ 0.25 (1)
μ (w) ≧ 600 mPa ・ s (2)
(Here, μ (w) is the viscosity in the case of ion-exchanged water, and μ (s) is the viscosity in the case of a 3.0% by mass sodium chloride aqueous solution.) A food product containing the xanthan gum according to claim 1.

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