JP6895554B2 - Methyl cellulose and foods containing it - Google Patents

Description

The present invention relates to a gelled composition and a food containing the same.

In recent years, the number of elderly people has increased due to the longevity society, and the number of people who have difficulty eating or swallowing due to aging-related deterioration of swallowing function and those who have difficulty eating or swallowing due to brain disease or oral or pharyngeal disorder are increasing. In particular, elderly people are less likely to have a swallowing reflex due to a decrease in eating or swallowing function, and aspiration causes water or food to enter the lungs from the bronchi, causing serious symptoms such as pneumonia. Therefore, there is a demand for a dietary form such as a jelly diet that can be easily orally ingested by persons who have difficulty eating or swallowing.

Conventionally, in order to adjust the hardness, adhesiveness or cohesiveness (easiness of cohesiveness) of foods required by people who have difficulty eating or swallowing, the foods are made into pastes or softened and served. ing. Therefore, the conventional diet for people who have difficulty eating or swallowing is not always satisfied with the appearance, texture, and the like as compared with the general diet. In addition, since the physical properties are controlled by using a low-temperature gelling agent when making a paste, it becomes soft and melts when warmed, and in many cases it deviates from the physical properties suitable for swallowing, so it is possible to provide it in a warm state. It was difficult. In particular, when serving food at a facility or hospital, it is necessary to heat-treat the food so that the core temperature of the food is maintained at 75 ° C. for 10 minutes or more before serving, and the low-temperature gelling agent melts. There was a problem that the form of food could not be maintained.

Therefore, in Patent Document 1, as a method for maintaining the hardness and adhesiveness of foods for people who have difficulty in eating or swallowing even when heated, methylcellulose or hydroxypropylmethylcellulose, which are gelling agents that coagulate by heating, agar, and carrageenan. A combination with a gelling agent that cools and solidifies, such as, has been proposed.

Japanese Unexamined Patent Publication No. 2014-236700

However, in the case of Patent Document 1, although the hardness or adhesiveness when gelled at a heating temperature equal to or higher than the gelling temperature of methyl cellulose or hydroxypropyl methyl cellulose can be maintained, the cooked food is actually eaten in a warm state thereafter. When the temperature reaches around 45 ° C., the gel state cannot be maintained and the solution becomes viscous. As a result, the adhesiveness increased and the food became sticky in the mouth, which was one of the causes of food clogging in the throat.
The present invention retains the form of the food at the heating temperature before the meal is served, prevents water separation due to heating, and then eats the food at around 45 ° C. in terms of hardness, adhesiveness and cohesiveness. It is an object of the present invention to provide a gelled composition capable of controlling (easiness of putting food together).

As a result of diligent studies to achieve the above object, the present inventors have made a combination of a predetermined methyl cellulose and a low-temperature gelling agent to stabilize the form of the food even from a high temperature state to a warm state, and the hardness of the food. , And have found that the adhesiveness and cohesiveness can be controlled, and have come to the present invention.
According to one aspect of the present invention, the storage elastic modulus G'(75 ° C.) of the 2.0 mass% aqueous solution at 75 ° C. is 3,000 to 5,500 Pa, and when the temperature returns from 75 ° C. to 45 ° C. Methyl cellulose having a storage elastic modulus G'(75 → 45 ° C.) at the return temperature of 2,000 to 3,300 Pa and a viscosity of a 2.0 mass% aqueous solution at 20 ° C. of 3,000 to 10,000 mPa · s. Provided are methyl cellulose having an average degree of substitution (DS) of methoxy groups per glucose unit of the methyl cellulose of 1.74 to 2.03, a food additive containing the methyl cellulose, and a food containing the methyl cellulose. ..

According to the present invention, the form of food can be maintained even at 75 ° C., and water separation from food due to heating can be reduced. Further, when the temperature is returned from 75 ° C. to 45 ° C., the food can be imparted with hardness, adhesiveness and cohesiveness that can be easily orally ingested by a person who has difficulty eating and swallowing.

(1) Methyl Cellulose According to the present invention, the storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution at 75 ° C. is 3,000 to 5,500 Pa, and when the temperature returns from 75 ° C. to 45 ° C. The storage elastic modulus G'(75 → 45 ° C.) of the 2.0 mass% aqueous solution at the return temperature is 2,000 to 3,300 Pa, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. is 3,000 to 3,000. Methyl cellulose at 10,000 mPa · s can be used.
For this methyl cellulose, for example, a step of stirring and mixing a cellulose pulp and a first alkali metal hydroxide solution to obtain alkali cellulose, and a step of reacting the alkali cellulose with a methylating agent to obtain a first reaction mixture. The step of blending the second alkali metal hydroxide solution with the first reaction mixture without further blending the methylating agent and stirring and mixing to obtain the second reaction mixture, and the second step. A method for producing methyl cellulose, which comprises at least a step of purifying the reaction mixture to obtain methyl cellulose, wherein the first alkali metal hydroxide in the first alkali metal hydroxide solution and the second alkali metal hydroxide solution are used. Obtained by a method for producing methyl cellulose in which the ratio of the mass of the first alkali metal hydroxide to the total mass of the second alkali metal hydroxide in the alkali metal hydroxide solution is preferably 50 to 86%. Be done.

Cellulose pulp is a material for ordinary methyl cellulose such as wood pulp and linter pulp. The intrinsic viscosity, which is an index of the degree of polymerization of cellulose pulp, can be appropriately selected according to the target aqueous viscosity of methyl cellulose, but is preferably 600 to 1,200 ml / g at 25 ° C. More preferably, it is 800 to 1000 ml / g. The intrinsic viscosity of cellulose pulp can be measured by a method according to the method A of JIS P8215.
Cellulose pulp contains cellulose and water, and the amount of "cellulose in cellulose pulp" in the present specification can be measured by a method conforming to the JIS P8215 A method.

The cellulose pulp is preferably powdered cellulose pulp crushed by a crusher. The pulp crusher is not particularly limited as long as it is possible to pulverize cellulose pulp, but a crusher such as a knife mill, a cutting mill, a hammer mill, a ball mill, or a vertical roller mill should be used. Can be done. The weight average particle size D ₅₀ of the powdered cellulose pulp is preferably 30 to 400 μm. The weight average particle diameter D ₅₀ of powdered cellulose pulp, in a Ro-Tap Shikifurui shaker, set up a mesh of different test sieve conforming to JIS Z8801, the powder pulp placed on the top sieve, vibrating or After sieving by tapping, the mass on and under the sieve is measured to obtain the mass distribution, and the average particle size at an integrated value of 50% is measured and obtained.

The step of obtaining alkali cellulose by stirring and mixing the cellulose pulp and the first alkali metal hydroxide solution will be described.
The alkali metal hydroxide solution is divided into two stages and blended like the first alkali metal hydroxide solution and the second alkali metal hydroxide solution. Here, the alkali metal hydroxide solution is not particularly limited, and solutions of sodium hydroxide, potassium hydroxide and the like can be mentioned, but an aqueous sodium hydroxide solution is preferable from an economical point of view. For example, sodium hydroxide is used as the first alkali metal hydroxide in the first alkali metal hydroxide solution and the second alkali metal hydroxide in the second alkali metal hydroxide solution. As described above, it is preferable to use the same type, but it is also possible to use different types of combinations, for example, sodium hydroxide is used as the former and potassium hydroxide is used as the latter.

The method for blending the alkali metal hydroxide solution is preferably to add the alkali metal hydroxide solution to the cellulose pulp, for example, a method of directly dropping the alkali metal hydroxide solution, an alkali metal hydroxide solution. There is a method of spraying in the form of a spray, but the method of spraying in the form of a spray is preferable because the obtained alkali cellulose has good uniformity.
The concentration of the alkali metal hydroxide in the alkali metal hydroxide solution is preferably 10 to 60% by mass, more preferably 30 to 50% by mass, from the viewpoint of etherification reaction efficiency and handling. The first alkali metal hydroxide and the second alkali metal hydroxide are preferably at the same concentration, but can have different concentrations.

The step of stirring and mixing the cellulose pulp and the alkali metal hydroxide solution is preferably performed in a reactor having an internal stirring structure. The reactor is preferably equipped with a measuring instrument capable of measuring the internal temperature.
Further, before stirring and mixing the first alkali metal hydroxide solution and cellulose pulp, oxygen in the reactor is removed by a vacuum pump or the like and replaced with an inert gas, preferably nitrogen, to obtain alkali metal hydroxide. It is preferable to suppress the depolymerization that occurs in the presence of substances and oxygen.

The amount of the first alkali metal hydroxide solution used is preferably 2.0 as the molar ratio of the first alkali metal hydroxide to cellulose in the cell rope pulp (first alkali metal hydroxide / cellulose). It is ~ 4.0, more preferably 2.7 ~ 3.5. If the molar ratio of the first alkali metal hydroxide to cellulose is less than 2.0, the gelation temperature may be excessively lowered and viscosity may not be developed, and methyl cellulose having high shape retention cannot be produced. In some cases. On the other hand, if it exceeds 4.0, methyl cellulose having high shape retention may not be produced.

First alkali metal hydroxide relative to the total mass of the first alkali metal hydroxide in the first alkali metal hydroxide solution and the second alkali metal hydroxide in the second alkali metal hydroxide solution The proportion of the mass of the substance is preferably 50 to 86%, more preferably 65 to 80%, still more preferably 65 to 75%. If the ratio of the mass of the first alkali metal hydroxide to the total mass of the first and second alkali metal hydroxides is less than 50%, the gelation temperature is lowered and the viscosity is not developed, and the viscosity is not developed. Methyl cellulose having high shape retention may not be produced. On the other hand, if the ratio of the mass of the first alkali metal hydroxide to the total mass of the first and second alkali metal hydroxides exceeds 86%, methyl cellulose having high shape retention may not be produced.

The internal temperature of the reactor when the cellulose pulp and the first alkali metal hydroxide are mixed, preferably the internal temperature of the reactor when the first alkali metal hydroxide solution is added to the cellulose pulp is uniform alkaline cellulose. From the viewpoint of obtaining the above temperature, the temperature is preferably 10 to 80 ° C, more preferably 30 to 70 ° C.
The compounding rate of the first alkali metal hydroxide in the first alkali metal hydroxide solution indicates the molar amount of the first alkali metal hydroxide added per unit time per mole of cellulose pulp. From the viewpoint of ensuring that one alkali metal hydroxide solution is uniformly mixed in the system, it is preferably 1.5 to 48 [mol / mol · hr], more preferably 4.8 to 18.6. [mol / mol · hr], more preferably 8 to 15 [mol / mol · hr].
After the addition of the first alkali metal hydroxide solution, it is also possible to continue stirring and mixing for another 5 to 30 minutes to make the alkali cellulose more uniform.

For the purpose of suppressing local heat generation in the reactor, an organic solvent that is not subjected to the methylation reaction, for example, dimethyl ether, is added to the system before, during, or after the addition of the first alkali metal hydroxide solution. can do.

Then, the obtained alkaline cellulose is reacted with a methylating agent to obtain a first reaction mixture.
Examples of the methylating agent include methyl chloride, dimethyl sulfate, methyl iodide and the like, and methyl chloride is preferable from the viewpoint of solubility of the obtained methyl cellulose in water and economic viewpoint.

The temperature inside the reactor when the methylating agent is reacted is preferably 40 to 90 ° C, more preferably 50 to 80 ° C from the viewpoint of reaction control.
The blending molar amount of the methylating agent is preferably 0.8 as the molar ratio of the methylating agent (methylating agent / total alkali metal hydroxide) to the total molar amount of the first and second alkali metal hydroxides. It is ~ 1.5, more preferably 1.0 ~ 1.3. If the molar ratio (methylating agent / total alkali metal hydroxide) is less than 0.8, the required amount of methyl group may not be replaced. On the other hand, it may be economically disadvantageous to add a methylating agent in excess of 1.5.
The method of blending the methylating agent is preferably to add the methylating agent to the alkaline cellulose. The addition time of the methylating agent is preferably 30 to 120 minutes, more preferably 40 to 90 minutes from the viewpoint of reaction control and productivity.
The degree of substitution (DS) of the methyl group of methyl cellulose in the first reaction mixture is preferably 0.75 to 1.68, more preferably 0.81 to 0.81 from the viewpoint of obtaining a desired viscosity or storage elastic modulus. It is 1.68, more preferably 0.99 to 1.37. Here, DS (degree of substation) indicates the average number of hydroxyl groups substituted with methyl groups per glucose ring unit of cellulose.

Subsequently, a second alkali metal hydroxide solution is added to the methylated first reaction mixture without further adding a methylating agent, and a second reaction mixture is obtained by stirring and mixing.
When the second alkali metal hydroxide solution is blended with the first reaction mixture, that is, when the blending of the second alkali metal hydroxide solution is started, preferably 80% by mass of the total amount of the methylating agent to be blended. After the addition of% or more is completed, more preferably after the addition of the methylating agent is completed. If the addition of the second alkali metal hydroxide solution is started before the addition of 80% by mass of the total amount of the methylating agent to be blended is completed, methyl cellulose having high shape retention may not be produced. ..

The amount of the second alkali metal hydroxide used in the second alkali metal hydroxide solution is preferably 0 as the molar ratio (second alkali metal hydroxide / cellulose) to cellulose in the cellulose pulp. It is 65 to 2.0, more preferably 0.88 to 1.48. If the molar ratio (alkali metal hydroxide / cellulose) is less than 0.65, methyl cellulose having high shape retention may not be produced, and if it exceeds 2.0, the gelation temperature is excessively lowered. In some cases, viscosity may not be exhibited, and methylcellulose having high shape retention may not be produced.

The temperature inside the reactor at the start of blending when blending the second alkali metal hydroxide solution with the first reaction mixture, preferably when adding the second alkali metal hydroxide solution to the first reaction mixture. The temperature inside the reactor at the start of addition is preferably 65 to 90 ° C, more preferably 75 to 85 ° C. If the internal temperature of the reactor at the start of addition of the second alkali metal hydroxide solution is less than 65 ° C., methyl cellulose having high shape retention may not be produced. Further, if the internal temperature of the reactor at the start of addition exceeds 90 ° C., the exothermic reaction due to the mercerization reaction by the alkali metal hydroxide and the exothermic reaction due to methylation may become uncontrollable. Further, from the viewpoint of obtaining methyl cellulose having high shape retention, the temperature inside the reactor when the compounding of the second alkali metal hydroxide solution is completed is preferably 80 to 100 ° C, more preferably 85 to 95 ° C. is there. The temperature at the start of addition is preferably lower than that at the completion of addition, and the temperature difference is preferably 3 to 20 ° C, more preferably 4 to 15 ° C.

The blending rate of the second alkali metal hydroxide in the second alkali metal hydroxide solution is such that the first reaction mixture is blended in a unit time per mole of cellulose in the cellulose pulp used as a starting material. The molar amount of the second alkali metal hydroxide is shown, preferably 0.5 to 9.6 [mol / mol · hr], more preferably 1.0 to 6.5 [mol / mol · hr], and even more preferably. Is 1.0 to 3.5 [mol / mol · hr]. If the compounding rate of the second alkali metal hydroxide is less than 0.5 [mol / mol · hr], the compounding time of the second alkali metal hydroxide becomes long, which leads to an extension of the reaction time. In some cases, it may not be possible to produce methylcellulose having high shape retention. On the other hand, even if the blending rate of the second alkali metal hydroxide exceeds 9.6 [mol / mol · hr], methyl cellulose having high shape retention may not be produced.

In the step of blending the second alkali metal hydroxide solution with the first reaction mixture, from the viewpoint of obtaining methylcellulose having high shape retention, from the start to the completion of blending of the second alkali metal hydroxide solution. During this period, it is preferable to mix the mixture while raising the temperature inside the reactor at a constant rate. The rate of temperature rise is preferably 3.0 to 50 ° C./hr, more preferably 8.0 to 45 ° C./hr, and even more preferably 8.0 to 30 ° C./hr.
In general, alkali cellulose obtained by mixing cellulose pulp and an alkali metal hydroxide solution becomes methyl cellulose by an etherification reaction with a methylating agent. In this case, the methylating agent in the reaction system is gradually consumed along with this etherification reaction. When the temperature inside the reactor is constant, the reaction rate of the etherification reaction gradually decreases with the consumption of the methylating agent in the reaction system. Therefore, by blending the second alkali metal hydroxide solution while raising the temperature inside the reactor at a constant rate, the reaction rate of the etherification reaction resulting from the consumption of the methylating agent in the reaction system can be reduced. Suppress and relatively increase the etherification reaction rate associated with the formulation of the second alkali metal hydroxide solution. Thereby, methyl cellulose having high shape retention can be obtained.

After blending the second alkali metal hydroxide solution, it is preferable to continue stirring and mixing to complete the etherification reaction.
The temperature inside the reactor during stirring and mixing after the preparation of the second alkali metal hydroxide solution is preferably 80 to 120 ° C., more preferably 85 to 100 ° C. from the viewpoint of reaction controllability. In order to terminate the reaction, it is preferable to heat after blending the second alkali metal hydroxide solution.
The stirring and mixing time after blending the second alkali metal hydroxide solution is preferably 10 to 60 minutes, more preferably 20 to 40 minutes from the viewpoint of productivity.

The obtained second reaction mixture can be purified into methyl cellulose in the same manner as in the usual method for purifying crude methyl cellulose. In the purification method, for example, the second reaction mixture and water at 60 to 100 ° C. are mixed in a stirring container, the salt generated as a side reaction during the reaction is dissolved in the stirring container, and then the desired purification is performed. In order to obtain methyl cellulose, the suspension from the stirring vessel is subjected to a separation operation to remove salts. For the separation operation, for example, a pressurized rotary filter can be used. After the separation operation, drying is performed using a dryer. As the dryer, for example, a conduction heat transfer type groove type stirring dryer can be used.
If necessary, the obtained methyl cellulose can be pulverized using a normal pulverizer such as a ball mill, a roller mill, or an impact crusher, and then classified by a sieve to adjust the particle size. Can be done.

The degree of substitution (DS) of the methyl group of methyl cellulose is preferably 1.61 to 2.03, more preferably 1.74 to 2.03. If the DS is less than 1.61, methylcellulose may not have high shape retention, while methods for producing methylcellulose with a degree of substitution greater than 2.03 include methylating agents and alkali metal hydroxides. Since the amount of the addition is large, it may be economically disadvantageous.
In general, DS represents the degree of substitution, which is the average number of hydroxyl groups substituted with methoxy groups per glucose ring unit of cellulose.
The degree of substitution of the methyl group of methyl cellulose was determined by J. G. Gobler, E.I. P. Samscl, andG. H. It can be measured by the method by Zeisel-GC described in Beaver, Talanta, 9,474 (1962).

The gel strength of methylcellulose is the storage elastic modulus G'(75 ° C.) of a 2.0% by mass aqueous solution at 75 ° C. and when it returns from 75 ° C. to 45 ° C., which allows the cooked food to be eaten in a warm state. It is expressed by the storage elastic modulus G'(75 → 45 ° C.) of a 0 mass% aqueous solution. In general, the storage elastic modulus represents the elastic component of a solution, that is, the component in which the deformation generated when a force is applied to an object returns to the original state when the force is removed, and is an index of gel strength.

The storage elastic modulus G'(75 ° C.) of the 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. is 3,000 to 5,500 Pa, preferably 3,500 to 5,300 Pa, and more preferably 3,800 to 5,000 Pa. , More preferably 4,000 to 4,800 Pa. If the storage elastic modulus G'(75 ° C.) is less than 3,000 Pa, the shape of the food cannot be maintained and the shape of the food is lost. On the other hand, when the storage elastic modulus G'(75 ° C.) exceeds 5,500 Pa, the strength of the gel becomes too hard, and the gel strength is maintained in a high state when the temperature returns from 75 ° C. to 45 ° C. People who have difficulty eating or swallowing cannot easily take it orally.

Further, the storage elastic modulus G'(75 → 45 ° C.) of the 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. is 2,000 to 3,600 Pa, preferably 2,300 to 3 , 300 Pa, more preferably 2,500 to 3,200 Pa, still more preferably 2,500 to 3,000 Pa. If the storage elastic modulus G'(75 → 45 ° C.) is less than 2,000 Pa, the hardness, adhesiveness and cohesiveness that can be easily taken orally by a person who has difficulty eating or swallowing cannot be obtained. Further, if the storage elastic modulus G'(75 → 45 ° C.) exceeds 3,600 Pa, the strength of the gel becomes too high, which is not preferable because it cannot be easily taken orally by a person who has difficulty eating or swallowing.
The storage elastic modulus G'(75 ° C.) and the storage elastic modulus G'(75 → 45 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose can be measured using, for example, MCR502, which is a rheometer manufactured by Antonio Par.

The preparation of a 2.0% by mass aqueous solution of methyl cellulose is carried out as follows.
Accurately weigh the amount corresponding to 6.0 g of the converted dry matter of methyl cellulose into a wide-mouthed bottle (container with a diameter of 65 mm and a height of 120 mm and a volume of 350 ml), add boiling water (98 ° C.) to make 300.0 g, and cover the container. Then, use a stirrer to stir at 350 to 450 rpm for 20 minutes until a uniform dispersion is obtained. Then, the obtained dispersion is dissolved in a water bath at 5 ° C. or lower for 40 minutes with stirring to prepare a sample solution.
The temperature of the sample measurement part of the rheometer was adjusted to 10 ° C in advance, and the prepared 2.0% by mass aqueous solution of methylcellulose was added to the marked line (a cylindrical container made of aluminum having a diameter of 30 mm and a height of 80 mm) of the CC27 measurement cup. 25 ml), set the frequency to 1 Hz, apply strain with an amplitude of 1% using a bob cylinder (diameter 26.7 mm and height 40.0 mm: CC27), and start measurement. The measuring unit raises the temperature from 10 ° C. to 2 ° C. per minute, and collects data at one point per minute. The storage elastic modulus when the sample measuring unit reached 75 ° C. was defined as the storage elastic modulus G'(75 ° C.) of the present invention. Further, the storage elastic modulus of the present invention is the storage elastic modulus when the sample measuring unit reaches 45 ° C. after being cooled by 1 ° C. per minute while being strained at a frequency of 1 Hz and an amplitude of 1% after reaching 75 ° C. The rate was G'(75 → 45 ° C).

The viscosity of the 2.0 mass% aqueous solution of methyl cellulose at 20 ° C. by a B-type viscometer is 3,000 to 10,000 mPa · s, preferably 4,000 to 8,000 mPa · s, more preferably 4,000 to 6 It is 000 mPa · s. If the viscosity of the 2.0 mass% aqueous solution is less than 3,000 mPa · s, the strength of the gel of the food containing methyl cellulose becomes low and the form of the food cannot be maintained. On the other hand, when the viscosity of the 2.0% by mass aqueous solution exceeds 10,000 mPa · s, the viscosity of the gelled composition increases and the adhesiveness increases. There is an increased risk of problems.
The viscosity of the B-type viscometer can be measured by the 16th revised Japanese Pharmacopoeia analysis method for methyl cellulose.

The gelation temperature of methylcellulose is evaluated using the relationship between the storage elastic modulus G'(30 → 80 ° C.) and the loss elastic modulus G''. In general, the loss elastic modulus represents a viscous component of a solution, that is, a component having a property that the fluid is deformed to generate resistance with the movement of the fluid, and is an index of gelation temperature.
The gelation temperature of the 2.0 mass% aqueous solution of methyl cellulose is preferably 40 to 55 ° C, more preferably 40 to 50 ° C, and even more preferably 40 to 45 ° C. If the gelation temperature is less than 40 ° C., the dissolution temperature of methyl cellulose in water becomes too low, and the methyl cellulose may not dissolve and the viscosity may not be sufficiently developed. On the other hand, if the temperature exceeds 55 ° C., the gel strength of the food containing methyl cellulose is low, and the form of the food may not be sufficiently maintained.

The gelling temperature of a 2.0 mass% aqueous solution of methyl cellulose can be measured using, for example, MCR502, a rheometer manufactured by Antonio Par.
The methylcellulose 2.0% by mass aqueous solution is prepared in the same manner as the sample solution having the storage elastic modulus G'(75 ° C.).
The temperature of the sample measurement part of the rheometer is adjusted to 30 ° C. in advance, and a 2.0% by mass aqueous solution of methylcellulose is poured up to the marked line (25 ml) of the CC27 measurement cup (cylindrical container having a diameter of 30 mm and a height of 80 mm). The frequency is set to 1 Hz, a strain with an amplitude of 1% is applied, and the measurement is started. The sample measuring unit raises the temperature to 80 ° C. by 2 ° C. per minute. Data is collected at 2 points per minute.
The storage elastic modulus G'(30 → 80 ° C.) and the loss elastic modulus G'' obtained by this measurement change as the temperature of the measurement system rises, and the loss elastic modulus G'(30 → 80 ° C.) and the storage elastic modulus G' The temperature at which (30 → 80 ° C.) was equal, that is, G'' / G'(30 → 80 ° C.) = 1, was defined as the gelling temperature.

(2) Gelled composition and foods containing it The gelled composition is used for foods such as homogeneous jelly-like foods, mousse-like foods, porridge, soft paste-like foods or jelly-like foods before meals are provided. Hardness, adhesiveness and cohesiveness (of foods) even at around 45 ° C, where the food can retain its morphology at the heating temperature of 75 ° C, prevent water separation due to heating, and then eat the food in a warm state. It can be blended for the purpose of controlling the ease of putting together.

The gelling composition contains at least the above-mentioned methyl cellulose, a low-temperature gelling agent, and a solvent.
The proportion of methylcellulose in the gelled composition is preferably 0.05 to 10% by mass from the viewpoint of making it hard, adherent, and cohesive so that a person who has difficulty eating or swallowing can easily take it orally.

The low-temperature gelling agent gels at a temperature lower than the gelation temperature of the methyl cellulose from the viewpoint of imparting shape retention to the food cooled in a temperature range lower than the gelation temperature of the methyl cellulose. The gelling temperature of the low temperature gelling agent is preferably 0 to 35 ° C. Examples of the low temperature gelling agent include gelatin and polysaccharides. Polysaccharides include agar, carrageenan, gellan gum, native gellan gum, xanthan gum and galactomannans (locust bean gum, glucomannan, cassia gum, tara gum) that gel by cooling an aqueous solution that has been heated and dissolved. , And other examples include silium seed gum, curdlan, etc., which can be used alone or in combination of two or more.
The proportion of the low temperature gelling agent in the gelling composition is preferably 0.05 to 30% by mass from the viewpoint of making it hard, adherent, and cohesive so that a person who has difficulty eating or swallowing can easily take it orally. Is.

Examples of the solvent include ion-exchanged water, distilled water, tap water, buffer solution and the like, and ice obtained from these can also be used.
The proportion of the solvent in the gelling composition is preferably 1 to 99% by mass from the viewpoint of making it hard, adhesive, and cohesive so that a person who has difficulty eating or swallowing can easily take it orally.

If necessary, the gelling composition may further contain additives such as sugars, sweeteners, organic acids, thickeners, and seasonings. The content of each of these additives varies depending on the use of the gelling composition, but from the viewpoint of suppressing the precipitation of the gelling composition, ingredients, etc. during heating and suppressing the separation of water from the food. Therefore, it is preferably 0.5 to 30% by mass.

The sugar is not particularly limited, but is glucose, fructose, sucrose, malt sugar, enzyme saccharified syrup, lactose, reduced starch saccharified product, isomerized liquid sugar, sucrose-bound syrup, oligosaccharide, reduced sugar, polydextrose, sorbitol, reduction. Lactose, trehalose, xylose, xylitol, martitol, erythritol, mannitol, fructose oligosaccharide, soybean oligosaccharide, galactooligosaccharide, milk fructose oligosaccharide, raffinose, lactulose, palatinose oligosaccharide and the like can be mentioned and used alone or two. Seeds and above can be used in combination.

Examples of the sweetener include sucralose, acesulfame potassium, stevia, aspartame and the like, and these can be used alone or in combination of two or more.
Organic acids include various fruit juices such as citric acid, lactic acid, gluconic acid, malic acid, tartaric acid, fumaric acid, acetic acid, glacial acetic acid, phytic acid, adipic acid, succinic acid, gluconodeltalactone, ascorbic acid, and citrus fruit juice. Etc., and these can be used alone or in combination of two or more.

As the thickener, alginic acid, carboxymethyl cellulose, farcellan, glucomannan, pectin, starch, and processing are used from the viewpoint of suppressing precipitation and separation of gelling agents and ingredients during heating and suppressing water separation from foods. Examples include starch, guar gum, phenuglique gum, cellulose, fine fibrous cellulose, fermented cellulose, crystalline cellulose, konjak mannan, glucomannan, tamarind, soybean protein, dietary fiber, etc., which may be used alone or in combination of two or more. Can be used.
Examples of the seasoning include glycine, sodium glutamate, amino acid seasoning and organic acids such as salt and acetic acid, and these can be used alone or in combination of two or more.

Next, a method for producing the gelled composition will be described.
As a method for producing a gelling composition, a production method in which methyl cellulose and a low-temperature gelling agent in the gelation composition are separately mixed with a solvent and then combined, and a production method in which methyl cellulose and a low-temperature gelling agent are simultaneously mixed in a solvent. There is a manufacturing method.

The dispersion liquid of methyl cellulose is prepared by putting methyl cellulose into a wide-mouthed bottle containing hot water and keeping it at 90 to 100 ° C., and stirring it with a stirrer to obtain a uniform dispersion liquid, so that the dispersion liquid is 350 to 450 rpm. It is produced by stirring for 10 to 30 minutes.
The solution of the low temperature gelling agent is dissolved by putting the low temperature gelling agent in a wide-mouthed bottle containing water or hot water and stirring it with a stirrer while keeping the temperature at 90 to 100 ° C. to obtain a uniform dispersion. It is produced by stirring at 350 to 450 rpm for 30 to 60 minutes. The temperature of the solvent is not particularly limited as long as the hot water in which the low-temperature gelling agent is dispersed is heated from a room temperature of 25 ° C. to a temperature at which the low-temperature gelling agent is dissolved.
Then, the dispersion liquid of the above-mentioned methyl cellulose maintained at 90 to 100 ° C. and the solution of the low-temperature gelling agent are stirred using a stirrer to obtain a gelling composition.

On the other hand, in the production method in which methyl cellulose and a low-temperature gelling agent are mixed in a solvent at the same time, methyl cellulose and a low-temperature gelling agent are simultaneously put into a wide-mouthed bottle containing water or hot water and kept at 90 to 100 ° C. It is produced by stirring with a stirrer at 350 to 450 rpm for 30 to 60 minutes until a uniform dispersion is obtained. At this time, it is confirmed by measuring the viscosity of the gelling composition whether or not the low temperature gelling agent is dissolved.

Next, the food containing the gelling composition will be described.
The food containing the gelling composition is not particularly limited, but can be obtained by adding an additive to the gelling composition or mixing it with a food material selected from, for example, vegetables, meat, fish and the like as a cooking ingredient. The content of the gelled composition in the food is preferably 1 to 70% by mass.
For foods containing a gelled composition such as homogeneous jelly-like foods, mousse-like foods, porridge, soft paste-like or jelly-like foods, the above-mentioned ingredients are liquefied or powdered by a mixer, mill, juicer, food processor or the like. , This can be mixed with the above-mentioned gelling composition using a mixing device, filled in a suitable container, and cooled to obtain a food product. In order to sufficiently gel the gelling composition, it is preferable to keep the temperature below the gelling temperature of the low temperature gelling agent and allow it to stand for 1 to 24 hours.

Ingredients such as vegetables, meat and fish are sterilized by heating in advance. The heat sterilization treatment is preferably performed at 70 to 180 ° C. by a direct heating method such as an injection type or an infusion type or an indirect heating method such as a scraping type, in addition to UHT, HTST, LTLT and the like.
Here, examples of the mixing device include a hand mixer, a homogenizer, a colloid mill, a static mixer, an in-line mixer, a disper mill and the like. For example, when using a home-use hand mixer, it is preferable to stir for 20 seconds under the condition of a rotation speed of 500 to 1500 times / minute. However, if the temperature drops below the gelation temperature of the low-temperature gelling agent during mixing, it becomes inhomogeneous, so it is necessary to mix while heating as necessary. Specifically, in gellan gum, gelation starts at 60 to 70 ° C. or lower, and non-uniform lumps are partially formed during mixing. Therefore, it is preferable to mix while heating at 80 ° C. or higher.
In addition, since the jelly food loses its original shape once with a mixer or the like compared to a general food, it is filled in an appropriate container (mold) such as silicone or metal in the shape of vegetables, meat, fish, etc. As a result, the appearance can be made to be the same as that of the actual food.
Further, as a cooling method, after filling in an appropriate container, cooling by allowing to cool, cooling by a refrigerator, and cooling by a quenching plasticizer such as a perfector or a combinator before filling can be mentioned.

The hardness, adhesiveness and cohesiveness of the obtained gelled product or the food containing the same can be measured using a texture analyzer. The hardness obtained by the texture analyzer is an index of the hardness of the gelled product or the food containing the gelled product. In addition, the adhesiveness obtained by the texture analyzer is an index of the stickiness of the gelled product or the food containing the gelled product. In general, the adhesiveness increases as the viscosity increases, but in people who have difficulty eating or swallowing, the increase in viscosity increases the swallowing pressure and the activity of esophageal smooth muscle, so that when eating. The burden will increase. Therefore, an increase in viscosity and adhesiveness is not preferable. If it is highly adherent, food lumps may stick to the mouth. Further, the cohesiveness obtained by the texture analyzer is an index of the ease of cohesion of the gelled product or the food containing the gelled product during chewing. If the cohesiveness is low, the food or the like will not be well organized due to chewing, which will be a burden when swallowed.
As the texture analyzer, for example, a texture analyzer TA-XTplus manufactured by Hidehiro Seiki Co., Ltd. and a small desktop testing machine EZ TEST manufactured by Shimadzu Corporation can be used.

Regarding the physical characteristics of foods suitable for people who have difficulty eating or swallowing, the Ministry of Health, Labor and Welfare has notified the special purpose food permission standards, and they are classified according to the criteria of permission standards 1 to III. Specifically, in the case of a homogeneous jelly-like food, the permission criteria 1 are: hardness of 2,500 to 10,000 ^{N / m 2} , adhesion of 400 J / m ³ or less, and cohesiveness of 0.2 to 0. It is said to be 6. In the case of homogeneous jelly-like or mousse-like foods, the hardness is 1,000 to 15,000 N / m ² , the adhesiveness is 1,000 J / m ³ or less, and the cohesiveness is 0.2 to 0 as the permission standard II. It is said to be 9.9. For foods such as porridge that is inhomogeneous and cohesive, soft paste or aspic, the hardness is 300 to 20,000 N / m ² and the adhesiveness is 1,500 J / m ³ or less as Permit Criteria III. Cohesiveness is classified as no standard.

The water separation during heating is evaluated by the amount of water separated from the gelled composition or the food containing the gelled composition or the oil and fat component contained in the food when heated so that the core temperature of the food becomes 75 ° C. For people who have difficulty eating or swallowing, low-viscosity solutions such as water are less likely to cause swallowing reflexes, causing water and food to enter the lungs through the bronchi and cause serious symptoms such as pneumonia. Become. From the viewpoint of preventing accidental ingestion, the separated amount of the solution is preferably 0 to 0.5 g, more preferably 0 to 0.1 g.

The gelled composition and the food containing the same are not particularly limited, but a microwave oven, a gas microwave oven, an oven, and a dryer are used so that the core temperature of the food is maintained at preferably 75 ° C. for 10 minutes or more before serving. It is heat-treated by baking, frying, steaming, etc. Then, the heat treatment is performed so that the core temperature of the food is preferably 75 to 90 ° C, more preferably 75 to 80 ° C.

Examples of synthesis and comparative synthesis of methylcellulose will be described below, and the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to Synthesis Examples and Examples.
Synthesis example 1
Wood pulp having an intrinsic viscosity of 800 ml / g was pulverized with a pulverizer to obtain powdered cellulose pulp. Of this powdered cellulose pulp, an amount of cellulose pulp corresponding to 6.0 kg in terms of cellulose content was charged into an internal stirring pressure-resistant reactor with a jacket, and vacuum nitrogen was replaced to sufficiently remove oxygen in the reactor.
Next, the inside was stirred while controlling the temperature so that the temperature inside the reactor was 60 ° C., and 49% by mass sodium hydroxide aqueous solution was used as the first alkali metal hydroxide solution, and the first sodium hydroxide was used. Alkaline cellulose was added by adding the first aqueous sodium hydroxide solution at an addition rate of 10.48 [mol / mol · hr] so that the molar ratio of cellulose (first sodium hydroxide / cellulose) was 2.62. And said.
Subsequently, 2.4 kg of dimethyl ether was added, and the temperature was adjusted so that the temperature inside the reactor was maintained at 60 ° C. After the addition of dimethyl ether, the molar ratio of the amount of methyl chloride to the total amount of the first and second sodium hydroxide (methyl chloride / total sodium hydroxide) was 1 while raising the temperature inside the reactor from 60 ° C to 80 ° C. Methyl chloride was added over 60 minutes to give a first reaction mixture. Following the addition of methyl chloride, a 49% by mass sodium hydroxide aqueous solution was used as the second alkali metal hydroxide solution, and the molar ratio of the second sodium hydroxide to cellulose (second sodium hydroxide / cellulose) was determined. A second aqueous sodium hydroxide solution was added at an addition rate of 3.20 [mol / mol · hr] so as to be 1.60 to prepare a second reaction mixture. The temperature inside the reactor at the start of the addition of the second sodium hydroxide solution was 77 ° C, and the temperature inside the reactor at the completion of the addition was 89 ° C. Was heated at 24 ° C./hr. After the preparation of the second aqueous sodium hydroxide solution was completed, stirring was continued for 30 minutes to complete the etherification reaction. The ratio of the mass of the first sodium hydroxide to the total mass of the first and second sodium hydroxides in the first and second sodium hydroxide aqueous solutions was 62.1%.
The obtained second reaction mixture was slurried by adding hot water at 95 ° C., washed with a rotary pressure filter, subsequently dried with a blower dryer, further pulverized with a ball mill, and sieved. After classification, methyl cellulose was obtained. The experimental conditions are shown in Table 1.
The DS of the obtained methyl cellulose was 1.81, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 4,500 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was 4,500 Pa, which was a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 2750 Pa, and the gelation temperature was 43 ° C. The results obtained are shown in Table 1.

Synthesis example 2
Methyl cellulose was obtained in the same manner as in Synthesis Example 1 except that powdered cellulose pulp obtained by pulverizing wood pulp having an intrinsic viscosity of 850 ml / g with a pulverizer was used.
The DS of the obtained methyl cellulose was 1.81, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 5,800 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was 4,750 Pa, which was a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 2,950 Pa, and the gelation temperature was 42 ° C. The results obtained are shown in Table 1.

Synthesis example 3
Methyl cellulose was obtained in the same manner as in Synthesis Example 1 except that powdered cellulose pulp obtained by pulverizing wood pulp having an intrinsic viscosity of 900 ml / g with a pulverizer was used.
The DS of the obtained methyl cellulose was 1.82, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 7,000 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was measured and found to be 5,010 Pa, which is a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 2,900 Pa, and the gelation temperature was 41 ° C. The results obtained are shown in Table 1.

Synthesis example 4
Methyl cellulose was obtained in the same manner as in Synthesis Example 1 except that powdered cellulose pulp obtained by pulverizing wood pulp having an intrinsic viscosity of 1,000 ml / g with a pulverizer was used.
The DS of the obtained methyl cellulose was 1.82, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 7,800 mPa · s.
The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was 5,200 Pa, which was a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 3,150 Pa, and the gelation temperature was 45 ° C. The results obtained are shown in Table 1.

Synthesis example 5
Methyl cellulose was obtained in the same manner as in Synthesis Example 1 except that powdered cellulose pulp obtained by pulverizing wood pulp having an intrinsic viscosity of 1,200 ml / g with a pulverizer was used.
The DS of the obtained methyl cellulose was 1.83, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 9,500 mPa · s.
The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was 5,400 Pa, which was a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 3,300 Pa, and the gelation temperature was 48 ° C. The results obtained are shown in Table 1.

Synthesis example 6
Cellulous pulp was charged into the reactor in the same manner as in Synthesis Example 1, and the inside was stirred while adjusting the temperature so that the temperature inside the reactor was 55 ° C., and 49% by mass sodium hydroxide was used as the first alkali metal hydroxide solution. Using an aqueous solution, the first was added at an addition rate of 12.04 [mol / mol · hr] so that the mass ratio of the first sodium hydroxide to cellulose (first sodium hydroxide / cellulose) was 3.01. An aqueous solution of sodium hydroxide was added to obtain alkaline cellulose.
Subsequently, in the same manner as in Synthesis Example 1, after obtaining the first reaction mixture, the temperature inside the reactor at the start of the addition of the second aqueous sodium hydroxide solution was 81 ° C., and the temperature inside the reactor at the completion of the addition was 89 ° C. Then, from the start of the addition of the second aqueous sodium hydroxide solution to the completion of the addition, the temperature inside the reactor was raised at 16.4 ° C./hr, and the molar ratio of the second sodium hydroxide to cellulose (second). Synthetic except that a second aqueous sodium hydroxide solution is added at an addition rate of 2.58 [mol / mol · hr] to make a second reaction mixture so that sodium hydroxide / cellulose) is 1.26. The procedure was the same as in Example 1. The ratio of the mass of the first sodium hydroxide to the total mass of the first and second sodium hydroxides in the first and second aqueous sodium hydroxide solutions was 70.5%.
Then, the obtained second reaction mixture was purified and pulverized in the same manner as in Synthesis Example 1 to obtain methyl cellulose. The experimental conditions are shown in Table 1.
The DS of the obtained methyl cellulose was 1.85, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 4,200 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was 4,150 Pa, which was a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 2,600 Pa, and the gelation temperature was 42 ° C. The results obtained are shown in Table 1.

Synthesis example 7
Cellulous pulp was charged into the reactor in the same manner as in Synthesis Example 1, and the inside was stirred while adjusting the temperature so that the temperature inside the reactor was 55 ° C., and 49% by mass sodium hydroxide was used as the first alkali metal hydroxide solution. Using an aqueous solution, the first was added at an addition rate of 11.39 [mol / mol · hr] so that the mass ratio of the first sodium hydroxide to cellulose (first sodium hydroxide / cellulose) was 2.85. An aqueous solution of sodium hydroxide was added to obtain alkaline cellulose.
Subsequently, after obtaining the first reaction mixture in the same manner as in Synthesis Example 1, the reaction machine internal temperature at the start of addition of the second sodium hydroxide solution was 79 ° C., and the reaction machine internal temperature at the completion of the addition was 91 ° C. , The temperature inside the reactor is raised at 24 ° C./hr from the start of the addition of the second aqueous sodium hydroxide solution to the completion of the addition, and the molar ratio of the second sodium hydroxide to cellulose (second sodium hydroxide / cellulose). The same procedure as in Synthesis Example 1 was carried out except that a second aqueous sodium hydroxide solution was added at an addition rate of 2.80 [mol / mol · hr] to prepare a second reaction mixture. It was. The ratio of the mass of the first sodium hydroxide to the total mass of the first and second sodium hydroxides in the first and second aqueous sodium hydroxide solutions was 67.0%.
Then, the obtained second reaction mixture was purified and pulverized in the same manner as in Synthesis Example 1 to obtain methyl cellulose. The experimental conditions are shown in Table 1.
Then, the obtained second reaction mixture was purified and pulverized in the same manner as in Synthesis Example 1 to obtain methyl cellulose. The experimental conditions are shown in Table 1.
The DS of the obtained methyl cellulose was 1.82, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 3,200 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0% by mass aqueous solution of methylcellulose at 75 ° C. was measured and found to be 3,400 Pa, which is a 2.0% by mass aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 2,550 Pa, and the gelation temperature was 42 ° C. The results obtained are shown in Table 1.

Synthesis example 8
Cellulose pulp was charged into the reactor in the same manner as in Synthesis Example 1 except that powdered cellulose pulp obtained by crushing wood pulp having an intrinsic viscosity of 600 ml / g with a crusher was used, and the temperature inside the reactor was set to 55 ° C. The inside is stirred while controlling the temperature so as to be, and a 49% by mass sodium hydroxide aqueous solution is used as the first alkali metal hydroxide solution, and the molar ratio of the first sodium hydroxide to the cellulose (the first hydroxide). The first aqueous solution of sodium hydroxide was added at an addition rate of 9.04 [mol / mol · hr] so that sodium / cellulose) became 2.26 to obtain alkaline cellulose.
Subsequently, after obtaining the first reaction mixture in the same manner as in Synthesis Example 1, the temperature inside the reactor at the start of the addition of the second sodium hydroxide solution was set to 80 ° C., and the temperature inside the reactor at the completion of the addition was set to 92 ° C. From the start of the addition of the second aqueous sodium hydroxide solution to the completion of the addition, the temperature inside the reactor is raised at 36 ° C./hr, and the molar ratio of the second sodium hydroxide to cellulose (second sodium hydroxide). / Cellulose) is 1.84, except that a second aqueous sodium hydroxide solution is added at an addition rate of 5.52 [mol / mol · hr] to prepare a second reaction mixture, as in Synthesis Example 1. The same was done. The ratio of the mass of the first sodium hydroxide to the total mass of the first and second sodium hydroxides in the first and second sodium hydroxide aqueous solutions was 55.1%.
Then, the obtained second reaction mixture was purified and pulverized in the same manner as in Synthesis Example 1 to obtain methyl cellulose. The experimental conditions are shown in Table 1.
The DS of the obtained methyl cellulose was 1.85, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 3,100 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was 3,200 Pa, which was a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 2,400 Pa, and the gelation temperature was 40 ° C. The results obtained are shown in Table 1.

Comparative synthesis example 1
Cellulose pulp was charged into the reactor in the same manner as in Synthesis Example 1, and the inside was stirred while adjusting the temperature inside the reactor to 40 ° C., and a 49 mass% sodium hydroxide aqueous solution was used as the first alkali metal hydroxide solution. First water at an addition rate of 7.88 [mol / mol · hr] so that the molar ratio of the first sodium hydroxide to cellulose (first sodium hydroxide / cellulose) is 1.97. An aqueous sodium oxide solution was added, and stirring was continued for another 10 minutes after the addition was completed.
Subsequently, 2.4 kg of dimethyl ether was added, and the temperature inside the reactor was adjusted so as to maintain 40 ° C. After the addition of dimethyl ether, methyl chloride was added in two steps in the same manner as the sodium hydroxide solution. The first methyl chloride was prepared over 25 minutes so that the molar ratio of the first methyl chloride to the first sodium hydroxide (first methyl chloride / first sodium hydroxide) was 1.1. It was added to give the first reaction mixture. After the addition of the first methyl chloride was completed, the temperature inside the reactor was raised from 40 ° C. to 80 ° C. over 40 minutes, and after reaching 80 ° C., stirring and mixing was continued for another 30 minutes.
Subsequently, while maintaining the internal temperature of the reactor at 80 ° C., a 49% by mass sodium hydroxide aqueous solution was used as the second alkali metal hydroxide solution, and the molar ratio of the second sodium hydroxide to cellulose (second). A 49 mass% sodium hydroxide aqueous solution was added at an addition rate of 15.31 [mol / mol · hr] so that sodium hydroxide / cellulose) was 2.55 to prepare a second reaction mixture. The temperature inside the reactor when the second aqueous sodium hydroxide solution was added was 80 ° C., and the temperature inside the reactor when the addition was completed was also 80 ° C. The ratio of the mass of the first sodium hydroxide to the total mass of the first and second sodium hydroxide in the first and second sodium hydroxide aqueous solutions is 43.6%.
Met.
Subsequently, while maintaining the internal temperature of the reactor at 80 ° C., the molar ratio of the second methyl chloride to the second methyl chloride and the second sodium hydroxide (second methyl chloride / second hydroxide) Sodium) was added over 30 minutes to a ratio of 1.1. After the addition of the second methyl chloride, the mixture was further stirred and mixed for 30 minutes while maintaining the internal temperature of the reactor at 80 ° C. Then, the temperature of the reactor was raised from 80 ° C. to 95 ° C. over 15 minutes to obtain crude methyl cellulose.
Then, the obtained crude methyl cellulose was purified and pulverized in the same manner as in Synthesis Example 1 to obtain methyl cellulose.
The DS of the obtained methyl cellulose was 1.85, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 5,000 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0% by mass aqueous solution of methyl cellulose at 75 ° C. was 5,100 Pa, which was a 2.0% by mass aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 3,850 Pa, and the gelation temperature was 34 ° C. The results obtained are shown in Table 1.

Comparative synthesis example 2
Cellulous pulp was charged into the reactor in the same manner as in Synthesis Example 4, and the inside was stirred while adjusting the temperature so that the temperature inside the reactor was 60 ° C., and 49% by mass sodium hydroxide was used as the first alkali metal hydroxide solution. Using an aqueous solution, the first was added at an addition rate of 16.44 [mol / mol · hr] so that the molar ratio of the first sodium hydroxide to cellulose (first sodium hydroxide / cellulose) was 4.11. An aqueous solution of sodium hydroxide was added to obtain alkaline cellulose.
Subsequently, after obtaining the first reaction mixture in the same manner as in Synthesis Example 4, the temperature inside the reactor at the start of the addition of the second aqueous sodium hydroxide solution was set to 80 ° C, and the temperature inside the reactor at the completion of the addition was set to 91 ° C. , The temperature inside the reactor is raised at 22 ° C./hr from the start of the addition of the second aqueous sodium hydroxide solution to the completion of the addition, and the molar ratio of the second sodium hydroxide to cellulose (second sodium hydroxide / cellulose). The same procedure as in Synthesis Example 1 was carried out except that a second aqueous sodium hydroxide solution was added at an addition rate of 0.92 [mol / mol · hr] to prepare a second reaction mixture. It was. The ratio of the mass of the first sodium hydroxide to the total mass of the first and second sodium hydroxides in the first and second sodium hydroxide aqueous solutions was 89.9%.
Then, the obtained second reaction mixture was purified and pulverized in the same manner as in Synthesis Example 1 to obtain methyl cellulose. The experimental conditions are shown in Table 1.
The DS of the obtained methyl cellulose was 1.82, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 4,000 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was measured to be 2,500 Pa, which is a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 1100 Pa, and the gelation temperature was 62 ° C. The results obtained are shown in Table 1.

Comparative synthesis example 3
Methyl cellulose was obtained in the same manner as in Comparative Synthesis Example 2 except that powdered cellulose pulp obtained by pulverizing wood pulp having an intrinsic viscosity of 1,400 ml / g with a pulverizer was used.
The DS of the obtained methyl cellulose was 1.82, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. by the B-type viscometer was 12,000 mPa · s. The storage elastic modulus G'(75 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose at 75 ° C. was 2,700 Pa, which was a 2.0 mass% aqueous solution of the return temperature when returning from 75 ° C. to 45 ° C. When the storage elastic modulus G'(75 → 45 ° C.) was measured, it was 1300 Pa, and the gelation temperature was 64 ° C. The results obtained are shown in Table 1.

Example 1
Adjust the temperature of 100 g of water in a 100 mL beaker to 95 ° C. with a bus stirrer (ES-100 RD manufactured by AS ONE), and stir with a stirrer (NZ-1000 manufactured by Tokyo Rika Kikai Co., Ltd.) at a condition of 500 times / minute. As a low-temperature gelling agent, 1 g of gellan gum (manufactured by DSP Gokyo Food & Chemical Co., Ltd.) and 1 g of methyl cellulose obtained in Synthesis Example 1 were added and stirred for 60 minutes. A solution in which a low-temperature gelling agent and methyl cellulose were mixed was filled in a cylindrical stainless steel container having a diameter of 40 mm and a height of 20 mm up to a height of 15 mm. The filled solution was allowed to stand in a refrigerator at 10 ° C. for 2 hours to obtain a gelled product. The obtained gelled product was quantitatively evaluated by the texture analyzer shown below (hardness, adhesiveness, cohesiveness) and sensory evaluation by 10 evaluators (shape retention, stickiness during chewing and chewing property). Was done. As for the water separation, the gelled product in the stainless steel container is used both when the core temperature of the gelled product is heated to 75 ° C. and when the core temperature of the gelled product reaches 45 ° C. after being allowed to stand at room temperature from 75 ° C. The solution that exuded to the surface when tilted was transferred to a petri dish and evaluated by measuring the mass. The results are shown in Table 2.

<Quantitative evaluation by texture analyzer: hardness, adhesiveness, cohesiveness>
The hardness, adhesiveness and cohesiveness of the gelled product in the stainless steel container were measured using a texture analyzer TA-XTplus (manufactured by Eiko Seiki Co., Ltd.). Specifically, when the core temperature of the gelled product was heated to 75 ° C., it was allowed to stand at room temperature from 75 ° C., and the measurement was performed in both cases where the core temperature of the gelled product reached 45 ° C. As a heating method, the gelled product in the stainless steel container was heated at 120 ° C. for 10 minutes with a blower dryer to bring the core temperature of the gelled product to 75 ° C. As a result, the hardness of the gelled product at a core temperature of 75 ° C. was 8,900 N / m ² , the adhesiveness was 150 J / m ³ , and the cohesiveness was 0.86. In addition, the gelled product has good shape retention without losing its shape, and the separation amount (water separation at 75 ° C.) of the solution exuded to the surface when the gelled product in the stainless steel container is tilted is 0.05 g. Met.
On the other hand, the hardness of the gelled product at a core temperature of 45 ° C. was 5,600 N / m ² , adhesiveness ^{was 160 J / m 3} , and cohesiveness was 0.88. Further, the gelled product has good shape retention without losing its shape, and the separation amount (water separation at 45 ° C.) of the solution exuded to the surface when the gelled product in the stainless steel container is tilted is 0 g. No liquid separation was observed.
The measurement conditions of the texture analyzer are as follows.
Measuring equipment: Texture analyzer TA-XTplus (manufactured by Hidehiro Seiki Co., Ltd.)
Measuring instrument: Circular type 20 mm in diameter, 8 mm in height Resin probe (P / 20 type)
Measurement mode: Compression test (compression twice)
Test speed: 10 mm / sec Clearance: 5 mm

<Sensory evaluation by 10 evaluators: shape retention, stickiness during chewing and chewing property>
The obtained gelled product and gelled food were evaluated not only by the above-mentioned texture analyzer but also by sensory evaluation by 10 evaluators.
The shape retention of the gelled composition was evaluated by 10 evaluators visually and by direct contact with the obtained gelled product. In addition, the sticky feeling and chewability of the gelled product at the time of chewing were evaluated by chewing the obtained gelled product by 10 evaluators. The sticky feeling at the time of chewing was judged by whether or not there was a feeling of sticking to the mouth at the time of chewing. Regarding chewability, it was judged whether or not it was necessary to chew many times when swallowing because it felt elasticity when chewing.
Each evaluation is performed in three stages of ○, Δ, and ×, and the evaluation criteria are as follows.
◯: 80% or more is evaluated as good △: 50% or more and less than 80% is evaluated as good ×: Less than 50% is evaluated as good

Example 2
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Synthesis Example 2 was used. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 3
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Synthesis Example 3 was used. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 4
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Synthesis Example 4 was used. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 5
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Synthesis Example 5 and agar (ultra-agar for long-term care food manufactured by Ina Food Industry Co., Ltd.) was used as a low-temperature gelling agent. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 6
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Synthesis Example 6 and agar (Ultra agar for long-term care edible by Ina Food Industry Co., Ltd.) were used as a low-temperature gelling agent. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 7
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Synthesis Example 7 and gelatin (manufactured by Wako Pure Chemical Industries, Ltd., gel strength 240 to 280 g / cm ^{2) were used as a low-temperature gelling agent.} .. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 8
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Synthesis Example 8 and gelatin (manufactured by Wako Pure Chemical Industries, Ltd., gel strength 240 to 280 g / cm ^{2) were used as a low temperature gelling agent.} .. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 9
Before gelling the low-temperature gelling agent in a refrigerator, the gelling composition obtained in Example 1 and the cooked spinach were crushed with a mixer to a solution state without solid content, and the solution was heated to 95 ° C. 1: The mixture was mixed at a ratio of 1 (mass ratio). The mixed solution was poured into a silicone mold, molded, and allowed to stand in a refrigerator at 10 ° C. for 2 hours to obtain a gelled product in the form of vegetables (that is, a gelled food). The gelled food was taken out from the mold, and various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 10
A meat-form gelled product (ie, gelled food) was obtained in the same manner as in Example 9 except that corned beef was used instead of the cooked spinach of Example 9. The gelled food was taken out from the mold, and various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Example 11
A fish-like gelled product (that is, a gelled food) was obtained in the same manner as in Example 9 except that mackerel boiled in water was used instead of the cooked spinach of Example 9. The gelled food was taken out from the mold, and various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.

Comparative Example 1
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Comparative Synthesis Example 1 was used. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.
Various physical properties of the gelled product obtained in Comparative Example 1 have a storage elastic modulus G'(75 → 45 ° C.) of 3850 Pa, which is larger than that of the present invention. Therefore, when the core temperature of the gelled product is 45 ° C., the hardness and cohesiveness are increased, and the chewability is deteriorated. It did not meet the requirements for homogeneous jelly-like or mousse-like foods of Permit Criterion II in the physical characteristics of foods suitable for people with eating or swallowing difficulties.

Comparative Example 2
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Comparative Synthesis Example 2 was used. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.
As for various physical properties of the gelled product obtained in Comparative Example 2, the storage elastic modulus G'(75 ° C.) and the storage elastic modulus G'(75 → 45 ° C.) of a 2.0 mass% aqueous solution of methyl cellulose are both in the present invention. Since it was out of the range of 1), sufficient shape retention was not obtained when heated to 75 ° C., and the shape of the gelled product could not be maintained.

Comparative Example 3
A gelled product was produced in the same manner as in Example 1 except that the methyl cellulose obtained in Comparative Synthesis Example 3 was used. With respect to the obtained gelled product, various physical properties were measured at various temperatures using a texture analyzer in the same manner as in Example 1, and sensory evaluation and water separation evaluation were performed by 10 evaluators. The results are shown in Table 2.
As for various physical properties of the gelled product obtained in Comparative Example 3, sufficient shape retention was not obtained when heated to 75 ° C., and after heating to 75 ° C., the gelled product was allowed to stand at room temperature to form a gelled product at 45 ° C. The adhesiveness at the time was 1,600 J / m ³ or more, and the gelled product had high adhesiveness.

From the results of Examples 1 to 11 and Comparative Examples 1 to 3, the hardness, adhesiveness and cohesiveness by the texture analyzer, the shape retention by the sensory evaluation by 10 evaluators, the sticky feeling at the time of chewing and the chewability. And the water separation was compared.
When the storage elastic modulus G'(75 ° C.) of methylcellulose is within the range of the present invention, the evaluator also retains the shape retention when the gelled composition and the food containing the gelled composition are heated to 75 ° C. or higher. is there. On the other hand, if the storage elastic modulus G'(75 → 45 ° C.) of methylcellulose does not meet the lower limit of the present invention when it is heated to 75 ° C. and then allowed to stand at room temperature to reach 45 ° C., the evaluator has a shape retention property. not enough. Furthermore, when the storage elastic modulus G'(75 → 45 ° C.) of methylcellulose exceeds the upper limit of the present invention, the evaluator feels elasticity at the time of chewing and finds it difficult to swallow, which is suitable for people who have difficulty eating or swallowing. Absent. Further, when the viscosity of the 2.0% by mass aqueous solution at 20 ° C. exceeded the upper limit of the present invention, more than half of the evaluators felt a sticky feeling at the time of chewing.
In this way, it is possible to quantitatively judge the result of the sensory evaluation by 10 evaluators based on the hardness, adhesiveness and cohesiveness obtained from the texture analyzer.
The present application is a divisional application with Japanese Patent Application No. 2016-110401 as the original application, and the claims of the original application immediately before the division are described as follows.
[Claim 1] The storage elastic modulus G'(75 ° C.) of the 2.0% by mass aqueous solution at 75 ° C. is 3,000 to 5,500 Pa, and the return temperature when returning from 75 ° C. to 45 ° C. The storage elastic modulus G'(75 → 45 ° C.) of the 0 mass% aqueous solution is 2,000 to 3,600 Pa, and the viscosity of the 2.0 mass% aqueous solution at 20 ° C. is 3,000 to 10,000 mPa · s. A gelling composition containing at least 0.05 to 10% by mass of a certain methyl cellulose, 0.05 to 30% by mass of a low-temperature gelling agent, and 1 to 99% of a solvent.
2. The gelling composition according to claim 1, wherein the gelation temperature of the 2.0 mass% aqueous solution of methyl cellulose is 40 to 55 ° C.
3. The gelling composition according to claim 1, wherein the average degree of substitution (DS) of methoxy groups per glucose unit of the methyl cellulose is 1.61 to 2.03.
4. The gelling composition according to claim 1, wherein the low-temperature gelling agent is one or more gelling agents selected from gelatin and polysaccharides.
[Claim 5] A food containing the gelling composition according to any one of claims 1 to 4.

Claims (4)

The storage elastic modulus G'(75 ° C.) of the 2.0% by mass aqueous solution at 75 ° C. is 3,000 to 5,500 Pa, and the return temperature of the 2.0% by mass aqueous solution when returning from 75 ° C. to 45 ° C. storage modulus G '(75 → 45 ℃) is 2,000～3,300Pa, and 20 the viscosity of 2.0% by weight aqueous solution at ° C. is a methylcellulose is 3,000~10,000mPa · s Methyl cellulose having an average degree of substitution (DS) of methoxy groups per glucose unit of the methyl cellulose of 1.74 to 2.03 . The methylcellulose according to claim 1, wherein the gelation temperature of the 2.0% by mass aqueous solution of methylcellulose is 40 to 55 ° C. The food additive containing methyl cellulose according to claim 1 or 2. The food containing the methyl cellulose according to claim 1 or 2.