WO2024014033A1 - Method for producing granules, and granules - Google Patents

Abstract

The present invention pertains to a method for producing granules which is equipped with: a step for mixing a solvent and one or more types of starting material selected from the group consisting of a crystalline sugar and a crystalline sugar alcohol, and obtaining a crystalline suspension in which some of the starting material is contained in a crystal state, without melting all the starting material and then crystallizing the melted starting material; and a step for spray-drying the crystalline suspension in low temperature conditions.

Description

Method for manufacturing granules and granules

The present invention relates to a method for producing granules and granules.

In the production of foods, pharmaceuticals, etc., it is extremely important to maintain the stability and ease of handling (fluidity) of materials in anticipation of various environmental changes such as temperature and humidity. Powderization is a method for maintaining the stability and fluidity of materials, and one method for powderization is spray drying.

Spray drying is a method of spraying a solution or suspension into a gas and rapidly drying it to obtain a dry powder. The drying temperature during spray drying is generally high. Enzymes, yeast, and microbial cells are denatured and deactivated by contact with high-temperature gases, and volatile fragrances easily evaporate, making it difficult to sufficiently retain their original properties. From the viewpoint of preventing such losses due to spray drying, proposals have been made so far (for example, Patent Document 1).

JP2021-106571A

Produce granules containing crystalline sugar and/or crystalline sugar alcohol, in which amorphous sugar and/or sugar alcohol are held in the gaps formed between the crystalline sugar and/or sugar alcohol. In order to achieve this, from the viewpoints of stability as crystals, ease of drying during spray drying of granules, and stability/flowability after spray drying, spray drying is carried out after completely dissolving the sugar and/or sugar alcohol. It is considered important to precipitate the crystals again beforehand. Therefore, when producing a suspension used for spray drying, the raw material sugar and/or sugar alcohol is completely dissolved, heated and cooled, and some crystals are precipitated again (crystal precipitation method). ) has been adopted. However, such a crystal precipitation method requires a complicated process and is difficult to implement if a device for crystal precipitation is not available. Furthermore, the precipitation operation may generate not only crystals of the desired size but also a large number of microcrystals, which may reduce the recovery rate of granules after spray drying.

One aspect of the present invention aims to provide a simple and efficient method for producing granules and granules obtained by the method.

The present invention provides the following inventions.
[1]
It contains at least one kind of raw material selected from the group consisting of crystalline sugar and crystalline sugar alcohol, and a part of the raw material is dissolved without dissolving all of the raw material and crystallizing the raw material after the dissolution. obtaining a crystal suspension containing in a crystalline state;
A method for producing granules, comprising the step of spray drying the crystal suspension under low temperature conditions.
[2]
The method according to [1], wherein the sugar and the sugar alcohol are monosaccharides, disaccharides, trisaccharides, and sugar alcohols thereof.
[3]
The method according to [1] or [2], wherein the raw material is at least one selected from the group consisting of palatinose, sucrose, and trehalose.
[4]
The method according to any one of [1] to [3], wherein the spray drying is performed at an inlet temperature of 0 to 60°C.
[5]
The method according to any one of [1] to [4], wherein the crystal suspension further contains a functional material.
[6]
The method according to [5], wherein the functional material is an enzyme, a microorganism, or a fragrance.
[7]
The method according to any one of [1] to [6], wherein the crystal suspension has a viscosity of 50 to 1550 mPa·s at 25°C.
[8]
The method according to any one of [1] to [7], wherein the crystalline sugar and/or sugar alcohol in the crystal suspension has an average particle size of 1.0 to 15.9 μm.
[9]
The method according to any one of [1] to [8], wherein the standard deviation of the average particle size of the crystalline sugar and/or sugar alcohol in the crystal suspension is 1.00 to 10.70 μm.
[10]
The method according to any one of [1] to [9], wherein the ratio of the average major axis to the average minor axis of the crystalline sugar and/or sugar alcohol in the crystal suspension is 1.00 to 1.70. .
[11]
The method according to any one of [1] to [10], wherein the ratio of the average major axis to the average minor axis of the particles constituting the granules is 1.00 to 3.10.
[12]
The method according to any one of [1] to [11], wherein the degree of caking of the granules is less than 10.0% by mass.
[13]
Granules containing at least one selected from the group consisting of crystalline sugar and crystalline sugar alcohol,
A part of the sugar and/or the sugar alcohol is in a crystalline state and the other part is in an amorphous state, and the ratio of the average major axis to the average minor axis of the particles constituting the granules is 3.1 or less. Granules.
[14]
The granule according to [13], wherein the sugar and the sugar alcohol are monosaccharides, disaccharides, trisaccharides, and sugar alcohols thereof.
[15]
The granule according to [13] or [14], wherein at least one selected from the group consisting of crystalline sugar and crystalline sugar alcohol is at least one selected from the group consisting of palatinose, sucrose, and trehalose.
[16]
The granule according to any one of [13] to [15], further containing a functional material.
[17]
The granule according to [16], wherein the functional material is an enzyme, a microorganism, or a fragrance.
[18]
The granules according to any one of [13] to [17], wherein the particles constituting the granules have an average particle diameter of 10.00 to 20.00 μm.
[19]
The granule according to any one of [13] to [18], wherein the standard deviation of the average particle diameter of the particles constituting the granule is 1.00 to 3.30 μm.
[20]
The granule according to any one of [13] to [19], wherein the degree of caking of the granule is less than 10.0% by mass.

According to one aspect of the present invention, it is possible to provide a method for easily and efficiently producing granules, and granules obtained by the method.

(A) shows a microscopic image of a crystal suspension obtained by the method of Example 1, and (B) shows a microscopic image of a crystal suspension obtained by the method of Comparative Example 1. (A) shows an electron microscope image of the granules obtained by the method of Example 3, and (B) shows an enlarged image of (A). (A) shows an electron microscope image of granules obtained by the method of Comparative Example 3, and (B) shows an enlarged image of (A). (A) shows the evaluation results of the hygroscopicity of the granules obtained by the method of Example 3, and (B) shows the evaluation results of the hygroscopicity of the granules obtained by the method of Comparative Example 3.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples.

<Method for producing granules>
The method for producing granules according to the present embodiment includes at least one type of raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols, and includes dissolving all of the raw materials and crystallizing the raw materials after the dissolution. The method includes a step (mixing step) of obtaining a crystal suspension in which a part of the raw material is contained in a crystalline state without performing the above steps, and a step of spray drying the crystal suspension under low temperature conditions (spray drying step).

<Mixing process>
In the mixing step, first, a crystal suspension containing at least one type of raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols and containing a portion of the raw material in a crystalline state is obtained.

As used herein, the term "crystalline sugar and/or sugar alcohol" means a solid sugar and/or sugar alcohol whose constituent atoms are three-dimensionally regularly repeated. As used herein, "sugar and/or sugar alcohol in an amorphous state" refers to a solid or liquid sugar and/or sugar alcohol that does not have such regular repeats.

The crystalline sugar and crystalline sugar alcohol are preferably monosaccharides, disaccharides, trisaccharides, and sugar alcohols thereof from the viewpoint of improving operability in the mixing step.

Examples of monosaccharides include glucose, galactose, mannose, fructose, allose, and allulose. Disaccharides include isomaltulose, sucrose, lactulose, lactose, maltose, trehalose, cellobiose, and the like. Trisaccharides include nigerotriose, maltotriose, raffinose, and the like. Isomaltulose is a disaccharide trademarked as "palatinose" by Mitsui Sugar Co., Ltd.

Examples of sugar alcohols include sorbitol, erythritol, xylitol, maltitol, lactitol, mannitol, α-glucopyranosyl-1,1-mannitol, α-glucopyranosyl-1,6-sorbitol, and the like.

The above-mentioned crystalline sugars and sugar alcohols may be used alone or in combination of two or more. The crystal suspension may contain two or more types of crystalline sugars, may contain two or more types of crystalline sugar alcohols, or may contain a combination of crystalline sugars and crystalline sugar alcohols. Two or more types may be contained. Although the method for producing granules according to this embodiment is a simple method, the average shortness of the particles constituting the granules can be obtained even when two or more types of crystalline sugars and alcohols are used (for example, when two types of sugars are used). Granules having a sufficiently small ratio of average major axis to diameter (for example, 3.1 or less) can be obtained. Granules in which the ratio of the average major axis to the average minor axis of the constituent particles is sufficiently small tend to have excellent stability and fluidity.

The content of crystalline sugar and/or sugar alcohol contained in the crystal suspension is preferably 30% by mass or more, based on the total amount of the crystal suspension, from the viewpoint of making it easier to obtain granules with excellent fluidity. The content is 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more. From the viewpoint of maintaining good operability in the mixing step and spray drying step, the content of crystalline sugar and/or sugar alcohol is preferably 90% by mass or less, more preferably 80% by mass or less, based on the total amount of crystal suspension. It is not more than 70% by mass, more preferably not more than 70% by mass.

The supernatant Brix value (Bx) of the crystal suspension is 20.00 or more, 25.00 or more, 27.00 or more, 29.00 or more, or 31.00 or more, from the viewpoint of making it easier to obtain granules with excellent fluidity. 85.00 or less, 75.00 or less, 65.00 or less, 55.00 or less, 45.00 or less, 40.00 or less, from the viewpoint of maintaining good operability in the mixing process and spray drying process. Or it may be 35.00 or less.

The Brix value (Bx) in this specification means the Ref Brix value calculated from the refractive index, and can be measured with a Brix meter (for example, a digital refractometer (RX-5000), manufactured by Atago Co., Ltd.). The method for measuring the supernatant Brix value of the crystal suspension is as described in Examples below.

From the viewpoint of making it easier to obtain granules with excellent fluidity, the crystallization rate of the crystal suspension is 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass. The content may be 55% by mass or more, or 60% by mass or more. From the viewpoint of maintaining good operability in the spray drying process, the crystallization rate may be 90% by mass or less, 85% by mass or less, 80% by mass or less, or 78% by mass or less. The crystallization rate in this specification is measured by the method described in the Examples below.

The crystallization rate can be determined by performing operations that physically or chemically add or remove crystals, such as filter filtration, centrifugation, gravity sedimentation, dissolution by adding water and/or heating, and adjusting consumption of crystal components due to chemical reactions. It can be adjusted by Adjustments can also be made by operations that increase the number of crystals, such as adding and mixing crystal components.

The crystal suspension only needs to contain crystal nuclei, and the size of the crystal nuclei is not particularly limited as long as it is a size that can stably exist in the crystal suspension. The size of the crystal nucleus may be, for example, larger than the critical crystal nucleus.

The viscosity of the crystal suspension is 1550 mPa at 25°C, since the decrease in the recovery rate of granules after spray drying is further suppressed and the occurrence of caking of granules after spray drying is further suppressed. s or less, 1400 mPa・s or less, 1300 mPa・s or less, 1200 mPa・s or less, 1100 mPa・s or less, 1000 mPa・s or less, 900 mPa・s or less, 800 mPa・s or less, 700 mPa・s or less, 600 mPa・s or less, or 500 mPa・It may be 50 mPa・s or more, 100 mPa・s or more, 200 mPa・s or more, 300 mPa・s or more, 400 mPa・s or more, 500 mPa・s or more, 600 mPa・s or more, 700 mPa・s or more, 800 mPa・s s or more, 900 mPa·s or more, 1000 mPa·s or more, or 1100 mPa·s or more. The viscosity of the crystal suspension may be from 50 to 1550 mPa·s at 25°C. The viscosity of the crystal suspension is measured by the method described in Examples below.

From the viewpoint of maintaining the fluidity of the granules, the average particle size of the crystalline sugar and/or sugar alcohol in the crystal suspension is 1.00 μm or more, 2.00 μm or more, 3.00 μm or more, 4.00 μm or more, It may be 5.00 μm or more, 6.00 μm or more, 7.00 μm or more, 8.00 μm or more, 9.00 μm or more, 10.00 μm or more, 11.00 μm or more, or 12.00 μm or more. The average particle diameter of the sugar and/or sugar alcohol in the crystalline state is 30.00 μm or less, 25.00 μm or less, 20.00 μm or less, 18.00 μm or less, 15.90 μm from the viewpoint of further suppressing the occurrence of granule collapse. Below, it may be 14.00 μm or less, 13.00 μm or less, 12.00 μm or less, or 11.00 μm or less. The average particle size of the crystalline sugar and/or sugar alcohol may be, for example, 1.00 to 15.90 μm.

The average particle size of the crystalline sugar and/or sugar alcohol in the crystal suspension can be determined by adding or removing a solvent or solute, changing the solvent temperature, dissolution time, stirring time, crushing with a stirrer or grinder, filtration, etc. It can be adjusted by crystallization operations such as sugar hydrolysis.

In this specification, the "average particle size of sugar and/or sugar alcohol in a crystalline state" can be measured with a digital microscope. For the measurement, for example, SKM-S31B-PC manufactured by Saito Optical Co., Ltd. can be used. The details of the method for measuring the average particle size are as described in the Examples below.

The standard deviation of the average particle size of the crystalline sugar and/or sugar alcohol in the crystal suspension is 10.70 μm or less, 9.00 μm or less, 8.00 μm or less, 7.00 μm or less, or 6.00 μm or less. It's good to be there. A small standard deviation of the average particle size means that the variation in the average particle size is small. By having the standard deviation of the average particle size within the above range, excessive viscosity increase can be easily suppressed, which further suppresses the adhesion of granules inside the spray dryer, and as a result, the recovery rate is further improved. Improved. The standard deviation of the average particle size of the crystalline sugar and/or sugar alcohol in the crystal suspension may be, for example, 1.0 μm or more, 3.0 μm or more, or 5.0 μm or more. The standard deviation of the average particle size of the crystalline sugar and/or sugar alcohol in the crystal suspension may be, for example, 1.00 to 10.70 μm.

In this specification, "standard deviation" refers to Microsoft (registered trademark) Excel's STDEV. This is the unbiased standard deviation obtained using the S function.

The average minor axis of the crystalline sugar and/or sugar alcohol in the crystal suspension may be 1.00 μm or more, 4.00 μm or more, 6.00 μm or more, or 8.00 μm or more, and 20.00 μm or less. , 15.0 μm or less, or 13.0 μm or less. The average major axis of the crystalline sugar and/or sugar alcohol in the crystal suspension may be 5.00 μm or more, 7.00 μm or more, or 9.00 μm or more, and 30.00 μm or less, 25.00 μm or less, Or it may be 20.00 μm or less.

From the viewpoint of maintaining the fluidity and stability of the granules, the ratio of the average major axis (unit: μm) to the average minor axis (unit: μm) of the sugar and/or sugar alcohol in the crystalline state in the crystal suspension is set to 5. 00 or less, 2.50 or less, 2.00 or less, 1.70 or less, or 1.50 or less, and may be 1.00 or more, 1.10 or more, or 1.15 or more. The ratio of the average major axis to the average minor axis may be, for example, 1.00 to 1.70. The standard deviation of the ratio of the average major axis (unit: μm) to the average minor axis (unit: μm) of the crystalline sugar and/or sugar alcohol in the crystal suspension is 0.50 or less, 0.45 or less, or It may be 0.40 or less, 0.05 or more, 0.10 or more, or 0.15 or more.

The crystal suspension contains a solvent. The solvent may be, for example, an organic solvent such as ethanol, methanol, acetone, isopropanol, or water.

The content of the solvent in the crystal suspension is 10% by mass or more, 20% by mass or more, or 30% by mass or more, based on the total mass of the solvent and raw materials, or based on the total mass of the crystal suspension. It may be 50% by mass or less, or 45% by mass or less.

The above-mentioned crystal suspension may be used as it is as a crystal suspension (spray liquid) to be spray-dried, or may be used as a spray liquid after being mixed with other components. Other components include sugars, sugar alcohols, solvents, functional materials, and mixtures thereof.

A functional material is not limited to any material or component that exhibits a certain function in a composition (for example, food, medicine, etc.) obtained by combining it with other materials. Functional materials may be materials that are affected by the surrounding environment such as moisture, heat, light, acids, oxygen, molecular movement, ultraviolet light, electrical interactions, physical stimulation, or even materials that lose their functionality when heated. good. More specifically, functional materials include amino acids, peptides (including hormones), proteins (including enzymes and antibodies), fatty acids, vitamins, minerals, microorganisms (for example, lactic acid bacteria, butyric acid bacteria, Bacillus natto, Bifidobacterium and Bacteria such as actinomycetes, molds and yeast), hormones other than peptides, fragrances, phages, antibiotics other than peptides, natural raw materials such as crude drugs, and industrial raw materials such as metals.

A crystal suspension (spray liquid) to be spray-dried is produced by mixing at least one kind of raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols with a solvent, so that some of the raw materials are crystallized. A step (Step A) of obtaining a crystal suspension A in which a part of the raw material is contained in a crystal state (step A), and a crystal suspension in which a part of the raw material is contained in a crystal state by mixing the crystal suspension A and a sugar solution and is spray-dried. It can be obtained by a method including a step (step B) of obtaining a suspension liquid B (spray liquid).

The mixing of the raw material and the solvent in step A is carried out so that the Brix value (Bx) may be 40 or more, 50 or more, 55 or more, or 60 or more, and 85 or less, 75 or less, or 70 or less. good.

In step A, crystal suspension A can be obtained, for example, by mixing raw materials and a solvent and stirring the resulting mixture for 1 to 3 hours while maintaining the temperature at 25 to 35 ° C. can. The rotation speed during stirring may be, for example, 250 to 400 rpm.

In crystal suspension A, supernatant Brix value, crystallization rate, average particle diameter of sugar and/or sugar alcohol in crystalline state, average major axis, average minor axis, ratio of average major axis to average minor axis, and standard deviation thereof The specific embodiments may be the same as those exemplified as the specific embodiments of the crystal suspension described above.

In step B, crystal suspension A and sugar solution are mixed. Mixing of crystal suspension A and sugar solution may be carried out while maintaining the temperature at 25-35°C.

The sugar solution contains sugar and/or sugar alcohol and a solvent. Part or all of the sugar and sugar alcohol contained in the sugar solution may be dissolved in a solvent. As the sugar and sugar alcohol, those mentioned above can be used. The sugar solution may contain one or more sugars and/or sugar alcohols. The sugar and/or sugar alcohol in the sugar solution may contain the same kind of sugar and/or sugar alcohol as the sugar and/or sugar alcohol in the crystal suspension A, or may contain a different kind.

A sugar solution can be obtained, for example, by mixing sugar and/or sugar alcohol and a solvent. The sugar solution may be obtained by mixing sugar and/or sugar alcohol with a solvent to dissolve the sugar and/or sugar alcohol at a temperature of 80° C. or higher. The sugar solution may be kept at 25-35°C after preparation.

The Brix value (Bx) of the sugar solution may be 50 or more, 55 or more, or 60 or more, and may be 85 or less, 75 or less, or 70 or less.

The mixing amount of the sugar solution may be 5 parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more, and 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or more, based on 100 parts by mass of the crystal suspension. It may be less than parts by mass.

Crystal suspension B contains a portion of at least one raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols in a crystalline state. The crystal suspension B can be directly spray-dried as a spray liquid.

Specifics of the supernatant Brix value, crystallization rate, average particle diameter of sugar and/or sugar alcohol in a crystalline state, average major axis, average minor axis, ratio of average major axis to average minor axis, and standard deviation of these in the spray liquid. The specific embodiments may be the same as or different from those exemplified as the specific embodiments of the crystal suspension described above.

The content of sugar and/or sugar alcohol in the spray liquid is 40% by mass or more, 50% by mass or more, or 60% by mass, based on the total mass of the solvent and raw materials, or based on the total mass of the crystal suspension. % or more, and may be 90% by mass or less, 80% by mass or less, or 70% by mass or less.

The spray liquid includes a first sugar raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols, and a first sugar raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols; A second sugar raw material different from the sugar raw material may be contained. The first sugar raw material may be, for example, isomaltulose. The second sugar raw material may contain one or more of the above-mentioned sugars or sugar alcohols, as long as they are different from the first sugar raw material, and may contain sucrose.

The content of the first sugar raw material is 70.0 parts by mass or more, 75.0 parts by mass or more, 80.0 parts by mass or more, 85.0 parts by mass or more with respect to 100 parts by mass of solids in the spray liquid. , 90.0 parts by mass or more, or 95.0 parts by mass or more, and 99.9 parts by mass or less, 95.0 parts by mass or less, or 90.0 parts by mass or less. As used herein, "solid content" refers to the total amount of the composition excluding the amount of solvent (eg, water).

When the spray liquid contains the first sugar raw material and the second sugar raw material, the content of the second sugar raw material is 1.0 parts by mass or more, 3 parts by mass or more based on 100 parts by mass of solids in the spray liquid. .0 parts by mass or more, 5.0 parts by mass or more, 8.0 parts by mass or more, 10.0 parts by mass or more, 12.0 parts by mass or more, or 15.0 parts by mass or more, and 30.0 parts by mass parts by weight or less, 25.0 parts by weight or less, 20 parts by weight or less, 15 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

When preparing a spray liquid containing a functional material, the timing of incorporating the functional material into the spray liquid is not particularly limited, but for example, after premixing the functional material and the sugar solution to prepare a mixed liquid, A spray liquid may be obtained by mixing the liquid mixture and crystal suspension A.

The content of the functional material may be 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.1 parts by mass or more, and 5 parts by mass or less, based on 100 parts by mass of the above-mentioned crystal suspension. , 3 parts by weight or less, or 1 part by weight or less. The amount of functional material added can be adjusted as appropriate depending on the type of functional material.

In the mixing step, all the raw materials are not dissolved and the raw materials are not crystallized after all the raw materials have been dissolved. Dissolution of all the raw materials can be confirmed visually, for example. Other methods for confirming the dissolution of all raw materials include, for example, observing crystallization induction using a microscope. When the crystal suspension dropped onto the slide glass is observed for 5 minutes using a microscope at room temperature of 25° C., it can be determined that all the raw materials have been dissolved if no crystal precipitation is observed.

Dissolution of all the raw materials is usually performed by heating a liquid containing the raw materials and a solvent, mixing the heated solvent and the raw materials, etc. The temperature of the liquid during heating or the temperature of the heated solvent is not particularly limited, and may be, for example, 70°C or higher or 75°C or higher, and 100°C or lower. In the above-mentioned mixing step, when preparing a crystal suspension, the solvent to be mixed with the raw materials is not heated in order to dissolve all of the raw materials.

Crystallization of the raw materials after all of the raw materials have been dissolved can be performed by a known method. Examples of the method of crystallizing the raw material after all the raw materials have been dissolved include a method of cooling a solution of the raw material (cooling crystallization method), a reaction crystallization method, and the like. In the mixing step described above, in addition to the operation of dissolving all the raw materials, the operation of crystallizing the raw materials is not performed.

When crystallization is performed by the cooling crystallization method, the temperature of the solution of the raw material by cooling (cooling temperature) is set depending on the type of crystalline sugar and/or sugar alcohol. The cooling temperature is typically 25°C or less or 20°C or less, and may be 5°C or more, 10°C or more, or 15°C or more.

<Spray drying process>
The spray drying process is a process of spray drying the above-mentioned crystal suspension (spray liquid) under low temperature conditions. Spray drying can be performed using a spray dryer in one embodiment. As the spray dryer, for example, OC-16 manufactured by Okawara Kakoki Co., Ltd. can be used.

Low-temperature conditions refer to conditions at a lower temperature (eg, 60° C. or lower) than the temperature at which conventional spray drying is performed (eg, higher than 60° C.). In this embodiment, since a crystal suspension containing a portion of the sugar and/or sugar alcohol in a crystalline state is used, suitable granules can be obtained even if spray drying is performed at a lower temperature than conventionally.

The low-temperature condition may be such that the function of the functional material is not lost. In this embodiment, for example, when an enzyme is included as the functional material, deactivation of the enzyme due to spray drying under high temperature conditions can be suppressed. When a fragrance is included as a functional material, volatilization of the fragrance due to spray drying under high temperature conditions can be suppressed.

The fact that spray drying is performed under low temperature conditions means that the inlet air temperature (inlet temperature) in the spray dryer is performed under the above-mentioned temperature conditions.

In one embodiment, the inlet air temperature in the spray drying step is preferably 60°C or less, 55°C or less, 50°C or less, 45°C or less, 40°C or less, 35°C or less, 30°C or less, 25°C or less, 20°C or less, ℃ or lower, or 15℃ or lower. The inlet air temperature may be, for example, 0°C or higher, 5°C or higher, or 10°C or higher. That is, the inlet air temperature in the spray drying process may be from 0 to 60°C, or may be from 0 to 50°C.

The outlet air temperature (exhaust air temperature) in the spray dryer may be, for example, 50° C. or less, 40° C. or less, 35° C. or less, 30° C. or less, 25° C. or less, 20° C. or less, or 15° C. or less, and 0. The temperature may be higher than or equal to 5°C, or higher than or equal to 10°C.

The liquid temperature of the crystal suspension in the spray drying step may be, for example, 60°C or lower, 50°C or lower, or 45°C or lower, or 10°C or higher, 15°C or higher, or 20°C or higher.

In spray drying, other conditions such as the supply amount of the crystal suspension, the ambient temperature, and the ambient humidity may be adjusted as appropriate.

For example, the atomizer rotation speed in spray drying may be 3000 rpm or more, 5000 rpm or more, or 10000 rpm or more, and may be 25000 rpm or less, 20000 rpm or less, or 18000 rpm or less.

The spray drying step may include an additional post-drying step, for example, for the purpose of adjusting the moisture content of the granules. The post-drying step may be, for example, blowing air on the granules attached to the can wall in a spray dryer for a predetermined period of time to further volatilize the moisture in the granules. Alternatively, the granules obtained by spray drying may be stored in a desiccator containing silica gel for a predetermined period of time.

The degree of caking of the granules may be less than 10.0% by weight or less than 9.5% by weight, 0.1% by weight or more, 0.5% by weight or more, 1.0% by weight or more, 1.5% by weight or more. It may be at least 2.0 mass%, at least 2.5 mass%, at least 3.0 mass%, or at least 4.0 mass%. The degree of caking of the granules refers to the percentage of the granules that do not pass through a 2 mm sieve and a 1 mm sieve after one week of spray drying, and is measured by the method described in the Examples below. Ru.

The recovery rate of the granules according to this embodiment may be 40.0 mass% or more, or 45.0 mass% or more, and 100.0 mass% or less, 90.0 mass% or less, or 80.0 mass% or less. , or 75.0% by mass or less. The recovery rate of granules is measured by the method described in Examples below.

<Granules>
The granules according to the present embodiment contain at least one selected from the group consisting of crystalline sugars and crystalline sugar alcohols, and some of the crystalline sugars and/or sugar alcohols are in a crystalline state and others are in a crystalline state. part is in an amorphous state. The ratio of the average major axis to the average minor axis of the particles constituting the granules is 3.1 or less. The granules can be obtained, for example, by the method for producing granules described above.

The granules may further contain a functional material. The detailed aspects of the crystalline sugar, the crystalline sugar alcohol, and the functional material are the same as those described above, so a description thereof will be omitted. The term "granule" as used herein refers to an aggregate of particles, and the particles constituting the granule (granule particles) contain one or more types selected from the group consisting of crystalline sugar and sugar alcohol.

The granules may contain two or more types of crystalline sugars, may contain two or more types of crystalline sugar alcohols, or may contain two or more types of crystalline sugars and crystalline sugar alcohols in combination. May contain.

The granules include a first sugar raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols, and a first sugar raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols; It may also contain a second sugar raw material different from the raw material. When the granules contain the first sugar raw material and the second sugar raw material, the fluidity of the granules and the stability of the functional material and the granules are better.

The first sugar raw material may be, for example, isomaltulose. The second sugar raw material may contain one or more of the above-mentioned sugars or sugar alcohols, as long as they are different from the first sugar raw material, and may contain sucrose.

The content of the first sugar raw material is 70.0 parts by mass or more, 75.0 parts by mass or more, 80.0 parts by mass or more, based on 100 parts by mass of the total amount of crystalline sugar and crystalline sugar alcohol. The amount may be 85.0 parts by weight or more, 90.0 parts by weight or more, or 95.0 parts by weight or more, and may be 99.9 parts by weight or less, 95.0 parts by weight or less, or 90.0 parts by weight or less.

When the granules contain the second sugar raw material, the content of the second sugar raw material is 1.0 parts by mass or more based on 100 parts by mass of the total amount of crystalline sugar and crystalline sugar alcohol, and 3. It may be 0 parts by mass or more, 5.0 parts by mass or more, 8.0 parts by mass or more, 10.0 parts by mass or more, 12.0 parts by mass or more, or 15.0 parts by mass or more, and 30.0 parts by mass. The amount may be 25.0 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less.

The granules according to one embodiment are composed of granule particles in which a portion of the crystalline sugar and/or sugar alcohol is in a crystalline state, and the sugar and/or sugar alcohol in the crystalline state are aggregated with each other. In this case, the other part (other part) of the crystalline sugar and/or sugar alcohol is in an amorphous state and is held in the gap formed by the aggregated crystalline sugar and/or sugar alcohol. is preferred. When the granules contain a functional material, it is preferable that the functional material is also held in the gaps formed between crystalline sugars and/or sugar alcohols.

The aggregation of crystalline sugars and/or sugar alcohols can be confirmed by observing the appearance of granules or the morphology of fractured surfaces of granules using a scanning electron microscope (SEM) or digital microscope. . It can be confirmed by the following method that the sugar and/or sugar alcohol in an amorphous state and the functional material are retained in the above-mentioned gap.
(1) Observe the morphology of the granules during heating using a differential scanning calorimeter (DSC, for example, Real View DSC (TA7000) manufactured by Hitachi High-Tech Science Co., Ltd.). As a result, it can be visually confirmed that sugars and sugar alcohols in an amorphous state undergo a glass transition due to temperature rise.
(2) Using a polarizing microscope (for example, a polarizing microscope (MT9200L) manufactured by Meiji Techno Co., Ltd.), visually confirm the difference in polarization between the crystalline state and the amorphous state.

The number of crystalline sugars and/or sugar alcohols (number of crystals) contained in the particles constituting the granules is, for example, 10 or more, and may be 50 or more, or 100 or more. The number of crystals may be 1000 or less. The number of crystals can be determined visually by observation using a scanning electron microscope.

The shape of the particles constituting the granules may be approximately spherical from the viewpoint of better fluidity of the granules. The particles constituting the granules may have irregularities on their surfaces in order to improve fluidity.

The average particle size of the granules is 10.00 μm or more, 20.00 μm or more, 40.00 μm or more, 60.00 μm or more, 80.00 μm or more, or It may be 90.00 μm or more, and for better solubility, it may be 200.00 μm or less, 150.00 μm or less, 140.00 μm or less, 135.00 μm or less, or 118 μm or less. The average particle size of the granules may be, for example, 20.00 to 118.00 μm.

The "average particle size of granules" in this specification can be measured using an electron microscope. For the measurement, for example, Miniscope TM3030 manufactured by Hitachi High-Technologies Corporation can be used. The details of the method for measuring the average particle diameter of the granules are as described in the Examples below.

The standard deviation of the average particle diameter of the granules may be 40 μm or less, or 30 μm or less, and may be 5 μm or more, or 10 μm or more, since the granules are less likely to solidify.

The average minor axis of the granules may be 80 μm or more, or 95 μm or more, and 150 μm or less, or 130 μm or less. The average major axis of the granules may be 75 μm or more, or 95 μm or more, and 200 μm or less, or 150 μm or less.

The ratio of the average major axis to the average minor axis of the granules is 1.40 or less, 1.20 or less, 1.10 or less, or 1.04 or less, since the stability and fluidity of the granules are better. Generally, it may be 1.00 or more, or 1.01 or more. The ratio of the average major axis to the average minor axis of the granules may be, for example, from 1.00 to 1.04. The standard deviation of the ratio of the average major axis to the average minor axis of the granules is 0.20 or less, or 0.12 μm or less, since the granules are easier to dry, less caking, and have better fluidity. It may be 0.01 μm or more.

The average particle size of the particles constituting the granules may be 5.00 μm or more, 10.00 μm or more, or 15.00 μm or more, and 50.00 μm or less, 40.00 μm or less, 30.00 μm or less, or 25.00 μm or less. Or it may be 20.00 or less. The average particle size of the particles constituting the granules may be, for example, 10.00 to 20.00 μm.

The standard deviation of the average particle diameter of the particles constituting the granules is 10.00 μm or less, 8.00 μm or less, 6.00 μm or less, 4.00 μm or less, or It may be 3.3 μm or less, 1.00 μm or more, or 2.00 μm or more. The standard deviation of the average particle diameter of particles constituting the granules may be, for example, 1.00 to 3.30 μm.

The average minor axis of the particles constituting the granules may be 5.0 μm or more, or 10.0 μm or more, and may be 30.0 μm or less, or 25.0 μm or less. The average major axis of the particles constituting the granules may be 10.0 μm or more, or 15.0 μm or more, and 50 μm or less, or 35 μm or less.

The ratio of the average major axis to the average minor axis of the particles constituting the granules is 3.1 or less. When the ratio of the average major axis to the average minor axis of the particles constituting the granules is 3.1 or less, the stability and fluidity of the granules are excellent. The ratio of the average major axis to the average minor axis of the particles constituting the granules is 2.8 or less, 2.5 or less, 2.2 or less, or 1.9 or less, for better stability and fluidity. It may be 0.5 or more, 1.0 or more, or 1.4 or more.

The standard deviation of the ratio of the average major axis to the average minor axis of the particles constituting the granules may be 0.4 or less, or 0.3 or less, or more than 0.0, or 0.1 or more.

The total pore volume of the granules is 0.0265 cm ³ /g or more, 0.0270 cm ³ /g or more, 0.0275 cm ³ /g or more, 0.0280 cm ³ /g or more, or 0.0290 cm ³ /g or more. It may be less than 0.0400 cm ³ /g, less than 0.0350 cm ³ /g, less than 0.0300 cm ³ /g, and less than 0.0290 cm ³ /g.

The total specific surface area of the granules may be 2.000 m ² /g or more, 4.000 m ² /g or more, 6.000 m ² /g or more, or 8.000 m ² /g or more, and 10.000 m ² /g Below, it may be 9.000 m ² /g or more or 8.5000 m ² /g or less.

The average pore diameter of the granules may be 60,000 Å or less, 40,000 Å or less, 20,000 Å or less, 10,000 Å or less, 5,000 Å or less, 1,000 Å or less, 800 Å or less, or 600 Å or less, from the viewpoint of better granule stability. The thickness may be 400 Å or more, or 550 Å or more.

The porosity of the granules may be 3.80% or more, 3.90% or more, or 3.95% or more, and 8.00% or less, 5.00% or less, 4.50% or less, or 4. It may be 10% or less.

The fragrance retention rate of the granules containing the fragrance may be 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100% or more, and 150% or less, 140% or less, or 130% or less. It may be.

The total pore volume, total specific surface area, average pore diameter, porosity, and fragrance retention rate of the granules can be measured by the method described in the Examples below.

The method for producing granules according to this embodiment includes a step of completely dissolving the raw material, a step of crystallizing the raw material, a step of drying by vacuum freezing, or a crystal suspension for the purpose of completely dissolving or crystallizing the raw material. Since the step of heating the granules before spray drying can be omitted, it is possible to manufacture granules using a simpler method than conventional methods.

The granules according to the present embodiment can be efficiently manufactured with simpler operations, and the occurrence of caking is suppressed. Furthermore, the granules according to the present embodiment can be manufactured efficiently with simpler operations, while also suppressing deterioration in hygroscopicity, fluidity, and jetability.

Since the granules are obtained by spray drying under low temperature conditions, when the granules contain functional materials, the functions of the included functional materials are less likely to be lost due to heat. In other words, even after the drying process, the granules retain the functionality of the functional material well. Normally, when obtaining granules by spray drying, it is difficult to obtain suitable granules unless spray drying is performed under higher temperature conditions. However, the granules according to this embodiment can be easily obtained even under low temperature conditions.

The granules according to the embodiments described above can be used, for example, as a material to be added to foods, food additives, pharmaceuticals, cosmetics, quasi-drugs, or pharmaceuticals, animal feed, fertilizers, fragrances, antibiotics, soil conditioners, etc. Can be used.

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to the following examples.

<Example 1>
(Preparation of crystal suspension)
Put 3.25 kg of Palatinose (registered trademark of Mitsui Sugar Co., Ltd., PST-N) and 1.75 kg of water into an 8 L metal container, dilute to Brix (Bx) 65, and suspend the crystals. I got the liquid. Thereafter, while maintaining the temperature of the crystal suspension at 30° C., it was stirred for 2 hours at 350 rpm with a stirrer (Shinto Kagaku Co., Ltd., Three-One Motor, BL-1200) to obtain a crystal suspension A1.

(Preparation of spray liquid)
900 g of granulated sugar (Mitsui Sugar Co., Ltd., GN) and 300 g of ion-exchanged water heated to 80° C. or higher were placed in a 3 L plastic jug and stirred until the sugar was completely dissolved. The obtained sugar solution was diluted with ion-exchanged water until Bx reached 60 to prepare 1.5 L of Bx60 sugar solution. The temperature of the prepared Bx60 sugar solution was maintained at 30° C. in a water bath (TAITEC Co., Ltd., PERSONAL-11). 0.96 kg of the above-mentioned Bx60 sugar solution was mixed with the crystal suspension A1 to prepare a spray liquid having a solid content ratio of palatinose:sucrose of 85:15.

(spray drying)
Approximately 4 kg of the spray liquid maintained at 30° C. was spray-dried using a spray dryer (Okawara Kakoki Co., Ltd., OC-16 (dry type)). The spray drying conditions were as shown below.
Air blowing temperature: 40℃
Exhaust air temperature: 28℃
Air blower inverter frequency: 60Hz
Exhaust air volume: 38Hz
Inner pressure control: slight positive pressure Atomizer rotation speed: 14,000 rpm (setting: 33Hz)
Raw material supply rate: 50mL/min, 4.0kg/h (setting: 8.5Hz)
Equipment: OC-16 (dry type)

<Example 2>
(Preparation of crystal suspension)
Crystal suspension was prepared in the same manner as in Example 1 to obtain crystal suspension A1, except that 6.5 kg of PST-N and 3.5 kg of water were used, and the rotation speed of the stirrer was changed to 300 rpm. Liquid A2 was obtained.

(Preparation of spray liquid)
1800 g of granulated sugar (Mitsui Sugar Co., Ltd., GN) and 600 g of ion-exchanged water heated to 80° C. or higher were placed in a 3 L plastic jug and stirred until the sugar was completely dissolved. The mixture was diluted with ion-exchanged water until Bx reached 60 to prepare 1.5 L of Bx60 sugar solution. The temperature of the prepared Bx60 sugar solution was maintained at 30° C. in a water bath (TAITEC Co., Ltd., PERSONAL-11). A fragrance-free sugar solution was prepared by mixing 1.9 kg of Bx60 sugar solution and 90.0 g of ion exchange water. 1.90 kg of the above-mentioned fragrance-free sugar solution was mixed with the crystal suspension A2 to prepare a spray liquid having a solid content ratio of palatinose:sucrose of 85:15.

(spray drying)
While maintaining approximately 10 kg of the spray liquid at 30° C., the entire amount was spray-dried using a Mono pump (3NTL08PUL, Heishin Giki Co., Ltd.). The spray drying conditions were as shown below.
Air blowing temperature: 40℃
Exhaust air temperature: 28-30℃
Air flow rate: 60Hz
Exhaust air volume: 38Hz
Static pressure inside the tower: slightly positive pressure Atomizer rotation speed: 14,000 rpm (setting: 33Hz)
Atomizer type: Disk type atomizer Raw material supply rate: 50mL/min, 4.0kg/h (setting: 8.5Hz)
Equipment: OC-16 (dry type)

<Example 3>
(Preparation and spray drying of crystal suspension)
A brown sugar flavor aqueous solution was prepared by mixing 19.0 g of brown sugar flavor (Kokuto Micron H-80210, Takasago International Corporation) and 71.0 g of ion-exchanged water. 1.9 kg of the Bx60 sugar solution obtained by the method described in "(Preparation of spray liquid)" of Example 2 and 90.0 g of the brown sugar flavor aqueous solution were mixed to prepare a flavored sugar solution. 1.90 kg of flavored sugar solution was mixed with the crystal suspension A2 obtained by the method of Example 2 to prepare a spray liquid having a solid content ratio of palatinose:sucrose of 85:15. Using the obtained spray liquid, spray drying was performed under the same conditions as in Example 2.

<Examples 4 to 7>
(Preparation of crystal suspension)
3.25 kg of PST-N and 2.4 kg of water were placed in an 8 L metal container and diluted to Bx57.5. Thereafter, the diluted product was stirred for 2 hours at 300 rpm with a stirrer (Shinto Kagaku Co., Ltd., Three-One Motor, BL-1200) while maintaining the temperature at 30° C. to obtain a crystal suspension (c1).

(Preparation of spray liquid)
1800 g of granulated sugar (Mitsui Sugar Co., Ltd., GN) or 1800 g of PST-N was placed in a 3 L plastic jug, and 1200 g of ion exchange water heated to 80° C. or higher was added, followed by stirring until the sugar was completely dissolved. By diluting each of the obtained sugar solutions with ion-exchanged water until Bx reaches 60, Bx60 sucrose syrup containing granulated sugar and Bx60 palatinose syrup containing PST-N are prepared as Bx60 sugar solution (a). was prepared. The prepared Bx60 sugar solution (a) was maintained at a temperature of 30° C. using a water bath (TAITEC Co., Ltd., PERSONAL-11).

The brown sugar flavor aqueous solution (b) was prepared by mixing 9.5 g of brown sugar flavor (Kokutou Micron H-80210, Takasago International Corporation) and 40.5 g of ion-exchanged water.

Bx60 sugar solution (a) and brown sugar flavor aqueous solution (b) were mixed to have the composition shown in Table 1, and the crystal suspension (c1) was mixed with the resulting mixture. In this way, a spray liquid having the composition shown in Table 2 was prepared.

(spray drying)
While maintaining the spray liquid at 30° C., the entire amount (6.7 kg) was spray-dried using a Mono pump (3NTL08PUL, Heishin Giki Co., Ltd.) under the following conditions.
Air blowing temperature: 30℃
Exhaust air temperature: 28.1-24.0℃
Air flow rate: 60Hz
Exhaust air volume: 38Hz
Static pressure inside the tower: slightly positive pressure Atomizer rotation speed: 14,000 rpm (setting: 33Hz)
Atomizer type: Disk type atomizer Raw material supply rate: 50mL/min, 4.0kg/h (setting: 8.5Hz)
Equipment: OC-16 (dry type)

After the spraying was completed, drying air was continued to be sent for 40 minutes without changing the operating conditions of the spray dryer to dry the interior of the dryer. Thereafter, the dried material was scraped off and collected.

<Comparative example 1>
(Preparation of comparative suspension)
3.25 kg of PST-N and 1.75 kg of water were placed in an 8 L metal container and boiled at 80° C. for 1 hour. After confirming that the sugar was completely dissolved, water was added to the metal container and adjusted to Bx65. The suspension in the metal container was cooled to 20°C using a water bath containing 7°C water. While stirring at 300 rpm, irradiation was performed for 15 minutes using an ultrasonic oscillator (SMT Corporation, ULTRA SONIC HOMOGENIZER, UH-600S) (memory 8, continuous irradiation). Thereafter, while maintaining the temperature of the contents at 30° C., the mixture was stirred with a stirrer at 300 rpm for 1 hour and 45 minutes to obtain comparative suspension B1.

(Preparation of spray liquid and spray drying)
A spray liquid was prepared and spray-dried in the same manner as in Example 1, except that comparative suspension B1 was used in place of crystal suspension A1.

<Comparative example 2>
(Preparation of comparative suspension)
Comparative suspension B2 was obtained in the same manner as the procedure for obtaining comparative suspension B1 in Comparative Example 1, except that 6.5 kg of PST-N and 3.5 kg of water were used.

(Preparation and spray drying of crystal suspension)
A spray liquid was prepared and spray-dried in the same manner as in Example 2, except that comparative suspension B2 was used in place of crystal suspension A2.

<Comparative example 3>
(Preparation and spray drying of comparative suspension)
1.90 kg of the flavored sugar solution mentioned above was mixed with comparative suspension B1 to prepare a spray liquid having a solid content ratio of palatinose:sucrose of 85:15. Using the obtained spray liquid, spray drying was performed under the same conditions as in Example 2.

<Comparative Examples 4 to 7>
(Preparation of comparative suspension)
3.25 kg of PST-N and 2.4 kg of water were placed in an 8 L metal container and boiled at 80° C. for 1 hour. After confirming that the sugar was completely dissolved, water was added to adjust the Bx to 57.5. The contents were cooled to 20°C by bathing the 8L volume metal container in 7°C water. While stirring at 300 rpm, irradiation was performed for 15 minutes using an ultrasonic oscillator (SMT Corporation, ULTRA SONIC HOMOGENIZER, UH-600S) (memory 8, continuous irradiation). Thereafter, while maintaining the temperature of the contents at 30° C., the mixture was stirred with a stirrer at 300 rpm for 1 hour and 45 minutes to obtain a comparative suspension (c2).

(Preparation of spray liquid and spray drying)
Spray liquids were prepared and spray-dried in the same manner as in Examples 4 to 7, except that the comparative suspension (c2) was used in place of the crystal suspension (c1).

<Brix value (Bx)>
Bx was measured with a Ref Bx meter (RX-5000α, manufactured by Atago Co., Ltd.).

<Crystallization rate>
The crystallization rate was determined by putting 1 g of the crystal suspension or spray into a 1.5 mL Eppendorf tube, centrifuging it for 1 minute at 16,000 rpm using a centrifuge (Sakuma Seisakusho Co., Ltd., M150IV), and removing the supernatant. The mass of the remaining crystals after removing and the mass of the crystal suspension or spray liquid were calculated by applying the following formula.
Crystallization rate (mass%) = remaining crystal mass (g) / (mass of crystal suspension or spray liquid (g)) x 100

<Viscosity>
The viscosity was measured at a liquid temperature of 25° C. using a B-type viscometer (Tokyo Keiki Co., Ltd., Model BL). Viscometer adapter no. 3 was attached, and the measuring part was immersed in the object for 15 seconds at a rotational speed of 12 rpm. The readings were then recorded. Based on the conversion coefficient of the B-type viscometer, the reading value was multiplied by 100 to calculate the viscosity (mPa·s) of the object.

<Appearance of granules>
The appearance of the obtained granules was evaluated using an electron microscope (TM3030-Plus, Hitachi High-Technologies Corporation).

<Evaluation of product recovery rate (yield)>
The product recovery rate (yield) (mass %) was determined by the ratio of the weight of the granules after spray drying (g) to the weight of solid content (g) in the spray liquid.

<Evaluation of water activity>
Water activity (%) was measured using a water activity measuring device (METER, Dew Point water activity Meter AquaLAb Series 4TE) using 5 g or 10 mL of granules.

Even if the Bx and crystallization rate are the same, the method of the example produces uniformly crystals with a moderately small crystal size in the crystal suspension and spray liquid, the viscosity is low, and the granules after spray drying are The recovery rate was good. In the methods of Examples and Comparative Examples, the water activities were equivalent.

<Evaluation of degree of granule caking>
(1) Sieve evaluation (some samples only)
1 to 2 kg of the obtained granules were placed in an aluminum pack (length under the zipper: 340 mm x 240 mm), sealed and stored at room temperature at 25°C for one week. The weight of the under sieve was measured, and the degree of caking was evaluated based on the following criteria.
- Weak: Less than 10% of the granules are on the sieve.
- Medium: 10% or more but less than 30% of the granules are on the sieve.
- Strong: More than 30% of the granules are on the sieve.

(2) Visual confirmation 500g of each granule, which had been sealed in an aluminum pack and stored at room temperature of 25°C for more than one month, was spread on black paper and the degree of caking was visually confirmed according to the following criteria. Table 6 shows the evaluation results of the granules obtained by the methods of Example 1 and Comparative Example 1.
- Weak: Less than 10% of the granules are solidified into lumps.
- Medium: 10% or more but less than 30% of the granules are solidified into lumps.
・Strong: More than 30% of the granules are solidified into lumps.

As shown in Table 5, most of the granules obtained by the conventional method (crystal precipitation method) in the comparative example showed moderate caking, whereas the granules produced by the method in the example showed no caking. Almost never confirmed.

<Crystal diameter of particles in crystal suspension and spray liquid>
The crystal suspension or spray liquid was dropped onto a slide glass, a cover glass was placed thereon, and the measurement was performed at a magnification of 1000 times. The average particle size is measured using a digital microscope (Saito Kogaku Co., Ltd., SKM-S31B-PC) for any 10 or more sugar crystals, and the particle size of each of the 10 or more sugar crystals that make up the sugar crystals. The average was taken. 1st when the distance in the first direction and the distance in the second direction orthogonal to the first direction intersect at the midpoint of each of 10 or more particles to be measured in the crystal suspension or spray liquid The distance in the direction and the distance in the second direction were measured as the horizontal width and the vertical width, respectively. The first direction is the same direction for all particles to be measured. Of the measured widths and lengths, the longer one was the major axis and the shorter one was the minor axis, and the averages of the particles to be measured were taken as the average major axis and the average minor axis. FIGS. 1A and 1B show microscopic images of crystal suspensions obtained by the methods of Example 1 and Comparative Example 1, respectively.

<Crystal diameter of granules and particles constituting the granules>
The granule diameter and the crystal diameter of the particles constituting the granules were measured using an electron microscope (Miniscope TM3030, manufactured by Hitachi High-Tech Corporation). Ten granules obtained by the methods of Examples and Comparative Examples were observed, the long width and short width of each granule were measured, and the average value of the granule diameter was determined. The long width and short width of 3 to 10 crystals contained in the granules were measured, and the average value of the crystal diameter in the granules was determined. FIG. 2 shows an electron microscope image of the granules obtained by the method of Example 3. FIG. 3 shows an electron microscope image of granules obtained by the method of Comparative Example 3.

<Standard deviation>
The average particle diameter, average major axis, average minor axis, and standard deviation of the ratio of the average major axis to the average minor axis are calculated using STDEV. Calculated using S function.

<Evaluation of fluidity, jetability and bulk density>
Regarding the granules of Examples and Comparative Examples, R. L. The "flowability index" and "jetability index" proposed by Carr were calculated (Carr, R.L. "Evaluating flow properties of solids." Chem. Eng. (1965) 72 (163-168)). Using a multifunctional powder property measuring instrument (Seishin Enterprise Co., Ltd., Multitester MT-02), the angle of repose (°), spatula angle (°), degree of compaction (%), and uniformity (-) of the granules were measured. Based on Carr's theory, an index corresponding to each measured value was obtained. A fluidity index was obtained by summing the index of each measurement value. A multifunctional powder physical property measuring instrument is used to determine the disintegration angle (°), difference angle (°), and degree of dispersion (%) of the granules, and the index corresponding to each measurement value obtained based on Carr's theory and the flow rate are calculated. By adding up the indices based on the sex index, the jet sex index was obtained. The temperature and humidity at the time of measurement were 25° C. and 50%.

The fluidity and jetability of the granules were evaluated based on Carr's evaluation criteria shown below.
Fluidity evaluation criteria Fluidity index value Level of fluidity 90-100 Best 80-89 Good 70-79 Fairly good 60-69 Fair 40-59 Not very good 0-19 Very poor

Jetability evaluation criteria Jetability index value Degree of jetness 80-100 Very strong 60-79 Fairly strong 40-59 Tendency 25-39 Possible 0-24 None

Although the granules obtained by the method of the example were obtained by a simpler operation, they had good fluidity and jetability similar to the method of the comparative example.

Regarding the angle of repose and uniformity, please refer to the Powder Engineering Terminology Dictionary (Powder Engineering Society of Japan, updated on May 17, 2021, URL: http://www.sptj.jp/powderpedia/words/10382/) The fluidity was separately evaluated based on Kerr's fluidity index table described above.

The bulk densities (loose bulk density, hardened bulk density, dynamic bulk density) of the granules of Examples and Comparative Examples were determined using a multifunctional powder physical property measuring device. The granules obtained by the method of the example showed the same bulk density as the method of the comparative example.

<Evaluation of hygroscopicity of granules>
The hygroscopicity (adsorption/desorption isotherm) of the granules obtained by each method of Example 3 and Comparative Example 3 was measured using a dynamic water vapor adsorption measuring device (Surface Measurement Systems Ltd., DVS Intrinsic). Using 10 mg of the sample, the relative humidity was increased in 5% increments from 0% to 90%, and then lowered to 0% using the same procedure. Maintain a constant relative humidity until the rate of change in water content (dm/dt) of the sample falls below 0.02 in 10 minutes, or even after 30 minutes if it does not reach 0.02%/min, and the temperature remains constant. It was kept at 25°C. The results of evaluating the hygroscopicity of the granules obtained by the method of Example 3 are shown in FIG. 4(A). The evaluation results of the hygroscopicity of the granules obtained by the method of Comparative Example 3 are shown in FIG. 4(B).

It was confirmed that the granules obtained by the method of the example showed the same adsorption/desorption isotherm as the granules obtained by the method of the comparative example, and had the same hygroscopicity.

<Evaluation of average pore diameter, total pore volume, porosity, and total specific surface area of granules>
Example 1 and Comparative Example 1 The average pore diameter, total pore volume, porosity, and total specific surface area of the granules obtained by each method were evaluated using a mercury intrusion pore size analyzer (Quantachrome, POREMASTER 60GT). 0.4 g of the sample was subjected to a mercury intrusion pore size analyzer and measured at 20°C.
Average pore diameter = Cumulative 50% pore diameter Total pore volume = Total amount of mercury injected (cm ³ )/Sample weight (g)
Porosity = sample pore volume (cm ³ ) x sample bulk density (g/cm ³ ) / sample weight (g) x 100
Total specific surface area = specific surface area assuming that the pores are open cylindrical (calculated from pore distribution and volume)

The granules obtained by the method of Example 1 had a smaller average pore diameter, higher total pore volume, higher total specific surface area, and higher porosity than the granules obtained by the method of Comparative Example 1.

<Evaluation of fragrance retention rate of granules>
The fragrance retention rates of the granules obtained by the methods of Examples 4 and 6 and Comparative Examples 4 and 6 were measured using a portable odor sensor (Shin Cosmos Electric Co., Ltd., XP-329IIIR). 50 g of the sample was placed in an aluminum pack (Nippon Seisakusha, Lamizip flat bag bottom open type AL-G) and sealed. In addition, for zero value setting, sealed aluminum packs without samples were used as standard products: 42.4 g of Palatinose (Mitsui Sugar Co., Ltd., PST-N), 7 g of granulated sugar (Mitsui Sugar Co., Ltd., GN). A sealed aluminum pack was prepared by mixing and adding 5 g of brown sugar flavoring and 0.125 g of brown sugar flavor (Kokutou Micron H-80210, Takasago International Corporation). After each aluminum pack was left standing at room temperature of 25°C for 3 hours, the scent intensity inside the aluminum pack was measured for 5 minutes using the monitoring mode of a portable odor sensor, and the highest scent intensity in 5 minutes was determined as the scent of the sample or standard product. The fragrance retention rate of each sample was calculated using the following formula.
Fragrance retention rate (%) = sample fragrance intensity/standard product fragrance intensity x 100
Note that the scent intensity inside the aluminum pack for setting the zero value was set to zero.

It was confirmed that the granules obtained by the method of the example showed the same or higher aroma retention than the granules obtained by the method of the comparative example with the same sugar content, and the aroma retention was the same or higher. .

Claims (19)

1. It contains at least one kind of raw material selected from the group consisting of crystalline sugar and crystalline sugar alcohol, and a part of the raw material is dissolved without dissolving all of the raw material and crystallizing the raw material after the dissolution. obtaining a crystal suspension containing in a crystalline state;
   Spray drying the crystal suspension under low temperature conditions,
   A method for producing granules, wherein the spray drying is performed at an inlet temperature of 0 to 60°C.
2. The method according to claim 1, wherein the sugar and the sugar alcohol are monosaccharides, disaccharides, trisaccharides, and sugar alcohols thereof.
3. The method according to claim 1 or 2, wherein the raw material is at least one selected from the group consisting of palatinose, sucrose, and trehalose.
4. The method according to claim 1 or 2, wherein the crystal suspension further contains a functional material.
5. The method according to claim 4, wherein the functional material is an enzyme, a microorganism, or a fragrance.
6. The method according to claim 1 or 2, wherein the viscosity of the crystal suspension is 50 to 1550 mPa·s at 25°C.
7. The method according to claim 1 or 2, wherein the crystalline sugar and/or sugar alcohol in the crystal suspension has an average particle size of 1.00 to 15.90 μm.
8. The method according to claim 1 or 2, wherein the standard deviation of the average particle diameter of the crystalline sugar and/or sugar alcohol in the crystal suspension is 1.00 to 10.70 μm.
9. The method according to claim 1 or 2, wherein the ratio of the average major axis to the average minor axis of the crystalline sugar and/or sugar alcohol in the crystal suspension is 1.00 to 1.70.
10. The method according to claim 1 or 2, wherein the ratio of the average major axis to the average minor axis of the particles constituting the granules is 3.1 or less.
11. The method according to claim 1 or 2, wherein the degree of caking of the granules is less than 10.0% by mass.
12. Granules containing at least one selected from the group consisting of crystalline sugar and crystalline sugar alcohol,
    A part of the sugar and/or the sugar alcohol is in a crystalline state and the other part is in an amorphous state,
    Granules, wherein the ratio of the average major axis to the average minor axis of the particles constituting the granules is 3.1 or less.
13. The granule according to claim 12, wherein the sugar and the sugar alcohol are monosaccharides, disaccharides, trisaccharides, and sugar alcohols thereof.
14. The granule according to claim 12 or 13, wherein at least one selected from the group consisting of crystalline sugar and crystalline sugar alcohol is at least one selected from the group consisting of palatinose, sucrose, and trehalose.
15. The granule according to claim 12 or 13, further comprising a functional material.
16. The granule according to claim 15, wherein the functional material is an enzyme, a microorganism, or a fragrance.
17. The granules according to claim 12 or 13, wherein the particles constituting the granules have an average particle diameter of 10.00 to 20.00 μm.
18. The granule according to claim 12 or 13, wherein the standard deviation of the average particle diameter of the particles constituting the granule is 1.00 to 3.30 μm.
19. The granules according to claim 12 or 13, wherein the degree of caking of the granules is less than 10.0% by mass.
    
    

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