JP7197743B1 - Method for producing granules and granules - Google Patents

Abstract

An object of the present invention is to provide a method for producing granules simply and efficiently. [Solution] At least one raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols is mixed with a solvent, all of the raw materials are dissolved, and the raw materials are crystallized after the dissolution. A method for producing granules, comprising the steps of: obtaining a crystal suspension in which a part of the raw material is contained in a crystalline state; and spray-drying the crystal suspension under low-temperature conditions. [Selection figure] None

Description

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

In the production of foods, pharmaceuticals, etc., it is very important to maintain the stability and ease of handling (fluidity) of materials, assuming various environmental changes such as temperature and humidity. A method of maintaining the stability and fluidity of the material is powderization, and one method of powderization is spray drying.

Spray drying is a method in which a solution or suspension is sprayed into gas and dried rapidly to obtain a dry powder. The drying temperature during spray drying is generally high. Enzymes, yeasts and cells are denatured and deactivated by contact with high-temperature gas, and volatilization of easily volatile fragrances proceeds easily, making it difficult to sufficiently retain their original properties. Proposals have been made so far from the viewpoint of preventing loss due to such spray drying (for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2021-106571

A granule containing crystalline sugar and/or crystalline sugar alcohol and having amorphous sugar and/or sugar alcohol held in gaps formed between crystalline sugars and/or sugar alcohols is produced. Therefore, from the viewpoint of stability as crystals, easy drying of granules during spray drying, stability and fluidity after spray drying, etc., after completely dissolving the sugar and / or sugar alcohol, spray drying Precipitation of crystals again is considered important. Therefore, when producing a suspension used for spray drying, a method of completely dissolving the raw material sugar and / or sugar alcohol, heating and cooling, and precipitating some crystals again (crystal precipitation method ) has been adopted. However, such a crystal precipitation method involves a complicated process, and was difficult to implement without an apparatus for precipitating crystals. Furthermore, the precipitation operation may generate not only crystals of the desired size but also a large number of fine crystals, and the recovery rate of the granules after spray-drying may be lowered.

An object of one aspect of the present invention is to provide a method for producing granules simply and efficiently, and granules obtained by the method.

The present invention provides each of the following inventions.
[1]
It contains at least one 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 crystallization of the raw material after dissolution. obtaining a crystal suspension contained in a crystalline state;
and 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 inlet temperature of the spray drying is 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 of [5], wherein the functional material is an enzyme, microorganism, or 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 diameter to the average minor diameter 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,
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 granule is 3.1 or less. granules.
[14]
The granules according to [13], wherein the sugar and the sugar alcohol are monosaccharides, disaccharides, trisaccharides and sugar alcohols thereof.
[15]
The granules according to [13] or [14], wherein at least one selected from the group consisting of crystalline sugars and crystalline sugar alcohols is at least one selected from the group consisting of palatinose, sucrose and trehalose.
[16]
The granules according to any one of [13] to [15], further containing a functional material.
[17]
The granules of [16], wherein the functional material is an enzyme, microorganism, or fragrance.
[18]
The granules according to any one of [13] to [17], wherein the particles constituting the granules have an average particle size of 10.00 to 20.00 μm.
[19]
The granules according to any one of [13] to [18], wherein the particles constituting the granules have an average particle size standard deviation of 1.00 to 3.30 μm.
[20]
The granules according to any one of [13] to [19], wherein the degree of caking of the granules is less than 10.0% by mass.

ADVANTAGE OF THE INVENTION According to one aspect of this invention, the granule obtained by the method of manufacturing a granule simply and efficiently and the said method can be provided.

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

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<Method for producing granules>
The method for producing granules according to the present embodiment contains at least one raw material selected from the group consisting of crystalline sugar and crystalline sugar alcohol, dissolving all the raw materials and crystallization of the raw materials after the dissolution. a step of obtaining a crystal suspension in which a part of the raw material is contained in a crystalline state (mixing step), 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 raw material selected from the group consisting of crystalline sugars and crystalline sugar alcohols and part of the raw materials in a crystalline state is obtained.

As used herein, "crystalline sugar and/or sugar alcohol" means solid sugar and/or sugar alcohol in which constituent atoms are three-dimensionally regularly repeated. As used herein, "amorphous sugar and/or sugar alcohol" refers to 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 the operability in the mixing step.

Monosaccharides include glucose, galactose, mannose, fructose, allose, allulose and the like. Disaccharides include isomaltulose, sucrose, lactulose, lactose, maltose, trehalose, cellobiose and the like. Trisaccharides include nigerotriose, maltotriose, raffinose and the like. Isomaltulose is a disaccharide registered as “palatinose” by Mitsui Sugar Co., Ltd. as a trademark.

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

The crystalline sugars and sugar alcohols described above may be used singly or in combination of two or more. The crystal suspension may contain two or more kinds of crystalline sugars, may contain two or more kinds of crystalline sugar alcohols, and may contain crystalline sugars and crystalline sugar alcohols in combination. You may contain 2 or more types. The method for producing the granules according to the present embodiment is a simple method, and even when two or more types of crystalline sugars and alcohols are used (for example, when two types of sugars are used), the average length of the particles constituting the particles can be reduced. Granules with a sufficiently small average length to diameter ratio (eg, 3.1 or less) can be obtained. Granules having a sufficiently small ratio of the average major diameter to the average minor diameter of the constituent particles tend to be excellent in stability and fluidity.

The content of the crystalline sugar and/or sugar alcohol contained in the crystal suspension is 30% by mass or more, preferably 30% by mass or more, based on the total amount of the crystal suspension, from the viewpoint of easily obtaining granules with excellent fluidity. It is 40% by mass or more, more preferably 45% by mass or more, and still 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 the crystalline sugar and/or sugar alcohol is preferably 90% by mass or less, more preferably 80% by mass, based on the total amount of the crystal suspension. % by mass or less, more preferably 70% by mass or less.

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 easily obtaining 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 the spray drying process Or it may be 35.00 or less.

The Brix value (Bx) in the present specification means the Ref Brix value calculated from the refractive index, and can be measured by a Brix meter (for example, 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.

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, and 50% by mass, from the viewpoint of easily obtaining granules with excellent fluidity. Above, 55% by mass or more, or 60% by mass or more. 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 from the viewpoint of maintaining good operability in the spray drying step. The crystallization rate in the present specification is measured by the method described in Examples below.

Crystallization rate can be determined by performing operations that physically or chemically add or remove crystals, such as filter filtration, centrifugation, gravity sedimentation, dissolution with water and/or heating, and adjustment of consumption of crystal components accompanying chemical reactions. can be adjusted by It can also be adjusted by an operation for increasing 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 at least as large as can stably exist in the crystal suspension. The size of the crystal nucleus may be, for example, the size of the critical crystal nucleus or larger.

The viscosity of the crystal suspension is 1550 mPa· at 25° C., because the decrease in the recovery rate of the granules after spray drying is further suppressed and the occurrence of caking of the 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 s s or less, 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 or more 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 size of the crystalline sugar and/or sugar alcohol is 30.00 μm or less, 25.00 μm or less, 20.00 μm or less, 18.00 μm or less, or 15.90 μm from the viewpoint of further suppressing the occurrence of granule disintegration. 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 the solvent or solute, changing the solvent temperature, dissolving time, stirring time, crushing with a stirrer or grinder, filtering, etc. It can be adjusted by a crystallization operation such as hydrolysis of sugar.

The "average particle size of crystalline sugar and/or sugar alcohol" as used herein can be measured with a digital microscope. For the measurement, for example, SKM-S31B-PC manufactured by Saito Kogaku 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 okay. A small standard deviation of the average particle size means that the variation in the average particle size is small. When the standard deviation of the average particle size is within the range described above, excessive viscosity increase is easily suppressed, which further suppresses adhesion of granules in the spray dryer, resulting in a higher recovery rate. be 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.

As used herein, "standard deviation" refers to Microsoft (registered trademark) Excel STDEV. It is the unbiased standard deviation obtained by 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 length of the sugar and/or sugar alcohol in the crystalline state in the crystal suspension may be 5.00 μm or more, 7.00 μm or more, or 9.00 μm or more, and may be 30.00 μm or less, 25.00 μm or less, Alternatively, it may be 20.00 μm or less.

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 selected from the viewpoint of maintaining the fluidity and stability of the granules. 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.

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

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 the total mass of the crystal suspension. may be present, and may be 50% by mass or less, or 45% by mass or less.

The crystal suspension described above 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 ingredients include sugars, sugar alcohols, solvents, functional materials and mixtures thereof.

A functional material is not limited as long as it is a material or a component that exhibits some function in a composition (for example, food, medicine, etc.) obtained in combination with other materials. A functional material may be a material that is affected by the surrounding environment such as moisture, heat, light, acid, oxygen, molecular motion, ultraviolet light, electrical interaction, or physical stimulation, and may be a material that loses its function due to heating. good. More specifically, functional materials include amino acids, peptides (including hormones), proteins (including enzymes and antibodies), fatty acids, vitamins, minerals, microorganisms (e.g., lactic acid bacteria, butyric acid bacteria, natto bacteria, bifidobacteria and bacteria such as actinomycetes, molds and yeasts), hormones other than peptides, fragrances, phages, antibiotics other than peptides, natural raw materials such as crude drugs, and industrial raw materials such as metals.

The crystal suspension (spray liquid) to be spray-dried is prepared, for example, by mixing at least one raw material selected from the group consisting of crystalline sugar and crystalline sugar alcohol with a solvent so that part of the raw material is crystallized. a step of obtaining a crystal suspension A contained in a crystalline state (step A); It can be obtained by a method including a step (step B) of obtaining a turbid liquid B (spray liquid).

The mixing of the raw material and the solvent in step A is performed 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 with a solvent and stirring the obtained 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, 250-400 rpm.

Supernatant Brix value, crystallization rate, average particle size of sugar and/or sugar alcohol in crystal state, average major axis, average minor axis, ratio of average major axis to average minor axis, and standard deviation thereof in crystal suspension A Such specific aspects may be the same as those exemplified as the specific aspects of the crystal suspension described above.

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

A sugar solution contains a sugar and/or sugar alcohol and a solvent. Some or all of the sugars and sugar alcohols contained in the sugar solution may be dissolved in the solvent. Sugar and sugar alcohol can use what was mentioned above. 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 type of sugar and/or sugar alcohol as in the crystal suspension A, or may contain a different type of sugar and/or sugar alcohol.

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

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

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

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

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

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 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 is selected from the group consisting of a first sugar raw material selected from the group consisting of crystalline sugar and a crystalline sugar alcohol, and a group consisting of crystalline sugar and a crystalline sugar alcohol, and and a second sugar raw material that is different from the sugar raw material. The first sugar source may be, for example, isomaltulose. The second sugar raw material may contain one or more of the above 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, or 85.0 parts by mass or more with respect to 100 parts by mass of the solid content in the spray liquid. , 90.0 parts by mass or more, or 95.0 parts by mass or more, and may be 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" means the total amount of the composition minus 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, .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 or less, 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.

When preparing a spray solution containing a functional material, the timing of adding the functional material to the spray solution is not particularly limited. The liquid mixture may be mixed with the crystal suspension A to obtain a spray liquid.

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 with respect to 100 parts by mass of the crystal suspension described above. , 3 parts by mass or less, or 1 part by mass or less. The amount of functional material to be added can be appropriately adjusted depending on the type of functional material.

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

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

Crystallization of the raw material after dissolution of all raw materials can be carried out by known methods. Examples of the method of crystallizing the raw material after dissolving all of the raw material include a method of cooling the solution of the raw material (cooling crystallization method) and a reactive crystallization method. In the mixing step described above, in addition to the operation of dissolving all the raw materials, the above-described crystallization operation is not performed.

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

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

A low temperature condition means a lower temperature condition (for example, 60° C. or less) than the temperature (for example, higher than 60° C.) used in conventional spray drying. In this embodiment, since a crystal suspension containing a part of the sugar and/or sugar alcohol in a crystalline state is used, suitable granules can be obtained even if the spray drying is carried out under lower temperature conditions than conventionally.

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

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

In one embodiment, the inlet air temperature in the spray drying process is preferably no greater than 60°C, no greater than 55°C, no greater than 50°C, no greater than 45°C, no greater than 40°C, no greater than 35°C, no greater than 30°C, no greater than 25°C, 20 °C or lower, or 15 °C 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, and 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. °C or higher, 5 °C or higher, or 10 °C or higher.

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, and may be 10° C. or higher, 15° C. or higher, or 20° C. or higher.

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

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 comprise a further post-drying step, for example for the purpose of adjusting the water content of the granules. The post-drying step may be, for example, blowing air for a predetermined time to the granules adhering to the can wall in the spray dryer to further volatilize the water content of 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 cohesion of the granules may be less than 10.0% by weight, or 9.5% by weight or less, and may be 0.1% by weight or more, 1.0% by weight or more, or 4.0% by weight or more. . The degree of solidification of granules means the ratio of the portion of the granules after one week of spray drying that does not pass through a sieve with an opening of 2 mm and a sieve with an opening of 1 mm, and is measured by the method described in Examples below. be.

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

<Granule>
The granules according to the present embodiment contain at least one selected from the group consisting of crystalline sugar and crystalline sugar alcohol, and part of the crystalline sugar and/or sugar alcohol is in a crystalline state, and part is amorphous. The ratio of the average major diameter to the average minor diameter of the particles constituting the granule 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 functional materials. Detailed aspects of the crystalline sugar, the crystalline sugar alcohol, and the functional material are the same as those described above, so descriptions thereof are omitted. The “granule” as used herein is an aggregate of particles, and the particles (granule particles) constituting the granules contain one or more selected from the group consisting of crystalline sugars and sugar alcohols.

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

The granules are selected from the group consisting of a first sugar raw material selected from the group consisting of crystalline sugar and a crystalline sugar alcohol, and the group consisting of crystalline sugar and a crystalline sugar alcohol, and the first sugar and 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 source may be, for example, isomaltulose. The second sugar raw material may contain one or more of the above 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, or 80.0 parts by mass or more with respect to the total amount of 100 parts by mass of the crystalline sugar and the crystalline sugar alcohol. It may be 85.0 parts by mass or more, 90.0 parts by mass or more, or 95.0 parts by mass or more, and may be 99.9 parts by mass or less, 95.0 parts by mass or less, or 90.0 parts by mass 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 with respect to the total amount of 100 parts by mass of the crystalline sugar and the crystalline sugar alcohol; 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 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.

A granule according to one embodiment is composed of granular particles in which a part of crystalline sugar and/or sugar alcohol is in a crystalline state, and the crystalline sugar and/or sugar alcohol are aggregated together. In this case, the other part (other part) of the crystalline sugar and/or sugar alcohol is in a non-crystalline state and is held in the gaps 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 retained in the gaps formed by the crystalline sugar and/or sugar alcohol.

Aggregation of crystalline sugars and/or sugar alcohols can be confirmed by morphological observation of the appearance of granule particles or the fracture surface of granule particles using a scanning electron microscope (SEM) or a digital microscope. . Whether the amorphous sugar and/or sugar alcohol and the functional material are held in the gap can be confirmed by the following method.
(1) Observe the morphology of the granules during heating with a differential scanning calorimeter (DSC, for example Realview DSC (TA7000) manufactured by Hitachi High-Tech Science Co., Ltd.). As a result, it can be visually confirmed that amorphous sugars and sugar alcohols undergo a glass transition due to the temperature rise.
(2) Using a polarizing microscope (for example, a polarizing microscope (MT9200L) manufactured by Meiji Techno Co., Ltd.), the difference in polarization between the crystalline state and the amorphous state is visually observed.

The number of crystalline sugars and/or sugar alcohols contained in the particles constituting the granules (the number of crystals) 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 observing with a scanning electron microscope.

The shape of the particles constituting the granules may be substantially spherical from the viewpoint of better fluidity of the granules. Particles constituting the granules may have uneven surfaces from the viewpoint of better 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 since the solubility is even better, 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, 20.00-118.00 μm.

The "average particle size of granules" as used herein can be measured with an electron microscope. For the measurement, for example, MiniscopeTM3030 manufactured by Hitachi High-Technologies Corporation can be used. The details of the method for measuring the average particle size of the granules are as described in Examples below.

The standard deviation of the average particle size of the granules may be 40 μm or less, or 30 μm or less, or 5 μm or more, or 10 μm or more, since the granules are more resistant to caking.

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

The ratio of the average long diameter to the average short diameter of the granules is 1.40 or less, 1.20 or less, 1.10 or less, or 1.04 or less because the stability and fluidity of the granules are further improved. It may be 1.00 or more, or 1.01 or more. The ratio of the average long diameter to the average short diameter of the granules may be, for example, 1.00 to 1.04. The standard deviation of the ratio of the average major diameter to the average minor diameter of the granules is 0.20 or less, or 0.12 μm or less, because the granules are more easily dried, less likely to caking, and more fluid. and 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 may be 50.00 μm or less, 40.00 μm or less, 30.00 μm or less, and 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, 10.00-20.00 μm.

The standard deviation of the average particle size 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 size of the particles constituting the granules may be, for example, 1.00-3.30 μm.

The average short diameter 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 and 25.0 µm or less. The average length of the particles constituting the granules may be 10.0 µm or more, or 15.0 µm or more, and may be 50 µm or less, or 35 µm or less.

The ratio of the average major diameter to the average minor diameter of the particles constituting the granules is 3.1 or less. When the ratio of the average major diameter to the average minor diameter of the particles constituting the granules is 3.1 or less, the granules have excellent stability and fluidity. The ratio of the average long diameter to the average short diameter of the particles constituting the granules is 2.8 or less, 2.5 or less, 2.2 or less, or 1.9 or less because the stability and fluidity are further improved. may be greater than or equal to 0.5, greater than or equal to 1.0, or greater than or equal to 1.4.

The standard deviation of the ratio of the average major diameter to the average minor diameter of the particles constituting the granules may be 0.4 or less, or 0.3 or less, or may be greater 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 0.0400 cm ³ /g or less, 0.0350 cm ³ /g or less, 0.0300 cm ³ /g or less, or 0.0290 cm ³ /g or less.

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 or more. Below, it may be 9.000 m ² /g or more or 8.5000 m ² /g or less.

From the viewpoint of further improving the stability of the granules, the average pore diameter of the granules may be 60000 Å or less, 40000 Å or less, 20000 Å or less, 10000 Å or less, 800 Å or less, or 600 Å or less, 200 Å or more, 400 Å or more, or It may be 550 Å or more.

The porosity of the granules may be 3.80% or more, 3.90% or more, or 3.95% or more; It may be 10% or less.

Fragrance-containing granules may have a fragrance retention rate of 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. can be

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

The method for producing granules according to the present 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 crystallization of the raw material. Since the step of heating before spray drying can be omitted, granules can be produced by a simpler method than the conventional method.

The granules according to the present embodiment can be produced efficiently with a simpler operation, while suppressing the occurrence of caking. Furthermore, the granules according to the present embodiment can be efficiently produced with simpler operations, while suppressing deterioration in hygroscopicity, fluidity and jetting properties.

Since the granules are obtained by spray-drying under low-temperature conditions, when the granules contain a functional material, the function of the contained functional material is not easily lost by heat. That is, the granules retain the function of the functional material well even after the drying process. Generally, when obtaining granules by spray drying, it is difficult to obtain suitable granules unless the spray drying is carried out under higher temperature conditions. However, the granules according to the present embodiment can be easily obtained even under low temperature conditions.

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

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to the following examples.

<Example 1>
(Preparation of crystal suspension)
3.25 kg of palatinose (registered trademark of Mitsui Sugar Co., Ltd.) (PST-N, Mitsui Sugar Co., Ltd.) and 1.75 kg of water were placed in an 8 L metal container, diluted to Brix (Bx) 65, and suspended in crystals. I got the liquid. Thereafter, while maintaining the temperature of the crystal suspension at 30° C., the mixture was stirred for 2 hours at 350 rpm with a stirrer (Three One Motor, BL-1200, Shinto Kagaku Co., Ltd.) 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 warmed to 80° C. or higher were placed in a 3-liter plastic mug and stirred until the sugar was completely dissolved. The resulting sugar solution was diluted with ion-exchanged water until Bx reached 60 to prepare 1.5 L of sugar solution with Bx60. The prepared sugar solution of Bx60 was maintained at a temperature of 30° C. in a water bath (Personal-11, Taitech Co., Ltd.). Crystal suspension A1 was mixed with 0.96 kg of the sugar solution of Bx60 described above to prepare a spray liquid having a palatinose:sucrose solid content ratio of 85:15.

(spray drying)
About 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 conditions for spray drying were as follows.
Air temperature: 40°C
Exhaust air temperature: 28°C
Blower inverter frequency: 60Hz
Exhaust air volume: 38Hz
Tower internal pressure: slight positive pressure Atomizer rotation speed: 14,000 rpm (setting: 33 Hz)
Raw material supply rate: 50 mL/min, 4.0 kg/h (setting: 8.5 Hz)
Equipment: OC-16 (dry)

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

(Preparation of spray liquid)
1,800 g of granulated sugar (Mitsui Sugar Co., Ltd., GN) and 600 g of ion-exchanged water warmed to 80° C. or higher were placed in a 3-liter plastic mug and stirred until the sugar was completely dissolved. It was diluted with ion-exchanged water until Bx became 60, and 1.5 L of sugar solution with Bx60 was prepared. The prepared sugar solution of Bx60 was maintained at a temperature of 30° C. in a water bath (Personal-11, Taitech Co., Ltd.). 1.9 kg of Bx60 saccharide solution and 90.0 g of deionized water were mixed to prepare a flavor-free saccharide solution. Crystal suspension A2 was mixed with 1.90 kg of the sugar solution without fragrance described above to prepare a spray liquid having a solid content ratio of palatinose:sucrose of 85:15.

(spray drying)
While maintaining about 10 kg of the spray liquid at 30° C., the entire amount was spray-dried using a mono pump (3NTL08PUL, manufactured by Hyoshinso Co., Ltd.). The conditions for spray drying were as follows.
Air temperature: 40°C
Exhaust air temperature: 28-30℃
Blow air volume: 60Hz
Exhaust air volume: 38Hz
Static pressure in tower: slightly positive pressure Atomizer rotation speed: 14,000 rpm (setting: 33 Hz)
Atomizer type: disk-type atomizer Material supply rate: 50 mL/min, 4.0 kg/h (setting: 8.5 Hz)
Equipment: OC-16 (dry)

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

<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 57.5 Bx. Thereafter, while maintaining the diluted product at a temperature of 30° C., it was stirred for 2 hours at 300 rpm with a stirrer (Three One Motor, BL-1200, Shinto Kagaku Co., Ltd.) to obtain a crystal suspension (c1).

(Preparation of spray liquid)
1,800 g of granulated sugar (Mitsui Sugar Co., Ltd., GN) or 1,800 g of PST-N was added to a 3-liter plastic mug, 1,200 g of deionized water warmed to 80° C. or higher was added, and the mixture was stirred until the sugar was completely dissolved. Each obtained saccharide solution was diluted with deionized water until Bx became 60, whereby Bx60 sucrose syrup containing granulated sugar and Bx60 palatinose syrup containing PST-N were prepared as Bx60 saccharide solution (a). and were prepared. The prepared saccharide solution (a) of Bx60 was kept at a temperature of 30° C. using a water bath (PERSONAL-11, Taitec Co., Ltd.).

The brown sugar flavoring aqueous solution (b) was prepared by mixing 9.5 g of brown sugar flavoring (Kokuto Micron H-80210, Takasago International Corporation) and 40.5 g of deionized water.

The sugar solution (a) of Bx60 and the brown sugar flavoring aqueous solution (b) were mixed so as to have the composition shown in Table 1, and the resulting mixture was mixed with the crystal suspension (c1). Thus, 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, manufactured by Hyoshinso Co., Ltd.) under the following conditions.
Air temperature: 30°C
Exhaust air temperature: 28.1-24.0°C
Blow air volume: 60Hz
Exhaust air volume: 38Hz
Static pressure in tower: slightly positive pressure Atomizer rotation speed: 14,000 rpm (setting: 33 Hz)
Atomizer type: disk-type atomizer Material supply rate: 50 mL/min, 4.0 kg/h (setting: 8.5 Hz)
Device: OC-16 (dry)

After the completion of spraying, dry air was continuously supplied for 40 minutes without changing the operating conditions of the spray dryer to dry the interior of the dryer. After that, 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-liter metal container and boiled in hot water at 80° C. for 1 hour. After confirming that the sugar was completely dissolved, the metal container was filled with water 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 with an ultrasonic oscillator (ULTRA SONIC HOMOGENIZER, UH-600S, manufactured by SMT Co., Ltd.) (memory 8, continuous irradiation). After that, while maintaining the temperature of the content at 30° C., the mixture was stirred with a stirrer at 300 rpm for 1 hour and 45 minutes to obtain a 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 the comparative suspension B1 was used instead of the 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 of Comparative Example 1, except that 6.5 kg of PST-N and 3.5 kg of water were used.

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

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

<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-liter metal container and boiled in hot water at 80° C. for 1 hour. After confirming that the sugar was completely dissolved, water was added to adjust Bx to 57.5. The contents were cooled to 20°C by immersing an 8L metal container in 7°C water. While stirring at 300 rpm, irradiation was performed for 15 minutes with an ultrasonic oscillator (ULTRA SONIC HOMOGENIZER, UH-600S, manufactured by SMT Co., Ltd.) (memory 8, continuous irradiation). Thereafter, while maintaining the temperature of the content at 30° C., the mixture was stirred for 1 hour and 45 minutes with a stirrer at 300 rpm to obtain a comparative suspension (c2).

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

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

<Crystallization rate>
The crystallization rate was determined by placing 1 g of the crystal suspension or spray liquid in a 1.5 mL Eppendorf tube, centrifuging at 16,000 rpm for 1 minute using a centrifuge (M150IV, Sakuma Seisakusho Co., Ltd.), and obtaining the supernatant. The mass of the remaining crystals and the mass of the crystal suspension or the sprayed liquid were calculated by applying the following equations.
Crystallization rate (% by mass) = Mass of remaining crystals (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., BL type). Viscometer adapter no. 3 was attached, and the measurement part was immersed in the object for 15 seconds at a rotational speed of 12 rpm. The reading was then recorded. Based on the conversion factor of the Brookfield viscometer, the reading was multiplied by 100 to calculate the viscosity (mPa·s) of the object.

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

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

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

Even if Bx and the crystallization rate are equivalent, the method of the example uniformly produces crystals with a moderately small crystal diameter in the crystal suspension and the spray liquid, has a low viscosity, and has a high degree of granules after spray drying. Good recovery was obtained. Water activity was comparable in the methods of Examples and Comparative Examples.

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

(2) Visual Confirmation 500 g each of granules sealed in an aluminum pack and stored at room temperature of 25° C. for 1 month or more were 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 in a lump.
Medium: 10% or more and less than 30% of the granules are solidified in a mass.
- Strong: 30% or more of the granules are solidified in a mass.

As shown in Table 5, many of the granules obtained by the comparative example of the conventional method (crystal precipitation method) showed moderate caking, whereas the granules produced by the method of the example showed no caking. hardly confirmed.

<Crystal diameter of particles in crystal suspension and spray liquid>
A crystal suspension or spray liquid was dropped onto a slide glass, a cover glass was placed thereon, and measurements were taken at a magnification of 1000 times. The method for measuring the average particle size is to use a digital microscope (SKM-S31B-PC, Saito Kogaku Co., Ltd.) to determine the particle size of each of the 10 or more sugar crystals that constitute the sugar crystals. took the average of For 10 or more particles to be measured in the crystal suspension or spray liquid, the first The directional distance and the second directional distance were measured as width and height, respectively. The first direction is the same direction for all particles to be measured. Of the measured widths and heights, the longer one is the major diameter and the shorter one is the minor diameter, and the average of the particles to be measured was taken as the average major diameter and the average minor diameter. 1(A) and (B) show microscopic images of crystal suspensions obtained by the methods of Example 1 and Comparative Example 1, respectively.

<Crystal size of granules and particles constituting the granules>
The granule size and the crystal size of particles constituting the granules were measured using an electron microscope (MiniscopeTM3030, Hitachi High-Tech Co., Ltd.). Ten granules obtained by the methods of Examples and Comparative Examples were observed, and the length and breadth of each granule were measured to determine the average granule diameter. The long width and short width of 3 to 10 crystals contained in the granules were measured to determine the average crystal diameter in the granules. 2 shows an electron microscope image of the granules obtained by the method of Example 3. FIG. 3 shows an electron microscope image of the granules obtained by the method of Comparative Example 3. FIG.

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

<Evaluation of Fluidity, Spoutability and Bulk Density>
For the granules of Examples and Comparative Examples, R.I. L. The "flowability index" and "flowability index" proposed by Carr were calculated (Carr, RL "Evaluating flow properties of solids." Chem. Eng. (1965) 72(163-168)). Using a multifunctional powder physical property measuring instrument (Seishin Enterprise Co., Ltd., Multitester MT-02), the angle of repose (°), spatula angle (°), degree of compression (%) and uniformity (-) of the granules were measured. Based on Carr's theory, an index corresponding to each measurement was obtained. A fluidity index was obtained by summing the indices of each measurement. With a multifunctional powder physical property measuring instrument, the collapse angle (°) and difference angle (°) of granules, and the degree of dispersion (%) are obtained, and the index corresponding to each measurement value obtained based on Carr's theory and the flow The jettability index was obtained by summing the indices based on the sex index. The temperature and humidity during the measurement were 25° C. and 50%.

The fluidity and jetting properties of the granules were evaluated based on Carr's evaluation criteria shown below.
Fluidity evaluation criteria Fluidity index value Degree of fluidity 90-100 Best 80-89 Good 70-79 Fairly good 60-69 Normal 40-59 Not so good 0-19 Very bad

Ejectivity evaluation criteria Ejectivity index value Degree of jetty 80-100 Very strong 60-79 Fairly strong 40-59 Tendency 25-39 Possibly 0-24 None

The granules obtained by the method of Examples had good fluidity and jetting properties similar to those of the method of Comparative Examples, although they were obtained by a simpler operation.

Regarding the angle of repose and uniformity, refer to the dictionary of powder engineering terms (Japan Society of Powder Technology, updated May 17, 2021, URL: http://www.sptj.jp/powderpedia/words/10382/) Fluidity was evaluated separately based on the Carr Fluidity Index table provided.

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 instrument. 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 (sorption/desorption isotherm) of the granules obtained by the respective methods of Example 3 and Comparative Example 3 was measured using a dynamic water vapor adsorption measurement device (Surface Measurement Systems Ltd., DVS Intrinsic). Using 10 mg of the sample, the relative humidity was increased by 5% from 0% to 90%, and then decreased to 0% by the same procedure. Maintain a constant relative humidity until the moisture content change rate (dm / dt) of the sample falls below 0.02 in 10 minutes, or until 30 minutes later even if it does not reach 0.02% / min, and the temperature is always 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 hygroscopic evaluation results 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>
The average pore diameter, total pore volume, porosity and total specific surface area of the granules obtained by the methods of Example 1 and Comparative Example 1 were evaluated using a mercury intrusion pore size analyzer (Quantachrome, POREMASTER 60GT). A 0.4 g 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 injected mercury (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 when pores are assumed to be open cylindrical (calculated from pore distribution and volume)

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

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

It was confirmed that the granules obtained by the method of the example exhibit an aroma retention rate similar to or higher than that of the granules obtained by the method of the comparative example having the same sugar content, and the aroma retention is equal to or higher than that of the granules obtained by the method of the comparative example having the same sugar content. .

Claims (19)

It contains at least one 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 crystallization of the raw material after dissolution. obtaining a crystal suspension contained in a crystalline state;
and 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 of claim 1, wherein said sugars and said sugar alcohols are monosaccharides, disaccharides, trisaccharides and sugar alcohols thereof. 3. The method according to claim 1 or 2, wherein said raw material is at least one selected from the group consisting of palatinose, sucrose and trehalose. 3. A method according to claim 1 or 2, wherein the crystal suspension further contains a functional material. 5. The method of claim 4 , wherein said functional material is an enzyme, microorganism, or fragrance. The method according to claim 1 or 2, wherein the crystal suspension has a viscosity of 50 to 1550 mPa·s at 25°C. 3. The method according to claim 1, wherein the crystalline sugar and/or sugar alcohol in the crystal suspension has an average particle size of 1.00 to 15.90 μm. 3. The method according to claim 1, 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. 3. The method according to claim 1, 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. 3. The method according to claim 1 or 2, wherein the ratio of the average major diameter to the average minor diameter of the particles constituting the granules is 3.1 or less. 3. The method according to claim 1 or 2, wherein the granules have a degree of cohesion of less than 10.0% by weight. Granules containing at least one selected from the group consisting of crystalline sugar and crystalline sugar alcohol,
part of the sugar and/or the sugar alcohol is in a crystalline state and the other part is in an amorphous state;
A granule, wherein the ratio of the average major axis to the average minor axis of particles constituting the granule is 3.1 or less. 13. Granules according to claim 12 , wherein said sugars and said sugar alcohols are monosaccharides, disaccharides, trisaccharides and sugar alcohols thereof. 14. The granules according to claim 12 or 13 , wherein at least one selected from the group consisting of crystalline sugars and crystalline sugar alcohols is at least one selected from the group consisting of palatinose, sucrose and trehalose. 14. Granules according to claim 12 or 13 , further comprising a functional material. 16. Granules according to claim 15 , wherein the functional material is enzymes, microorganisms or perfumes. 14. The granules according to claim 12 or 13 , wherein the particles constituting said granules have an average particle size of 10.00 to 20.00 μm. The granules according to claim 12 or 13 , wherein the particles constituting the granules have an average particle size standard deviation of 1.00 to 3.30 µm. 14. Granules according to claim 12 or 13 , wherein the degree of caking of the granules is less than 10.0% by weight.

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