JP2024015757A - Powdery composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powdery composition which has a large proportion of a supported hydrophilic organic solvent, with the volatilization of the solvent being inhibited, and has excellent flowability as a powder.

SOLUTION: A powdery composition includes a hydrophilic organic solvent supported on a powdered substrate. The powdered substrate includes sorbitol having a specific surface area according to a BET-type one point method of 5 m²/g or more and a pore volume according to a mercury intrusion technique of 0.45 mL/g or more. The impregnation proportion of the hydrophilic organic solvent in the powdery composition is 1 to 50 wt.%.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a powder composition comprising a hydrophilic organic solvent supported on a powdered substrate.

Hydrophilic organic solvents such as ethanol and acetic acid are used in a variety of products, such as food and beverages, cosmetics, fragrances, pharmaceuticals, quasi-drugs, and daily necessities, depending on the purpose.

Such hydrophilic organic solvents are liquid at room temperature and are inconvenient to handle when stored in bags or incorporated into powder formulations, so the use of powdered hydrophilic organic solvents is increasing. . Examples of powdering methods for hydrophilic organic solvents include powdering by supporting a hydrophilic organic solvent on a powdered base material, and powdering by suspending a powdered base material in a hydrophilic organic solvent and drying. something is known. However, when a powder composition is prepared using a conventional method of powdering a hydrophilic organic solvent supported on a powder base material, the proportion of the hydrophilic organic solvent is small and the hydrophilic organic solvent evaporates quickly. When using a powder composition, the proportion of the hydrophilic organic solvent becomes even smaller. Furthermore, even in powdering methods that involve a drying step, the proportion of the hydrophilic organic solvent was similarly small because volatilization was promoted by heating.

Patent Document 1 proposes powdered brewed vinegar obtained by adsorbing and mixing concentrated brewed vinegar with anhydrous sodium acetate or dextrin to form a powder. However, powdered brewed vinegar using anhydrous sodium acetate or dextrin has a small proportion of concentrated brewed vinegar that can be supported, and the concentrated brewed vinegar is easily volatilized. Moreover, the fluidity of the obtained powdered brewed vinegar was not sufficient.

Patent Document 2 proposes an alcohol-containing powder obtained by mixing an alcohol-containing liquid with alkenylsuccinate starch and pulverizing the mixture. However, since a heating operation is performed in the drying process, volatilization of alcohol is promoted, and the proportion of alcohol supported in the obtained powder composition was small. Further, there were also problems such as the work process being complicated.

Patent Document 3 proposes an acetic acid-containing powder composition obtained by mixing an acetic acid-containing liquid with alkenylsuccinate starch, but this composition has the same problems as Patent Document 2 above. Ta.

Patent Document 4 proposes a powdered liquor obtained by mixing alcohol with a powdered base material such as dextrin. However, the fluidity of the obtained powdered liquor was not sufficient, and the supported alcohol was easily volatilized.

Therefore, there has been a desire for a powder composition in which a hydrophilic organic solvent is pulverized, which has excellent fluidity as a powder, and in which volatilization of the hydrophilic organic solvent is suppressed.

Japanese Patent Application Publication No. 2006-087389 JP2009-247350A Japanese Patent Application Publication No. 2010-4865 Japanese Patent Application Publication No. 2016-123284

An object of the present invention is to provide a powder composition that has a large proportion of supported hydrophilic organic solvent, has excellent fluidity as a powder, and has suppressed volatility of the hydrophilic organic solvent.

As a result of extensive studies, the present inventors have completed the present invention by discovering that the above problems can be solved by supporting a hydrophilic organic solvent on a powdered base material containing a specific sorbitol.

That is, the present invention provides a powder composition in which a hydrophilic organic solvent is supported on a powdered base material, and the powdered base material has a specific surface area of 5 m 2 /g or more by the BET single point method, and a fine surface area of 5 m ² /g or more by the mercury intrusion method. Provided is a powder composition containing sorbitol having a pore volume of 0.45 mL/g or more and having a proportion of a hydrophilic organic solvent in the powder composition (hereinafter referred to as impregnation rate) of 1 to 50% by weight.

The present invention will be explained in detail below. The hydrophilic organic solvent that can be used in the powder composition of the present invention needs to be liquid at room temperature. Substances that are solid or semi-solid at room temperature cannot be used because they are difficult to support on the powdered base material. Note that in the present invention, normal temperature is about 25°C.

Hydrophilic organic solvents include alcohol, carboxylic acids with linear saturated hydrocarbon chains, acetone, pyridine, ethylamine, diethylamine, N-methyl-2-pyrrolidone, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and , unsaturated carboxylic acids such as acrylic acid. Preferred hydrophilic organic solvents include alcohols and carboxylic acids having a linear saturated hydrocarbon chain.

The hydrophilic organic solvent used in the present invention may contain water. When using a hydrophilic organic solvent containing water, the water content is preferably 15% by weight or less, more preferably 12% by weight or less, and even more preferably 0.01 to 10% by weight. .

Examples of the alcohol include methanol, ethanol, propanol, isopropanol, glycerol, ethylene glycol, diethylene glycol, propylene glycol, etc., with ethanol and propanol being preferred, and ethanol being more preferred.

Examples of the carboxylic acid having a linear saturated hydrocarbon chain include formic acid, acetic acid, propionic acid, butyric acid, etc., with acetic acid and propionic acid being preferred, and acetic acid being more preferred.

A mixture of two or more types of hydrophilic organic solvents may be used, or a mixture of two or more types of powder compositions each containing one type of hydrophilic organic solvent may be used. For example, by manufacturing a powder composition in which ethanol and acetic acid are separately supported on a powdered base material, and mixing or using them together, it becomes possible to apply ethanol and acetic acid simultaneously.

The powdered base material used in the present invention has a specific surface area of 5 m ² /g or more by the BET single point method and a pore volume of 0.45 mL/g or more by the mercury porosimetry method (herein referred to as porous sorbitol). ). Preferably, the powdered base material consists only of porous sorbitol.

The porous sorbitol used in the present invention may be adjusted to have an average particle size in a specific range, and the average particle size in this case is determined using a laser diffraction particle size distribution analyzer (Mastersizer (registered trademark) 3000). , manufactured by Malvern Co., Ltd.), preferably 1 to 600 μm, more preferably 20 to 550 μm, and even more preferably 30 to 500 μm.

Porous sorbitol can be produced, for example, by kneading molten sorbitol and ethanol and then drying the mixture under reduced pressure. In one preferred embodiment, the method for producing porous sorbitol of the present invention includes the following steps:
a) a step of supplying molten sorbitol and ethanol into a kneading device;
b) a step of kneading molten sorbitol and ethanol in a kneading device while maintaining it at 50 to 78 °C, and c) drying the kneaded product obtained in b) under reduced pressure at 25 to 90 °C and 100 to 30,000 Pa. It includes a step of removing ethanol.

Furthermore, the above manufacturing method will be explained more specifically. First, in step a), 10 to 70 parts by weight of molten sorbitol and 30 to 90 parts by weight of ethanol are fed into a kneading device. The amount fed into the kneading device is preferably 15 to 68 parts by weight of molten sorbitol and 32 to 85 parts by weight of ethanol, more preferably 20 to 65 parts by weight of molten sorbitol and 35 to 80 parts by weight of ethanol. be.

The water content contained in the ethanol used in step a) is, for example, 10% by weight or less. The amount of water contained in ethanol is preferably 8% by weight or less, more preferably 5% by weight or less, even more preferably 2% by weight or less, particularly preferably 0% by weight (ethanol only). The smaller the amount of water contained in ethanol, the more the specific surface area of the produced porous sorbitol tends to improve.

Next, in step b), the molten sorbitol and ethanol in the kneading device are kneaded while being maintained at 50 to 78°C. By maintaining the temperature in the kneading device at 50 to 78° C., molten sorbitol and ethanol can be kneaded without rapidly solidifying the molten sorbitol in the kneading device and while suppressing volatilization of ethanol. The temperature inside the kneading device is preferably 55 to 78°C, more preferably 60 to 75°C.

In step c), the kneaded product obtained in step b) is dried under reduced pressure at 25 to 90° C. and 100 to 30,000 Pa to remove ethanol and obtain porous sorbitol. Drying under reduced pressure is performed using, for example, a reduced pressure dryer such as an evaporator. The porous sorbitol obtained in step c) can be pulverized or sized using a blender or the like to form a powder.

As the apparatus used for producing the above-mentioned porous sorbitol, kneading machines such as a KRC kneader, a horizontal kneader, and a vertical kneader can be mentioned.KRC kneaders and horizontal kneaders are preferable in terms of quality, and are excellent in balance with production efficiency. The KRC kneader is more preferable.

The specific surface area of the powdered base material that can be used in the present invention is 5 m ² /g or more, preferably 6 to 50 m ² /g, and more preferably 7 to 30 m ² /g.

The specific surface area as used in the present invention means a value measured by the BET single point method using, for example, MONOSORB (manufactured by Yuasa Ionics Co., Ltd.) or an equivalent specific surface area measuring device. For example, the specific surface area can be measured under the following measurement conditions.
[Measurement condition]
Method: BET single point method Carrier gas: Nitrogen/helium mixed gas (N ₂ :He=30:70)
Measurement gas flow rate: 15cc/min Degassing conditions: 60°C, 20 minutes

The pore volume of the powdered base material that can be used in the present invention is 0.45 mL/g or more, preferably 0.5 to 3 mL/g, and more preferably 0.55 to 2.5 mL/g.

The pore volume in the present invention means a value measured by mercury porosimetry using, for example, Pascal 240 (manufactured by Thermo Fisher Scientific) or an equivalent pore volume measuring device.

By mixing the powdered base material and the hydrophilic organic solvent, the hydrophilic organic solvent can be supported on the powdered base material. For example, the hydrophilic organic solvent is supported on the powdered base material by adding and mixing the hydrophilic organic solvent little by little to the powdered base material at a weight ratio that achieves a desired impregnation rate.

In the powder composition of the present invention, the impregnation rate of the hydrophilic organic solvent to the powdered base material is 1 to 50% by weight, preferably 5 to 48% by weight, and the impregnation rate is 10 to 45% by weight. %, and even more preferably an impregnation rate of 15 to 40% by weight. When the impregnation rate is less than 1% by weight, the amount of sorbitol, which is a powder base material, in the powder composition increases relatively, so the taste and physical properties of the added substance tend to change, and when the impregnation rate exceeds 50% by weight, In this case, the hydrophilic organic solvent is exposed on the surface of the powder composition, which tends to deteriorate fluidity. The impregnation rate in the present invention means the ratio of the weight of the hydrophilic organic solvent to the total weight of the hydrophilic organic solvent and the powdered base material.

The angle of repose of the powder composition of the present invention is preferably 30 to 60°, more preferably 35 to 58°, even more preferably 40 to 55°. When the angle of repose is less than 30°, scattering tends to become high, and when the angle of repose exceeds 60°, fluidity tends to deteriorate.

The angle of repose in the present invention means a value measured by the cylindrical rotation method, for example, with a cylindrical rotation method angle of repose measuring instrument (Tsutsui Rikagaku Kikai Co., Ltd.) or an equivalent measuring instrument.

When the powder composition of the present invention supports ethanol, the volatilization rate of ethanol is preferably 1 to 25%, more preferably 2 to 24%, and 3 to 23%. More preferred. When the volatilization rate exceeds 25%, the supported ethanol tends to volatilize quickly and the amount of ethanol retained tends to decrease. If the volatilization rate is less than 1%, it will be difficult to use it for purposes of volatilizing ethanol.

When the powder composition of the present invention supports acetic acid, the volatilization rate of acetic acid is preferably 1 to 10%, more preferably 1.5 to 9.5%, and more preferably 2 to 9%. It is more preferable that When the volatilization rate exceeds 10%, the supported acetic acid tends to volatilize quickly and the amount of acetic acid retained tends to decrease. If the volatilization rate is less than 1%, it will be difficult to use it for purposes of volatilizing acetic acid.

In the present invention, the volatilization rate refers to the rate of weight loss of the hydrophilic organic solvent volatilized after the powder composition is left standing in an environment of 25° C. and 50% relative humidity for 5 minutes.

The powder composition of the present invention can be used in various fields such as food and beverages, cosmetics, fragrances, pharmaceuticals, quasi-drugs, and daily necessities, depending on the purpose of the hydrophilic organic solvent.

One preferred embodiment using the powder composition of the present invention is an ethanol volatilization agent in which a powder composition containing ethanol is sealed in a bag or the like made of an alcohol-permeable film.

Another preferred embodiment using the powder composition of the present invention is a powdered liquor using a powder composition containing ethanol.

Another preferred embodiment using the powder composition of the present invention includes a seasoning preparation using a powder composition containing ethanol or acetic acid alone, or a combination of a powder composition containing ethanol and a powder composition containing acetic acid. , pH adjusters, shelf life enhancers, preservatives, antiseptics, cleaning and disinfecting agents, etc.

Another preferred embodiment using the powder composition of the present invention is exemplified by powdered vinegar using a powder composition containing acetic acid.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Test example 1 (preparation of powdered base material)
The materials shown below were melt-kneaded in the proportions (wt%) and under the conditions shown in Table 1, and the crystallized kneaded product was dried under reduced pressure using a rotary evaporator under the conditions shown in Table 1 to obtain powdered base material 1. The obtained powdered base material was pulverized using a blender shown below at 15,700 rpm for 30 seconds. The specific surface area, pore volume, and average particle diameter of the powdered base materials 1 and 6 to 10 after pulverization were measured under the following conditions. For powdered base materials 2 to 5, the kneaded material did not crystallize when melted and kneaded for 30 minutes, so the evaluation was completed without measuring the specific surface area, pore volume, and average particle diameter.

<Materials>
・Sorbitol 1: Powdered sorbitol “Ueno” 20M (manufactured by Ueno Food Techno Co., Ltd., sorbitol purity 92%)
・Sorbitol 2: Partec (registered trademark) SI 150 (manufactured by Merck & Co., sorbitol purity 98.4%)
・Maltitol: Powdered maltitol “Ueno” 60M (manufactured by Ueno Food Techno Co., Ltd.)
・Xylitol: Primary xylitol (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・Maltose: Sunmalt (registered trademark) Midori (manufactured by Hayashibara Co., Ltd.)
・Dextrin: Max 1000EX-C (Matsuya Chemical Industry Co., Ltd.)
・Pregelatinized starch: F Smash (registered trademark) (manufactured by Futamura Chemical Co., Ltd.)
・Ethanol: Fermented ethanol (95 degrees, manufactured by Daiichi Alcohol Co., Ltd., ethanol 92.3% by weight)
・Ion exchange water <kneading device>
・KRC: KRC kneader (S2 type, manufactured by Kurimoto Iron Works Co., Ltd.)
・Horizontal: Horizontal kneader (semi-KC-6 type, manufactured by Satake Co., Ltd.)
<Blender>
・Blender (16Speed Blender, manufactured by Oster)

Measurement of specific surface area The powdered base material was placed in a measurement cell (volume: 1.7 cm ³ ) to a capacity of approximately 1/2, and measured using a BET type specific surface area meter (MONOSORB, manufactured by Yuasa Ionics Co., Ltd.) under the following conditions. It was measured with
[Measurement condition]
Method: BET single point method Carrier gas: Nitrogen/helium mixed gas (N ₂ :He=30:70)
Measurement gas flow rate: 15cc/min Degassing conditions: 60°C, 20 minutes

Measurement of Pore Volume Pore volume was measured using a mercury porosimeter (Pascal 240, manufactured by Thermo Fisher Scientific).

Measurement of Average Particle Size The average particle size was measured using a laser diffraction particle size distribution analyzer (Mastersizer (registered trademark) 3000, manufactured by Malvern).

Examples 1-2 and Comparative Examples 1-10
Preparation of ethanol powder composition
60 g of the powdered base material produced in the above test example was placed in a resin bag, and 20 g of the following ethanol was added little by little while shaking to prepare a powder composition with an impregnation rate of 25% by weight (Example 1 and Comparative Example 1). , 3, 5, 7, 9). Further, powder compositions with an impregnation rate of 40% by weight were prepared in the same manner except that the amount of ethanol was changed to 40 g (Example 2 and Comparative Examples 2, 4, 6, 8, 10).
<Hydrophilic organic solvent>
・Reagent grade ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Ethanol 99.5% by weight, water content 0.2% by weight)

Measurement of Angle of Repose 150 mL of the powder composition was placed in a glass cylindrical container, and the angle of repose was measured using a cylindrical rotation method angle of repose measuring device (Tsutsui Rikagaku Kikai Co., Ltd.). The results are shown in Table 2.

Measurement of volatilization rate After putting 1 g of the powder composition into a glass petri dish with an inner diameter of 41 mm, the lid was opened in an environment of 25 ° C. and 50% relative humidity, and after leaving it for 5 minutes, the volatilization rate was calculated using the following formula. The results are shown in Table 2.
Volatilization rate (%) of powder composition = (A-B)/C×100
A: Weight of powder composition (g)
B: Weight of powder composition after standing for 5 minutes (g)
C: Weight of hydrophilic organic solvent in powder composition (g)

The powder compositions of the present invention (Examples 1 and 2) have a lower angle of repose and a lower volatilization rate than the powder compositions of Comparative Examples 1 to 10, so they have excellent fluidity and a higher It was confirmed that it carried ethanol.

Examples 3-4 and Comparative Examples 11-20
Preparation of acetic acid powder composition
A powder composition was prepared in the same manner as in the above example except that ethanol was replaced with acetic acid shown below, and the angle of repose and volatilization rate were measured. The results are shown in Table 3.
<Hydrophilic organic solvent>
・Reagent special grade acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Acetic acid 99.7% by weight, water content 0.25% by weight)

The powder compositions of the present invention (Examples 3 and 4) have a lower angle of repose and a lower volatilization rate than the powder compositions of Comparative Examples 11 to 20, so they have excellent fluidity and a higher It was confirmed that it supported 100% of acetic acid.

Example 5
Manufacture of ethanol volatile agent
Each component was blended in the proportions shown in Table 4 to produce an ethanol volatile agent. The ethanol volatilizing agent is one form of a formulation using the powder composition of the present invention.
<Materials>
・Vermiculite (manufactured by Asahi Kogyo Co., Ltd.)
・Activated carbon (manufactured by Takeda Pharmaceutical Company Limited)

Example 6
Manufacture of food preservative formulations
Each component was blended in the proportions shown in Table 5 to produce a food preservative formulation. The food preservative formulation is one form of formulation using the powder composition of the present invention.
<Materials>
・Shirako protein: Shirako protein extract (manufactured by Ueno Food Techno Co., Ltd.)

Example 7
Production of seasoned vinegar
Each component was blended in the proportions shown in Table 6 to produce seasoned vinegar. The seasoned vinegar is one form of a formulation using the powder composition of the present invention.
<Materials>
・Dextrin: Max 1000EX-C (manufactured by Matsutani Chemical Industry Co., Ltd.)
・Maltose: Sunmalt (registered trademark) S (manufactured by Hayashibara Co., Ltd.)
・Purified salt: Special grade purified salt (manufactured by Nippon Salt Manufacturing Co., Ltd.)

Claims (6)

A powder composition comprising a hydrophilic organic solvent supported on a powdered base material,
The powdered base material contains sorbitol having a specific surface area of 5 m ² /g or more by the BET single point method and a pore volume of 0.45 mL / g or more by the mercury intrusion method,
A powder composition in which the impregnation rate of a hydrophilic organic solvent in the powder composition is 1 to 50% by weight. The powder composition according to claim 1, having an angle of repose of 30 to 60°. The powder composition according to claim 1 or 2, wherein the hydrophilic organic solvent is ethanol or acetic acid. Claim 3, wherein the hydrophilic organic solvent is ethanol, and the volatilization rate of ethanol is 1 to 25% as calculated by the following formula when left standing for 5 minutes in an environment of 25° C. and 50% relative humidity. The powder composition described in .
Volatilization rate (%) of powder composition = (A-B)/C×100
A: Weight of powder composition (g)
B: Weight of powder composition after standing for 5 minutes (g)
C: Weight of hydrophilic organic solvent in powder composition (g) Claim 3, wherein the hydrophilic organic solvent is acetic acid, and the volatilization rate of acetic acid calculated by the following formula is 1 to 10% when left for 5 minutes in an environment of 25° C. and 50% relative humidity. The powder composition described in .
Volatilization rate (%) of powder composition = (A-B)/C×100
A: Weight of powder composition (g)
B: Weight of powder composition after standing for 5 minutes (g)
C: Weight of hydrophilic organic solvent in powder composition (g) The powder composition according to claim 1 or 2, comprising a powder composition containing ethanol and a powder composition containing acetic acid.