JP3075942B2 - Inclusion method of oily substance and inclusion compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for encapsulating a volatile oily substance such as a fragrance or an organic antibacterial agent, and an inclusion compound thereof.

[0002]

2. Description of the Related Art Conventionally, allyl isothiocyanate (chemical formula: C ₄ H ₅ NS, Allyl IsoTioCyan
ate: hereinafter referred to as AITC) is known to have an excellent bactericidal action, a bacteriostatic action, and an antibacterial action for suppressing the growth of mold. Further, since AITC is a natural product and has high safety, it was considered that the AITC is used for preserving food.

[0003] However, AITC has a peculiar pungent odor and is inconvenient to handle, and when the AITC is used in food, the pungent odor adversely affects the aroma and taste of the food. Has disadvantages. Furthermore, A
ITC has the disadvantage that it is not stable because of its high volatility, and it is also an unstable substance that quickly oxidizes and changes to a garlic-like odor.

Therefore, in order to avoid each of the above disadvantages,
JP-A-3-224437 discloses an inclusion compound in which AITC is included in cyclodextrin. The clathrate compound was prepared by adding 0.3 to 3 parts by weight of water to 1 part by weight of cyclodextrin, and adding 0.1 to 0.
After adding 2 parts by weight, kneading with a kneader or the like for 30 minutes to several hours to allow the AITC to be included in the cyclodextrin, moisture is evaporated by hot-air drying or the like, and pulverized to powder the clathrate. It is manufactured by a so-called kneading method.

[0005] The powder produced by such a kneading method becomes granular with a distorted shape. When the present inventors prepare the powder, AITC and cyclodextrin are included in equimolar amounts. It is known that the saturated inclusion amount of AITC in cyclodextrin (about 8
AIT in cyclodextrin (% by weight)
The inclusion rate indicating the ratio of the actual amount of inclusion of C was 60%.

[0006]

However, in the above-mentioned conventional clathrate compound, AITC is formed from the surface of the granular clathrate compound.
Will evaporate, but its surface area is small,
Since the inclusion rate is low, the transpiration rate of the AITC is slowed down, and depending on the food, there is a problem that the bactericidal action and the bacteriostatic action of the AITC cannot be sufficiently exhibited.

[0007]

According to the first aspect of the present invention, there is provided a method for enclosing an oily substance, comprising the steps of:
When the oily substance is included in the cyclodextrin in the mixed liquid obtained by mixing the aqueous solution of the cyclodextrin and the oily substance in the stirring tank, the rotation axis of the turbine is rotated by the blades of the turbine rotating in the mixed liquid. While forming a substantially parallel flow of the mixed liquid and causing the mixed liquid to convect in the stirring tank, the mixed liquid is moved by the tip of the blade of the turbine that moves in a direction substantially perpendicular to the flow direction of the mixed liquid. It is characterized by stirring.

[0008] The inclusion compound of an oily substance according to claim 2 of the present invention is obtained by granulating a mixture obtained by the inclusion method according to claim 1, and comprises an oily substance in cyclodextrin. The inclusion rate, which indicates the ratio of the amount of inclusion of the oily substance in the cyclodextrin to the amount of the saturated inclusion, is 80% or more.

That is, 1 part by weight of cyclodextrin and 1 to 10 parts by weight of water are mixed to prepare a mixed solution in which cyclodextrin is dispersed in water.
While stirring the mixture at a turbine speed of 500 to 20,000 rpm with a convection high-speed stirrer, 0.01 to 0.2 parts by weight of an oily substance was gradually added to 1 part by weight of cyclodextrin, and after the addition was completed, By continuing stirring for 10 to 3 hours, a mixed solution containing an inclusion compound having an inclusion ratio of 80% or more is obtained.

The convection type high-speed stirrer forms a flow of the mixed liquid substantially parallel to the rotation axis of the turbine by the blades of the turbine rotating in the mixed liquid, and convects the mixed liquid in the stirring tank. The mixture is agitated by the tip of the blade of the turbine which moves in a direction substantially perpendicular to the flow direction of the mixture.

Examples of the oily substance include isothiocyanates such as AITC, hinokitiol and terpenes, which are volatile at room temperature and have a bactericidal / bacteriostatic action.
Examples include wasabi extract, horseradish extract, mustard extract, horseradish extract, essential oil of fruit, and balm such as spices and flowers.

As the cyclodextrin, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, or a mixture of at least two of them can be used. In particular, β-cyclodextrin is preferably used because it is inexpensive.

In the above-mentioned granulation of the mixed liquid, if the cyclodextrin in the mixed liquid is 90% by weight or more, the viscosity of the mixed liquid becomes high, which is not suitable for granulation. The inclusion compound having a desired average particle size can be obtained by changing the content of cyclodextrin in the mixture within the range of 1 to 90% by weight.

The granulation method is not particularly limited as long as the obtained particles are porous and can be formed into a substantially spherical shape having a particle size of 200 μm or less. A granulation method can be used. In addition, a granulation method obtained by freeze-drying and then pulverizing, or a high-speed stirring type granulation method may be used.

When the spray drying granulation method is used as the above method, the blowing temperature is 100 to 200 ° C., and the discharging temperature is 50 to 120.
° C, by adjusting the solid concentration of the mixture containing the clathrate, the liquid temperature, the blast temperature and exhaust air temperature during spray drying, the peripheral speed of the rotating disk of the rotating disk type sprayer during spray drying, etc. It is possible to obtain a granulated clathrate compound having any moisture, powder particle size and bulk density according to the purpose of use and the target food.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to FIG. In the method of inclusion of an oily substance, when an AITC as an oily substance is gradually added to a suspension of cyclodextrin by dropping or the like to form an inclusion compound in which the AITC is included in cyclodextrin,
A high-speed convection-type stirrer is used to efficiently stir the suspension to increase the clathrate of the clathrate from 60% to 80% or more.

As shown in FIG. 1, the stirrer has a cylindrical stirring tank 1 having a bottom and a stirring section 2 which is detachable from the stirring tank 1. Although not shown, the stirring unit 2 includes a motor, a drive shaft 3 connected to a rotation shaft of the motor, and a turbine 4 integrally rotating with the drive shaft 3 at a tip end of the drive shaft 3. Have.

The turbine 4 has a disk-shaped base 4a that rotates integrally with the drive shaft 3, and a number of blades 4b provided around the base 4a. Each of the blades 4b convects the mixed liquid 1a in the stirring tank 1, and
It is for stirring, and is oblique to the base 4a,
In other words, they are attached radially outward with respect to the base 4a and in directions separated from each other in the rotation axis direction of the drive shaft 3.

A substantially cylindrical stator 5 is mounted on the agitating section 2 such that the drive shaft 3 is rotatably supported on the turbine 4.
And a plurality of stator lots 6 for fixing the stator 5 at predetermined intervals to a motor support (not shown).

The stator 5 has a cylindrical bearing portion 5a.
Are provided for rotatably supporting the turbine 4, and a discharge path 5 b of the mixed liquid is formed by the outer peripheral surface of the bearing portion 5 a and the inner peripheral surface of the stator 5, while the tip of the stator 5 On the side, a suction port 5c having a smaller diameter than the inner circumference of the stator 5 is formed.

Further, the agitator 2 has a radial baffle-shaped commutation plate 7 between the support (not shown) of the motor and the stator 5 for smoothly convection of the mixed liquid 1a.
Penetrates the drive shaft 3 and each stator lot 6,
It is provided movably along the rotation axis direction of the drive shaft 3. The commutation plate 7 is provided with a lock mechanism (not shown) capable of temporarily fixing the commutation plate 7 at a predetermined position.

The stirring section 2 is attached to the stirring tank 1 by inserting the turbine 4 coaxially from above into the vicinity of the bottom of the stirring tank 1.
The commutation plate 7 is set so that the direction of flow of the mixed solution from above is changed to the inner wall of the stirred tank 1 in the upper layer of the mixed solution 1 a in the stirred tank 1.

The operation of such a stirrer will be described. The pressure difference between both surfaces of the blades 4b of the turbine 4 generated by the high-speed rotation of the turbine 4 acts like a pump, and the mixing in the stirring tank 1 is performed. The liquid 1a is sucked through a suction port 5c, which is a lower part of the stator 5, and is discharged upward from a discharge port on the upper part of the stator 5.

The rising flow of the mixed liquid 1 a is changed by the commutation plate 7 on the upper surface, descends along the inner surface of the stirring tank 1, and reaches the bottom of the stirring tank 1 again. The mixed liquid 1a in such a stirring tank 1 is constantly stirred while convection.

At this time, the blades 4b rotating at a high speed with respect to the stator 5 rotate so as to traverse the flow of the mixed liquid 1a in a direction substantially perpendicular to the flow of the mixed liquid 1a.
Can generate a strong shear force, impact, and turbulence on the flowing liquid mixture 1a, and the liquid mixture 1a is agitated by such shear force, impact, and turbulence,
The size of oil droplets of AITC, which is an oily substance contained in the liquid mixture 1a, can be reduced.

Example 1 Next, an example of an inclusion method using the above-mentioned stirrer and an example of its inclusion compound will be described. First, 1500 g of purified water and then 900 g of β-CD are put into the stirring tank 1, and the turbine 4 is rotated at 5000 rpm to obtain purified water and β.
While stirring the mixed solution 1a comprising
100 g gradually, and then turbine 4
The mixture was rotated at 0 rpm and stirred for 90 minutes, and AITC was included in the mixture 1a with β-CD to obtain an inclusion slurry.

Subsequently, from the clathrate slurry, a granulated body of the CD compound of AITC was prepared by spray drying granulation method.
00 g was obtained. The obtained granule was a spherical powder having a particle size of 10 to 50 μm.

The operating conditions in the above-mentioned spray-drying granulation method are as follows: the blowing temperature, which is the temperature of the outlet of hot air to the spray-drying chamber, is 150 ° C., and the temperature of the outlet of the granules from the spray-drying chamber is A certain exhaust air temperature is 70 ° C, and the rotation speed of the atomizer for spraying the clathrate slurry into the spray drying chamber is 28000 rpm.
Set to.

Example 2 Next, another example of the inclusion method using the above-mentioned stirrer and its inclusion compound will be described. First, 1200 g of purified water and then 900 g of β-CD are put into the stirring tank 1, and the turbine 4 is rotated at 5000 rpm to stir the mixed solution 1 a composed of purified water and β-CD while stirring the AIT.
After gradually adding 100 g of C, the turbine 4
Spin at 000 rpm and stir for 120 minutes, then mix 1a
AITC was included in β-CD to obtain an inclusion slurry.

Subsequently, a granulated body of the CD compound of AITC was prepared from the clathrate slurry by spray drying granulation.
00 g was obtained. The obtained granule was a spherical powder having a particle size of 10 to 50 μm.

The operating conditions in the above-mentioned spray-drying granulation method are as follows: the blowing temperature, which is the temperature of the outlet of hot air to the spray-drying chamber, is 150 ° C., and the temperature of the outlet of the granules from the spray-drying chamber is A certain exhaust air temperature is 70 ° C, and the rotation speed of the atomizer for spraying the clathrate slurry into the spray drying chamber is 13000 rpm.
Set to.

[Comparative Example] Next, the clathrate compound of the comparative example for comparison with the present invention will be described. First, 900 g of β-CD and 100 g of AITC are added to 1000 g of purified water, kneaded well, and kneaded with AITC. Inclusion to CD was performed. The obtained clathrate was vacuum-dried and then pulverized to obtain 900 g of a granular AITC CD clathrate.

Next, each clathrate compound of each of Examples 1 and 2 and Comparative Example was used as a sample, each sample was allowed to stand, and the amount of evaporated AITC in each sample was measured by gas chromatography.

In the method for measuring the amount of evaporation of AITC, about 0.2 g of each sample was weighed, wrapped in a nonwoven fabric, and sealed in a 1100 ml glass container in an environment of 95% humidity. The concentration of AITC in the air in this glass container was measured for
The measurement was performed by gas chromatography every hour, 50 hours, and 168 hours. The results are shown in Table 1. The measurement conditions of the gas chromatography method are as follows.

Measurement conditions Detector: FID Column: PEG20M (column length 25 m, column diameter 0.
25 mm, film thickness 0.25 μm) Inlet temperature: 200 ° C Detector temperature: 230 ° C Carrier gas: He 11.3 psi (70 ° C) The column oven temperature of the gas chromatography device is 70 ° C (1 min) -5 ° C / Heat up to 100 ℃ in min-40
After heating to 220 ° C at ℃ / min, 1.75min at 220 ° C
A retained temperature rise pattern was used.

[0036]

[Table 1]

As is clear from the results shown in Table 1, the sample of each example showed a larger amount of AITC transpiration than the sample of the comparative example, and the AITC concentration was changed to the AITC concentration ( 0.03ppm) or more
Was more effectively exhibited.

Next, the inclusion ratio of AITC in each of the above Examples and Comparative Examples was measured. First, the measurement method will be described. Each sample, which is a CD inclusion compound of AITC, is hydrolyzed with hydrochloric acid, and the total sugar content of the hydrolyzate is measured by a modified Somogi-Nelson method. The content was calculated. The water content in each of the samples was measured by the Karl Fischer method.

From the measured weight of each sample used, the CD content and the water content obtained from the total sugar content were subtracted to obtain the AITC content. Let the above AITC content be X, and
The inclusion rate (%) of TC was determined.

Inclusion rate (%) = (X / 8) × 100 It is known that AITC is included in β-CD at a molar ratio of 1 to 1, and the molecular weight of AITC is about
Since the molecular weight of 99, β-CD is about 1134, AIT
The limit of inclusion of C to β-CD is about 8%. Therefore, in this example, the inclusion rate was 100% when the content of AITC in each sample was 8%. Table 2 shows the results.
It was shown to.

[0041]

[Table 2]

As is clear from Table 2, each of the samples of Examples 1 and 2 showed a higher inclusion rate than the sample of the comparative example, and even with such a high inclusion rate, the high inclusion rate shown in Table 1 was obtained. It can be seen that the transpiration rate and its high transpiration rate are maintained.

As described above, in the clathration method of the above embodiment, the use of the stirring section 2 causes the mixed liquid 1a to be vigorously stirred, and the AITC and the CD to come into contact with a high probability. Due to the shearing function of the blades 4b of the turbine 4 in 2, the oil droplets of the AITC become smaller due to the impact or turbulence caused by the blades 4b, so that the AITC and the CD come into contact with a higher probability.

Therefore, it was difficult to completely cover the AITC in the inclusion step using an ordinary stirrer, for example, a propeller stirrer. However, when the stirrer 2 of this embodiment is used, it takes several tens minutes. It becomes easier to allow AITC to be more completely included in the CD by stirring.

In the clathrate compound of the above embodiment, the clathrate can be 80% or more, which is larger than the conventional 60%, so that the evaporation rate of AITC can be increased, and
While preventing oxidation of ITC and improving stability, AIT
The evaporation rate of the AITC can be controlled by the amount of inclusion of C, and the generation of unpleasant odors due to the AITC can be reduced while maintaining the bactericidal action of the AITC at a predetermined level.

In addition, the granules of the clathrate compound of each of the above-mentioned examples can exert their bactericidal and bacteriostatic effects more in an environment of high humidity, that is, in an environment where various germs are easily proliferated. It is an oily, pungent ingredient contained in mustard and wasabi, and is a compound that is safe for the human body at normal intake. Therefore, it can be suitably used for preserving foods such as fresh foods.

In the above inclusion method, the use of a homogenizer for stirring was also considered, but had the following disadvantages, and the inclusion rate could not be increased as compared with the conventional method. That is, in the homogenizer, AIT
The oil droplets of C can be made smaller by high pressure, but at this time, the liquid temperature usually rises by about 10 ° C.

When this and inclusion by CD are performed,
Since it is desirable that the liquid temperature be constant from a high temperature during the inclusion process, if a homogenizer is used, the inclusion temperature cannot be increased because the liquid temperature rises during the inclusion process. ing.

The reason for this is that the higher the temperature, the larger the pore size of the molecules of the CD becomes, so that the inclusion of the CD becomes easier because the CD containing the oily substance is cooled. Can be more completely included.

[0050]

According to the method for enclosing an oily substance according to claim 1 of the present invention, as described above, an oily substance is contained in a mixture of an aqueous solution of cyclodextrin and an oily substance in a stirring tank. When enclosing the cyclodextrin, the blades of the turbine rotating in the mixture form a flow of the mixture substantially parallel to the rotation axis of the turbine, and the mixture is convected in the stirring tank. A method in which the mixture is agitated by the tip of the blade of the turbine which moves in a direction substantially perpendicular to the flow direction of the mixture.

Therefore, the above method is intended to reduce the inclusion ratio of the oily substance to cyclodextrin by the above stirring,
Since the amount can be increased more than before, for example, the amount of transpiration of the oily substance can be improved, and the amount of transpiration can be controlled, so that the application range of the clathrate compound can be expanded.

The inclusion compound of an oily substance according to claim 2 of the present invention is obtained by granulating the mixture obtained by the inclusion method according to claim 1 as described above, and comprises cyclodextrin. The inclusion rate indicating the ratio of the inclusion amount of the oily substance in the cyclodextrin to the saturated inclusion amount of the oily substance in the above is 80% or more.

Therefore, in the above structure, since the inclusion rate is 80% or more, when allyl isothiocyanate having a bactericidal action is used as the oily substance, the amount of the allyl isothiocyanate evaporated can be increased. Therefore, the germicidal action can be exhibited more effectively.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a stirrer used in a method for enclosing an oily substance in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Stirring tank 1a Mixed liquid 4 Turbine 4b Blade

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // A01N 47/46 A01N 47/46 C07B 63/02 C07B 63/02 B C11B 9/00 C11B 9/00 Z (58) Survey Field (Int. Cl. ⁷ , DB name) C08B 37/16 CA (STN)

Claims (2)

(57) [Claims] 1. When an oily substance is included in a cyclodextrin in a mixed liquid of an aqueous solution of cyclodextrin and an oily substance in a stirring tank, the blade is rotated by a turbine blade in the mixed liquid. A tip of the blade of the turbine that moves in a direction substantially perpendicular to the flow direction of the mixed liquid while forming a flow of the mixed liquid substantially parallel to the rotation axis of the turbine and causing the mixed liquid to convect in the stirring tank. A method of clathrating an oily substance, wherein the mixture is stirred. 2. A mixture obtained by granulating the mixture obtained by the inclusion method according to claim 1, wherein the amount of inclusion of the oily substance in cyclodextrin relative to the amount of saturated inclusion of the oily substance in cyclodextrin is determined. An inclusion compound, wherein the inclusion ratio indicating the ratio is 80% or more.