Kestose crystal

Abstract

The present application relates to ketose crystals.

Description

Kestos decision

[0001] This application relates to Kestos determination.

[0002] Kestose is a type of fructooligosaccharide, and has been confirmed to have an effect of enhancing immunoglobulin A (IgA) antibody production, suppressing immunoglobulin E (IgE) antibody production, activating the proliferation of intestinal bifidobacteria, and improving atopic dermatitis in infants. Therefore, it is industrially useful to efficiently produce kestose in order to utilize its utility as an allergy suppressing composition, allergy suppressing food, and allergy suppressing agent.

[0003] However, Kestose powder is amorphous and highly hygroscopic, making it easily sticky, with poor flowability and sensitivity to ambient humidity. This makes it prone to hardening like candy during storage, making handling extremely inconvenient. Therefore, a technology is needed to manufacture Kestose crystalline particles with improved flowability and low hygroscopicity, making them easier to handle and use, similar to sugar.

[0004] An example of the present application is to provide a kestos crystal having a specific diffraction angle pattern.

[0005] Another example of the present application is to provide a sweetener comprising kestos crystals having a specific diffraction angle pattern.

[0006] Another example of the present application is to provide a fructooligosaccharide comprising a kestose crystal according to an example of the present application.

[0007] Another example of the present application is to provide a method for producing a kestose crystal having a specific diffraction angle pattern, comprising the steps of: adding a seed having a span value of 0.5 or more and 2.5 or less to a kestose solution; and cooling the kestose solution or vacuum concentrating the kestose solution to obtain a kestose crystal.

[0008] An example of the present application relates to a kestos crystal having an X-ray powder diffraction (XRD) pattern comprising characteristic peaks at positions of 2θ diffraction angles 15.63°, 12.90°, and 18.85° in X-ray powder diffraction (XRD) analysis.

[0009] Another example of the present application relates to a sweetener comprising a kestose crystal according to an example of the present application.

[0010] Another example of the present application relates to fructooligosaccharides comprising kestose crystals according to an example of the present application.

[0011] Another example of the present application relates to a method for producing a kestose crystal according to an example of the present application, comprising the steps of: adding a seed having a span value of 0.5 or more and 2.5 or less to a kestose solution; and cooling the kestose solution or vacuum concentrating the kestose solution to obtain a kestose crystal.

[0012]

[0013] Hereinafter, the present application will be described in more detail.

[0014] According to an example of the present application, the Kestos crystal may have an X-ray powder diffraction (XRD) pattern including peaks at positions of 2θ diffraction angles 15.63°, 12.90°, and 18.85° in X-ray powder diffraction (XRD) analysis.

[0015] According to an example of the present application, the kestos crystal may have an X-ray powder rotation pattern comprising three highest relative intensity peaks at positions of 2θ diffraction angles 15.63°, 12.90°, and 18.85° in X-ray powder diffraction (XRD) analysis. Furthermore, the kestos crystal may have an X-ray powder diffraction pattern comprising a second highest relative intensity peak at a position of 2θ diffraction angle 12.90°, or 15.63° in X-ray powder diffraction (XRD) analysis. Furthermore, the kestos crystal may have an X-ray powder diffraction pattern comprising a third highest relative intensity peak at a position of 2θ diffraction angle 18.85°, or 15.63° in X-ray powder diffraction (XRD) analysis.

[0016] For example, the above-described Kestos crystal may have an X-ray powder diffraction (XRD) pattern comprising peaks at positions of 2θ diffraction angles 15.63°, 12.90°, 18.85°, and 24.27°; 2θ diffraction angles 15.63°, 12.90°, 18.85°, and 20.90°; or 2θ diffraction angles 15.63°, 12.90°, 18.85°, and 22.36°.

[0017] For example, the above-mentioned Kestos crystal may have an X-ray powder diffraction pattern including peaks at positions of 2θ diffraction angles 15.63°, 12.90°, 18.85°, 20.90°, and 24.27° in X-ray powder diffraction (XRD) analysis.

[0018] For example, the above-mentioned Kestos crystal may have an X-ray powder diffraction pattern including peaks at positions of 2θ diffraction angles 15.63°, 12.90°, 18.85°, 24.27°, and 22.36° in X-ray powder diffraction (XRD) analysis.

[0019] The above peak may be a peak having a relative intensity of 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more. The relative intensity of the peak is expressed as a relative numerical percentage based on 100% of the intensity of the peak having the maximum intensity.

[0020] Among the above peaks, several peaks in the order of highest relative intensity, or peaks with a relative intensity greater than a certain value, may be the main peaks that determine the crystalline form.

[0021] For example, the major peaks may be 1 to 5, 1 to 4, 1 to 3, or 1 to 2 peaks having the highest relative intensities.

[0022] For example, the major peak may be a peak having a relative intensity of 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more.

[0023] For example, the above Kestos crystal may have an X-ray powder diffraction (XRD) pattern that includes characteristic peaks at positions of 2θ diffraction angles 15.63°, 12.90°, and 18.85°; 18.85°, 12.90°, and 15.63°; or 12.90°, 15.63°, and 18.85°, in order of relative intensity from highest to lowest peak.

[0024] For example, the above-described Kestos crystal may have an X-ray powder diffraction (XRD) pattern that includes characteristic peaks at positions of 2θ diffraction angles 15.63°, 12.90°, 18.85°, and 20.90°; 18.85°, 12.90°, 15.63°, and 24.27°; or 12.90°, 15.63°, 18.85°, and 24.27°, in order of relative intensity from highest to lowest peak.

[0025] For example, the above-described Kestos crystal may have an X-ray powder diffraction (XRD) pattern that includes characteristic peaks at positions of 2θ diffraction angles of 15.63°, 12.90°, 18.85°, 20.90°, and 24.27°; 18.85°, 12.90°, 15.63°, 24.27°, and 22.36°; or 12.90°, 15.63°, 18.85°, 24.27°, and 20.90°, in order of relative intensity from highest to lowest peak.

[0026] For example, the above-described Kestos crystal may have an X-ray powder diffraction (XRD) pattern in which a peak with the highest relative intensity is located at a 2θ diffraction angle of 12.90°, 15.63°, or 18.85° in X-ray powder diffraction (XRD) analysis.

[0027] When the 2θ diffraction angle is expressed as a numerical value in this specification, the 2θ diffraction angle may mean a specified numerical value of ±0.5°, ±0.4°, ±0.3°, ±0.2°, or ±0.1°.

[0028] The D[4,3] (volume average particle diameter) of the Kestos crystal according to an example of the present application may be 170 μm or more, 180 μm or more, 190 μm or more, 200 μm or more, 210 μm or more, 220 μm or more, 230 μm or more, 240 μm or more, 250 μm or more, 260 μm or more, 270 μm or more, 280 μm or more, 290 μm or more, 300 μm or more, 310 μm or more, 320 μm or more, 330 μm or more, 340 μm or more, 350 μm or more, 360 μm or more, 370 μm or more, or 380 μm or more. The upper limit of the above D[4,3] (volume average particle diameter) may be, for example, 1,000 μm or less, 900 μm or less, 800 μm or less, 700 μm or less, 600 μm or less, 500 μm or less, or 400 μm or less.

[0029] The average surface area of ​​the Kestos crystal according to an example of the present application is 0.1 m 2 / g or less, 0.09 m 2 / g or less, 0.08 m 2 / g or less, 0.07 m 2 / g or less, 0.06 m 2 / g or less, 0.05 m 2 / g or less, 0.04 m 2 / g or less, 0.035 m 2 / g or less, 0.03 m 2 / g or less, or 0.025 m 2 / g or less. The lower limit of the average surface area is, for example, 0.001 m 2 / g or more, 0.005 m 2 / g or more, or 0.01 m 2 / g can be more than that.

[0030] The span value of the Kestos decision according to an example of the present application is 0.5 to 2.2, 0.5 to 2.1, 0.5 to 2, 0.5 to 1.9, 0.5 to 1.8, 0.5 to 1.7, 0.5 to 1.6, 0.5 to 1.5, 0.5 to 1.4, 0.5 to 1.3, 0.5 to 1.25, 0.5 to 1.2, 0.5 to 1.1, 0.6 to 2.2, 0.6 to 2.1, 0.6 to 2, 0.6 to 1.9, 0.6 to 1.8, 0.6 to 1.7, 0.6 to 1.6, 0.6 to 1.6 1.5 or less, 0.6 or more but 1.4 or less, 0.6 or more but 1.3 or less, 0.6 or more but 1.25 or less, 0.6 or more but 1.2 or less, 0.6 or more but 1.1 or less, 0.7 or more but 2.2 or less, 0.7 or more but 2.1 or less, 0.7 or more but 2 or less, 0.7 or more but 1.9 or less, 0.7 or more but 1.8 or less, 0.7 or more but 1.7 or less, 0.7 or more but 1.6 or less, 0.7 or more but 1.5 or less, 0.7 or more but 1.4 or less, 0.7 or more but 1.3 or less, 0.7 or more but 1.25 or less, 0.7 or more but 1.2 or less, 0.7 or more but 1.1 or less, 0.8 or more but 2.2 or less, 0.8 or more but 2.1 or less, 0.8 or more but 2 or less, 0.8 or more but 1.9 or less, It can be 0.8 to 1.8, 0.8 to 1.7, 0.8 to 1.6, 0.8 to 1.5, 0.8 to 1.4, 0.8 to 1.3, 0.8 to 1.25, 0.8 to 1.2, 0.8 to 1.1, 1±0.5, 1±0.4, 1±0.3, 1±0.2, or 1±0.15.

[0031] The above span value is a value representing the size distribution of particles, and is an indicator of the difference between the largest and smallest particles in the particle size distribution. The farther the span value is from 1, the greater the difference in particle size, and the closer the span value is to 1, the more uniformly the particle sizes are distributed. The above span value can be calculated using the following mathematical equation 1:

[0032] [Mathematical Formula 1]

[0033] Span= (D 90 -D 10 ) / D 50

[0034] In the above mathematical expression 1, D 90 , D 50 and D 10 represent the particle sizes at the cumulative 90%, 50% and 10% of the smallest particles in the cumulative particle size distribution, respectively.

[0035] The ratio of the major diameter to the minor diameter of the Kestos crystal according to an example of the present application may be 1 to 8, 1 to 7, 1 to 6, 1 to 5.5, 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1 to 1.5.

[0036] The melting temperature (Tm) of the Kestos crystal according to an example of the present application may be 180°C or higher, 190°C or higher, 195°C or higher, 200°C or higher, or 205°C or higher. The upper limit of the melting temperature may be, for example, 220°C or lower, 215°C or lower, or 210°C or lower.

[0037] The melting enthalpy of the kestos crystal according to an example of the present application may be 80 J / g or more, 85 J / g or more, 90 J / g or more, 95 J / g or more, 100 J / g or more, 105 J / g or more, 110 J / g or more, or 115 J / g or more. The upper limit of the melting enthalpy may be, for example, 130 J / g or less, 125 J / g or less, or 120 J / g or less.

[0038] According to an example of the present application, the Kestos crystal may contain less than 1.4 wt%, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, 1 wt% or less, 0.9 wt% or less, 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, 0.3 wt% or less, 0.25 wt% or less, or 0.2 wt% or less of nystose. The lower limit of the nystose content may be, for example, more than 0 wt%, 0.001 wt% or more, 0.01 wt% or more, or 0.1 wt% or more.

[0039] The electrical conductivity of the melt of the Kestos crystal according to an example of the present application may be 2.5 μS / cm or less, 2 μS / cm or less, 1.5 μS / cm or less, 1.4 μS / cm or less, 1.3 μS / cm or less, 1.2 μS / cm or less, 1.1 μS / cm or less, 1 μS / cm or less, 0.9 μS / cm or less, 0.8 μS / cm or less, 0.7 μS / cm or less, or 0.6 μS / cm or less. The lower limit of the electrical conductivity may be, for example, greater than 0 μS / cm, greater than 0.001 μS / cm, greater than 0.01 μS / cm, or greater than 0.1 μS / cm.

[0040] The brightness (L value) of the Kestos crystal according to an example of the present application may be 97.5 or less, 97 or less, 96 or less, 95 or less, 94.5 or less, 94 or less, 93.9 or less, 93.5 or less, 93 or less, or 92.5 or less. The lower limit of the brightness may be, for example, 50 or more, 60 or more, 70 or more, 80 or more, or 90 or more.

[0041] The yellowness (b value) of the Kestos crystal according to an example of the present application may be 0.6 or less, 0.5 or less, 0.45 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, 0.2 or less, 0.19 or less, 0.18 or less, 0.17 or less, 0.16 or less, or 0.15 or less. The lower limit of the yellowness may be, for example, 0.001 or more, 0.01 or more, or 0.1 or more.

[0042] The whiteness of the Kestos crystal according to an example of the present application may be 95 or less, 90 or less, 85 or less, 84 or less, or 83 or less. The lower limit of the whiteness may be, for example, 50 or more, 60 or more, 70 or more, or 80 or more.

[0043] The angle of repose of the Kestos crystal according to an example of the present application may be 47° or less, 46° or less, 45° or less, 44° or less, 43° or less, 42° or less, 41° or less, 40° or less, 39° or less, or 38.5° or less. The lower limit of the angle of repose may be, for example, 20° or more, 25° or more, 30° or more, or 35° or more.

[0044] According to an example of the present application, the hardness of the Kestos crystal after applying a surface pressure of the same weight for 2 hours under conditions of a temperature of 45°C and a relative humidity of 85% may be 1,400 g or less, 1,300 g or less, 1,200 g or less, 1,100 g or less, 1,000 g or less, 950 g or less, or 900 g or less. The lower limit of the hardness may be, for example, 500 g or more, 600 g or more, 700 g or more, or 800 g or more.

[0045] According to an example of the present application, when a surface pressure of the same weight is applied for 2 hours under conditions of a temperature of 45°C and a relative humidity of 85%, the hardness increase rate may be 120% or less, 110% or less, 100% or less, 95% or less, 90% or less, 80% or less, 70% or less, 65% or less, 60% or less, 55% or less, or 50% or less.

[0046] Another example of the present application relates to a sweetener comprising a kestose crystal according to an example of the present application.

[0047] Another example of the present application relates to fructooligosaccharides comprising kestose crystals according to an example of the present application.

[0048] Another example of the present application relates to a method for producing kestose crystals, comprising the steps of adding a seed to a raw material kestose solution; and cooling the raw material kestose solution or evaporating and concentrating the raw material kestose solution to obtain kestose crystals.

[0049] In the present example, it was confirmed that particle size and yield were improved depending on the span value of the seed crystal added during the production of Kestos crystals. Specifically, even when the average particle size of the seed crystals was the same, when seed crystals with a span value close to 1 were used, it was possible to produce Kestos crystals with a large average particle size, even distribution, low impurity content, and excellent flowability, and the crystallization yield was also improved.

[0050] The above-mentioned seed has a span value of 0.5 or more and 2.5 or less, 0.5 or more and 2.4 or less, 0.5 or more and 2.3 or less, 0.5 or more and 2.2 or less, 0.5 or more and 2.1 or less, 0.5 or more and 2 or less, 0.5 or more and 1.9 or less, 0.5 or more and 1.8 or less, 0.5 or more and 1.7 or less, 0.5 or more and 1.6 or less, 0.5 or more and 1.5 or less, 0.5 or more and 1.4 or less, 0.5 or more and 1.3 or less, 0.5 or more and 1.2 or less, 0.5 or more and 1.1 or less, 0.6 or more and 2.5 or less, 0.6 or more and 2.4 or less, 0.6 or more and 2.3 or less, 0.6 or more and 2.2 or less, 0.6 or more and 2.1 or less, 0.6 or more and 2 or less, 0.6 Above 1.9 and below, 0.6 and above 1.8 and below, 0.6 and above 1.7 and below, 0.6 and above 1.6 and below, 0.6 and above 1.5 and below, 0.6 and above 1.4 and below, 0.6 and above 1.3 and below, 0.6 and above 1.2 and below, 0.6 and above 1.1 and below, 0.7 and above 2.5 and below, 0.7 and above 2.4 and below, 0.7 and above 2.3 and below, 0.7 and above 2.2 and below, 0.7 and above 2.1 and below, 0.7 and above 2 and below, 0.7 and above 1.9 and below, 0.7 and above 1.8 and below, 0.7 and above 1.7 and below, 0.7 and above 1.6 and below, 0.7 and above 1.5 and below, 0.7 and above 1.4 and below, 0.7 and above 1.3 and below, 0.7 and above 1.2 Below, 0.7 or more and 1.1 or less, 1±0.9, 1±0.8, 1±0.7, 1±0.65, 1±0.6, 1±0.5, 1±0.4, or 1±0.3. The seed crystals may have an average particle size of 300 μm or less, 250 μm or less, 10 to 300 μm, 50 to 300 μm, 10 to 250 μm, 50 to 250 μm, 100 to 300 μm, 100 to 250 μm, 150 to 300 μm, or 150 to 250 μm. The average particle size may be a D(4,3) average particle size.

[0051] The crystallization yield of the above manufacturing method may be 40% or more, 45% or more, 50% or more, 53% or more, or 55% or more.

[0052] The solid content of the above raw material ketose solution may be 70 wt% or more, 75 wt% or more, or 80 wt% or more.

[0053] The kestose content of the above raw material kestose solution may be 80 wt% or more, 85 wt% or more, or 90 wt% or more based on 100 wt% of the total solid content.

[0054] The above-mentioned seed may be added in an amount of 0.01 to 1 wt%, 0.05 to 1 wt%, 0.1 to 1 wt%, 0.01 to 0.5 wt%, 0.05 to 0.5 wt%, or 0.1 to 0.5 wt% based on 100 wt% of the solid content of the above-mentioned Kestos solution.

[0055] The above cooling may be cooling the temperature of the raw material kestos solution to a temperature of 20 to 40°C, and specifically, may be cooling the temperature of the raw material kestos solution from a temperature of 50 to 70°C to a temperature of 20 to 40°C.

[0056] The above evaporation and concentration may be performed by additionally supplying the raw material Kestos solution at a temperature of 50 to 70°C.

[0057] The Kestos crystal according to an example of the present application has a specific diffraction angle pattern, improved flowability and improved solidification characteristics, thereby increasing ease of use and providing excellent storage stability.

[0058] Figure 1 is an optical microscope photograph of the Kestos crystal of Comparative Example 1 of the present application.

[0059] Figure 2 is an optical microscope photograph of the Kestos crystal of Example 2 of the present application.

[0060] Figure 3 is an optical microscope photograph of the Kestos crystal of Example 3 of the present application.

[0061] Figure 4 is an optical microscope photograph of the Kestos crystal of Example 4 of the present application.

[0062] Hereinafter, the present application will be described in more detail with reference to the following examples. However, these examples are merely intended to illustrate the present application, and the scope of the present application is not limited by these examples.

[0063]

[0064] Example 1: Preparation of Kestos Crystalline Solution

[0065] After putting 45 kg of water heated to 55℃ into a saccharification tank, 55 kg of sugar was added and stirred for 1 to 2 hours to completely dissolve the sugar crystals. After that, the pH was adjusted to 6.5 to 7.0, and β-fructofuranosidase derived from Aspergillus niger, an enzyme for producing syrup with a high kestose content, was added and reacted for 24 to 48 hours according to the manufacturing method disclosed in Korean Patent Publication No. 10-2018-0078065. At this time, in the enzyme reaction section where the sugar content remained at 26 wt%, 4N NaOH was used to adjust the pH to 7.6 or higher, and at the same time, the mixture was heated to 80℃ for 2 hours to inactivate the enzyme. When the enzyme inactivation was complete, it was concentrated to a solid content of 40 to 60 wt% through decolorization / filtration and ion purification processes.

[0066] Afterwards, high-purity separation was performed using SMB filled with Na+ type separation resin and concentration was performed to obtain a raw material for crystallization containing kestose in an amount of 85 wt% or more of the total solid content. Specifically, as the raw material for crystallization manufactured above, a raw material kestose solution having a solid content of 82.5 wt% and containing 92.7 wt% of kestose, 4.2 wt% of nystose, and 3.1 wt% of sugar in the total solid content was obtained.

[0067] <Conditions for analysis of kestose content and sugar composition>

[0068] - Analysis equipment: HPLC Agilent, 1100 Series

[0069] - Column: Shodex Asahipak NH2P-50 4E

[0070] - Injection volume: 10㎕

[0071] - Flow rate: 1ml / min

[0072] - Column temperature: 30℃

[0073] - Mobile phase: Acetonitrile 70%

[0074] - Detector: RI detector

[0075]

[0076] Example 2: Preparation of Kestos crystals using a cooling method (1)

[0077] A crystallization process was performed by slowly cooling the temperature to precipitate crystals using a crystallization solution containing 92.7 wt% of kestose, 4.2 wt% of nystose, and 3.1 wt% of sugar prepared in Example 1.

[0078] Specifically, in a crystallization solution having an initial temperature of 60°C, pH 7.0 to 7.5, and a solid content of 82.5 wt%, seed crystals having a D(4,3) average particle size of 200 μm and a span value of 1.622 were added in an amount of 0.3 wt% based on the solid content weight of the crystallization solution. At this time, the supersaturation degree was 1.01 to 1.15, and crystallization was performed by cooling to 30°C at the same rate of cooling at a cooling rate of -0.5°C / hour.

[0079] The above-mentioned cooled solution was centrifuged to remove the mother liquor, thereby obtaining kestose crystals in the first stage. The kestose crystals obtained in the first stage were washed with cooling water and dried to recover the kestose crystals.

[0080] The purity analysis of the manufactured Kestos crystals was performed by HPLC analysis using the same method as in Example 1. The purity of the manufactured Kestos crystals was 99.0 wt%, and the crystallization yield was 45.5%.

[0081]

[0082] Example 3: Preparation of Kestos crystals using a cooling method (2)

[0083] A crystallization process was performed by slowly cooling the temperature to precipitate crystals using a crystallization solution containing 92.7 wt% of kestose, 4.2 wt% of nystose, and 3.1 wt% of sugar prepared in Example 1.

[0084] Specifically, seed crystals having an average particle size of D(4,3) of 200 μm and a span value of 0.714 were added to a crystallization solution having an initial temperature of 60°C, pH of 7.0 to 7.5, and a solid content of 82.5 wt%, at 0.3 wt% relative to the solid content weight of the crystallization solution. At this time, the supersaturation degree was 1.01 to 1.15, and crystallization was performed by cooling to 30°C at the same rate at a cooling rate of -0.5°C / hour.

[0085] The above-mentioned cooled solution was centrifuged to remove the mother liquor, thereby obtaining kestose crystals in the first stage. The kestose crystals obtained in the first stage were washed with cooling water and dried to recover the kestose crystals.

[0086] The purity analysis of the manufactured Kestos crystals was performed by HPLC analysis using the same method as in Example 1. The purity of the manufactured Kestos crystals was 99.7 wt%, and the crystallization yield was 53.9%.

[0087]

[0088] Example 4: Preparation of Kestos crystals using evaporation and concentration method (1)

[0089] A crystallization solution having a solid content of 60 wt% and a pH of 7.0 to 7.5, containing 92.7 wt% of kestose, 4.2 wt% of nystose, and 3.1 wt% of sugar prepared in Example 1, was introduced into a reactor at a temperature of 60°C and under vacuum to make up 25% of the reactor volume, and primary vacuum concentration was performed in the reactor to make the solid content 82.5 wt%.

[0090] At a stock solution concentration having a supersaturation degree of 1.01 to 1.10, 0.3 wt% of seeds with an average particle size of D(4,3) of 200 μm and a span value of 0.714 were added to the crystallization stock solution based on the solid content, and slowly stirred to generate crystal nuclei. While maintaining a vacuum, the same volume of the crystallization stock solution prepared in Example 1 was additionally added, and the crystals were grown while performing secondary concentration so as to maintain a solid content of 82.5 wt% and a constant supersaturation degree. At this time, without lowering the temperature, the solution was added under a constant temperature condition of 50 to 70°C, and concentrated to a solid content of 82.5 wt% so as to maintain a supersaturation degree of 1.01 to 1.15. As crystals grow, microcrystals may also precipitate. Therefore, before adding additional stock solution, a small amount of water was added to dissolve the microcrystals, and then the stock solution was added to prevent the microcrystals from inhibiting crystal particle growth. The above-mentioned method of adding stock solution and adding water was repeated a total of four times.

[0091] After the manufactured kestose crystals were discharged from the reactor, the mother liquor was removed by centrifugal dehydration to obtain the kestose crystals in the first stage, and the kestose crystals obtained in the first stage were washed with cooling water and then dried to recover them.

[0092] The purity analysis of the above-mentioned manufactured Kestos crystals was performed using HPLC analysis in the same manner as in Example 1. The purity of the above-mentioned manufactured Kestos crystals was 99.8 wt%, and the crystallization yield was 55.7%.

[0093]

[0094] Comparative Example 1: Production of Kestos crystals using a cooling method (3)

[0095] A crystallization process was performed by slowly cooling the crystal solution containing 92.7 wt% of kestose, 4.2 wt% of nystose, and 3.1 wt% of sugar prepared in Example 1 to precipitate crystals.

[0096] Specifically, seed crystals having an average particle size of 200 μm and a span of 2.531 of D(4,3) were added at 0.3 wt% based on the weight of the solids to a crystallization solution having an initial temperature of 60°C, pH 7.0 to 7.5, and a solids content of 82.5 wt%. At this time, the supersaturation degree was 1.01 to 1.15, and the mixture was cooled to 30°C at a constant cooling rate of -0.5°C / hour. The mother liquor was removed by centrifugal dehydration, and the crystals obtained by the first crystallization were washed with cooling water and then dried to recover kestose crystals. The purity of the manufactured kestose crystals was analyzed by HPLC using the same method as in Example 1, and the purity of the manufactured kestose crystals was 98.6 wt%, and the crystal yield was 39.4%.

[0097]

[0098] Test Example 1: Particle Characterization

[0099] The average particle size and particle size distribution of the Kestos crystals manufactured in Examples 2 to 4 and Comparative Example 1 were measured using a laser diffraction type particle size analysis device, and the measured specific surface area values ​​and span values ​​are listed in Table 1.

[0100] - Particle size analysis equipment: Laser Diffraction particle analyzer, Mastersizer 2000 (MALVERN Panalytical Ltd.)

[0101] - Dispersion Unit: Hydro 2000 MU (wet type)

[0102] - Dispersion solvent: Isopropyl alcohol

[0103] As shown in Table 1, the Kestos crystal according to an example of the present application has a large size with an average particle size of 270 μm or more and a particle size of 0.05 μm or more. 2 / g or less. In addition, the Kestos crystal particles according to an example of the present application showed a very uniform particle shape with a span value in the range of 1±0.3.

[0104] Sample average particle size (㎛) (Vol. Weighted Mean D[4,3]) Average specific surface area (Specific surface area, ㎡ / g) Span value (Span) Comparative example 1161.20.1102.214 Exemplary example 2275.40.0471.247 Exemplary example 3326.30.0310.904 Exemplary example 4385.10.0220.897

[0105]

[0106] Test Example 2: X-ray diffraction (XRD) analysis

[0107] The Kestos crystals obtained in Examples 2 to 4 and Comparative Example 1 were subjected to X-ray diffraction analysis under the following analysis conditions, and the top five peaks of the X-ray diffraction pattern of the Kestos crystals according to one example of the present application were selected in order of high to low relative intensity (Relative Intensity %) and listed in Table 2.

[0108] - Analysis instrument: D / MAX-2200 Ultima / PC

[0109] - Manufacturer: Rigaku International Corporation (Japan)

[0110] - X-ray sauce system target: sealed tube Cu

[0111] - Tube voltage: 45 kV / Tube current: 200 mA

[0112] - Scan range: 5 to 90° 2θ

[0113] - Step size: 0.02°

[0114] - Scan speed: 5° / min

[0115] Comparative Example 1 Example 2 Example 3 Example 4 Angle 2-Theta degreeRelative Intensity % Angle 2-Theta degreeRelative Intensity % Angle 2-Theta degreeRelative Intensity % Angle 2-Theta degreeRelative Intensity %18.99100.015.62100.018.81100.012.91100.022.2358.312.8898.412.9087.115.6590.712.9954.318.8476.115.6380.418.8964.911.1046.520.8862.524.2758.024.2859.29.4944.224.2659.922.3651.020.9152.8

[0116] As shown in Table 2, the kestose crystal according to an example of the present application, which was manufactured by performing a crystallization process while adjusting the span value of the seed crystal to 2.5 or less during the manufacture of the kestose crystal, had an X-ray powder diffraction (XRD) analysis showing characteristic peaks at positions of 2θ diffraction angles of 15.63±0.5°, 12.90±0.5°, and 18.85±0.5°. Specifically, the kestose crystal according to an example of the present application had an X-ray powder diffraction (XRD) analysis showing characteristic peaks at positions of 2θ diffraction angles of 15.63±0.5°, 12.90±0.5°, 18.85±0.5°, and 24.27±0.5°. The X-ray powder diffraction patterns of the Kestos crystals of Examples 2 and 4 additionally included a characteristic peak at a position of 20.90±0.5°. The X-ray powder diffraction pattern of the Kestos crystals of Example 3 additionally included a characteristic peak at a position of 22.36±0.5°. On the other hand, in the case of Comparative Example 1, in which a seed crystal having a span value exceeding 2.5 was used in the production of the Kestos crystals, the characteristic peaks of the X-ray powder diffraction patterns of the Kestos crystals appeared differently.

[0117] Therefore, the Kestos crystals according to an example of the present application, manufactured by controlling the span value of the seed crystal during the crystallization process, had a specific crystal shape. In contrast, the crystals of Comparative Example 1 not only had very small particle sizes, but also differed in external crystal shape from the crystals according to an example of the present application.

[0118]

[0119] Test Example 3: Analysis of crystal morphology and crystal particle size

[0120] Optical microscope photographs of the Kestos crystals obtained in Examples 2 to 4 and Comparative Example 1, measured at a magnification of X100, are shown in FIGS. 1 to 4 (FIG. 1: Comparative Example 1; FIG. 2: Example 2; FIG. 3: Example 3; FIG. 4: Example 4). In addition, the major diameter (length) and minor diameter (width) of six samples each of the Kestos crystals manufactured in Examples 2 to 4 and Comparative Example 1 were measured, and the particle diameter ratio (= major diameter / minor diameter) was calculated and shown in Table 3. Specifically, the ratio of the major diameter length (μm) was shown with the minor diameter length (μm) as 1.

[0121] No. Comparative Example 1 Example 2 Example 3 Example 4 #17.164.211.751.31 #29.655.891.151.32 #37.924.311.461.34 #48.654.711.861.22 #510.565.631.751.25 #69.835.341.241.35 Average 8.965.021.541.30

[0122] Kestose crystals have a rectangular hexahedron or a crystal structure close to it. As shown in Table 3, the Kestose crystals of Examples 3 and 4 formed an orthorhombic crystal shape close to a square shape, with each crystal plane growing uniformly. As the crystal planes grow uniformly, the major diameter / minor diameter ratio tends to decrease, and it is interpreted that the increased uniformity of seed crystals during the production of Kestose crystals had a positive effect on crystal growth.

[0123]

[0124] Test Example 4: Differential Scanning Calorimetry (DSC) Analysis

[0125] DSC analysis of the kestos crystals manufactured in Examples 2 to 4 and Comparative Example 1 was performed, and the specific DSC analysis conditions are as follows.

[0126] - Equipment name: DSC[differential scanning calorimetry]

[0127] - Manufacturer: Perkin Elmer

[0128] - Method: 30 to 250℃, 10℃ / min heating, N2 gas purge

[0129] (Refer to standard method: ASTM D 3418)

[0130] The results of DSC analysis of the above Kestos crystals are shown in Table 4.

[0131] Sample Tm(℃)ΔH(J / g)Comparative Example 1176.4676.7Example 2198.6682.1Example 3202.5799.7Example 4205.72116.0

[0132] As a result of the above DSC analysis, the Kestos crystal according to an example of the present application was measured to have a high Tm value and a high heat capacity. In the DSC analysis of a crystal, the higher the heat capacity, the more difficult it is to melt, and the higher the heat capacity and the narrower the endothermic peak width, the more uniform and hard the crystal is formed. Considering the heat capacity and endothermic peak enthalpy values ​​of the Kestos crystals of Examples 2 to 4, it was confirmed that the Kestos crystal according to an example of the present application was formed more uniformly and hard.

[0133]

[0134] Test Example 5: Impurity Analysis

[0135] Qualitative analysis of nystose and ionic substances was performed as impurity components remaining in the kestose crystals manufactured in Examples 2 to 4 and Comparative Example 1. The nystose content (wt%) was analyzed by HPLC in the same manner as in Example 1, and the ionic substances were analyzed by dissolving the kestose crystals in a 10% solution and then conducting conductivity analysis using an electrical conductivity meter (Aquasearcher multi meter AB33M1, Ohaus). The analysis results are shown in Table 5.

[0136] SampleNistos content (wt%)Conductivity (μS / cm)Comparative Example 11.42.51Example 21.01.87Example 30.31.25Example 40.20.55

[0137] If the crystal particles do not grow well and are formed as fine crystals, it is difficult to dehydrate and wash the mother liquor between the crystal particles. If dehydration and washing are not performed properly, the impurity content increases, and in particular, since nystose is a tetrasaccharide, it has a higher viscosity than kestose, making it difficult to remove during the dehydration process. It is possible to determine whether the kestose crystals have been dehydrated and washed well from the nystose content remaining in the crystals. This also significantly affects the crystal purity. As shown in Table 5, the nystose content of the kestose crystals of Examples 2 to 4 was very low at 1 wt% or less, and the conductivity value was low at 2.0 μS / cm or less. This appeared to be because the particles of the kestose crystals according to an example of the present application were uniform and large, so impurities were well removed during the dehydration and washing process.

[0138]

[0139] Test Example 6: Appearance Characteristics Analysis

[0140] The brightness (L value), redness (a value), yellowness (b value) and whiteness of the Kestos crystals manufactured in Examples 2 to 4 and Comparative Example 1 were measured using a colorimeter (Spectro color meter SA-2000, Nippon Denshoku Industries co., Ltd.) and a whiteness tester (Whiteness Tester C-130, KETT electric laboratory), and the results are shown in Table 6.

[0141] Sample color difference value (color) Whiteness L*a*b*Whitness index Comparison Example 197.6-0.04 0.6 99 6.4 Example 294.0-0.03 0.4 187.3 Example 393.7-0.03 0.2 48 3.2 Example 492.1-0.02 0.1 58 2.6

[0142] The closer the whiteness is to white, the higher the value is. Sugar generally shows a whiteness level of 80 to 86. If a lot of fine particles are contained or the particle surface is dull, the whiteness value may be higher due to the difference in light scattering. The kestose crystals of Examples 2 to 4 showed a whiteness similar to that of sugar compared to the kestose crystals of Comparative Example 1, and showed a difference in color value, such as a lower yellowness (b value) measured in the color difference value analysis. If the yellowness is high, it can be inferred that the mother liquor of the crystal is attached to the crystal particles during the dehydration and washing process after crystallization. If even a very small amount of the mother liquor remains on the particles, it can induce browning or promote solidification during long-term storage. The kestose crystal according to an example of the present application showed a low yellowness, which means that the crystal particles were formed uniformly, so that washing was performed smoothly during the dehydration process.

[0143]

[0144] Test Example 7: Flow Analysis of Kestos Crystals

[0145] Each of the Kestos crystals manufactured in Examples 2 to 4 and Comparative Example 1 was prepared in an amount of 150 g, and the angle of repose was measured using an automatic stirring type angle of repose measuring device (Manufacturer: K-one Nano., Ltd., Model: BT-200DA). The Kestos crystal samples were passed through a special funnel fixed at a certain height on a completely flat reference plate of the measuring device in a certain volume, and the angle of repose of the cone-shaped crystals piled up on the reference plate was measured, and the results are shown in Table 7. Since the angle of repose is measured by measuring the slope of the crystals piled up on the reference plate when they no longer flow, a smaller angle of repose means better flowability.

[0146] Sample angle of repose, flowability (Angle of repose, °) Comparative example 147.7 Example 240.0 Example 338.8 Example 438.1

[0147] As shown in Table 7, the Kestos crystals of Examples 2 to 4 had improved particle flowability compared to the Kestos crystals of Comparative Example 1. This can increase the user convenience of the Kestos crystal product, and for example, the convenience can be improved when introducing the Kestos crystals or transporting them through a line.

[0148]

[0149] Test Example 8: Analysis of the hardness of Kestos crystals

[0150] 50 g of the Kestos crystal samples manufactured in Examples 2 to 4 and Comparative Example 1 were each sealed in the same PE zipper bag with the surface evenly smoothed without applying external pressure. The samples were stored for 2 hours under constant temperature and humidity conditions of 45°C and 85% relative humidity. In order to reproduce the caking phenomenon that may occur when storing crystal products loaded, the samples that had absorbed moisture under constant temperature and humidity conditions were sealed in PE zipper bags, and a weight having the same weight as the sample was used to apply pressure to the surface to induce caking. The hardness increase rate (%) of each sample after 2 hours of storage is shown in Table 8. The conditions for measuring the hardness after caking are as follows.

[0151] - Equipment name: Texture analyzer TAXTplus (stable micro systems)

[0152] - Cylinder probe: 25mmϕ Perspex

[0153] - Test speed: 2mm / sec

[0154] - Trigger force: 5g

[0155] Hardness before sample storage (Force (g)) Hardness after storage (Force (g)) Hardness increase rate (%) Comparative example 1615.81403.5127.91 Example 2611.51181.893.26 Example 3602.2978.762.52 Example 4600.5892.548.63

[0156] As shown in Table 8, the Kestos crystal of Example 4 showed the least surface solidification, whereas the Kestos crystal of Comparative Example 1 showed the highest solidification hardness, exhibiting a hardness increase rate of over 120%. This solidification phenomenon is greatly affected by the external environment during long-term storage, and can be accelerated as the storage load increases. However, it was confirmed that the Kestos crystal according to an example of the present application improved storage stability by alleviating the degree of surface solidification even under harsh storage conditions. Therefore, the Kestos crystal according to an example of the present application can provide significant help industrially by improving storage stability during packaging, storage, transportation, and distribution of products.

Claims

1. A Kestose crystal having an X-ray powder diffraction pattern comprising peaks at 2θ diffraction angles of 15.63±0.5°, 12.90±0.5° and 18.85±0.5° in X-ray powder diffraction (XRD) analysis.

2. A Kestos crystal having an X-ray powder diffraction pattern including peaks at positions of 2θ diffraction angles of 15.63±0.5°, 12.90±0.5°, 18.85±0.5°, and 24.27±0.5° in X-ray powder diffraction (XRD) analysis of claim 1.

3. A Kestos crystal having an X-ray powder diffraction pattern including peaks at positions of 2θ diffraction angles of 15.63±0.5°, 12.90±0.5°, 18.85±0.5°, and 20.90±0.5° in X-ray powder diffraction (XRD) analysis of claim 1.

4. A Kestos crystal having an X-ray powder diffraction pattern including peaks at positions of 2θ diffraction angles of 15.63±0.5°, 12.90±0.5°, 18.85±0.5°, and 22.36±0.5° in X-ray powder diffraction (XRD) analysis of claim 1.

5. A Kestos crystal in the first paragraph, wherein the peak is a peak having a relative intensity of 40% or more.

6. In the first paragraph, the Kestos crystal has a D[4,3] (volume average particle diameter) of 170 μm or more.

7. In the first paragraph, the average surface area of ​​the Kestos crystal is 0.1 m 2 / g or less, Kestos decision.

8. A Kestos crystal in the first paragraph, wherein the span value of the Kestos crystal is 0.5 or more and 2.2 or less.

9. A Kestos crystal in the first paragraph, wherein the ratio of the major diameter to the minor diameter of the Kestos crystal is 1 to 8.

10. A Kestos crystal in the first paragraph, wherein the melting temperature (Tm) of the Kestos crystal is 180°C or higher.

11. A Kestos crystal in the first paragraph, wherein the melting enthalpy of the Kestos crystal is 80 J / g or more.

12. A kestose crystal in the first paragraph, wherein the kestose crystal contains less than 1.4 wt% of nystose.

13. In the first paragraph, the electrical conductivity of the melt of the Kestos crystal is 2.5 μS / cm or less.

14. A Kestos crystal in the first paragraph, wherein the brightness of the Kestos crystal is 97.5 or less.

15. A Kestos crystal in the first paragraph, wherein the yellowness of the Kestos crystal is 0.6 or less.

16. A Kestos crystal in the first paragraph, wherein the whiteness of the Kestos crystal is 95 or less.

17. A Kestos crystal in the first paragraph, wherein the angle of repose of the Kestos crystal is 47° or less.

18. A Kestos crystal having a hardness increase rate of 120% or less after applying surface pressure of the same weight for 2 hours under conditions of a temperature of 45°C and a relative humidity of 85% in the first paragraph.

19. A sweetener comprising a kestose crystal according to any one of claims 1 to 18.

20. Fructooligosaccharide comprising a kestose crystal according to any one of claims 1 to 18.

21. A step of adding a seed having a span value of 0.5 or more and 2.5 or less to the raw material Kestos solution; and Comprising a step of cooling the above raw material Kestos solution or evaporating and concentrating the above raw material Kestos solution to obtain Kestos crystals. A method for producing a Kestos crystal according to any one of claims 1 to 18.

22. A manufacturing method in claim 21, wherein the seed has an average particle diameter of 300 μm or less.

23. A manufacturing method in claim 21, wherein the seed is added in an amount of 0.01 to 1 wt% based on 100 wt% of the solid content of the Kestos solution.

24. A manufacturing method according to claim 21, wherein the crystallization yield of the manufacturing method is 40% or more.

25. A manufacturing method in claim 21, wherein the cooling is performed by cooling the temperature of the raw material Kestos solution to a temperature of 20 to 40°C.

26. A manufacturing method in claim 21, wherein the evaporation concentration is performed by additionally supplying the raw material Kestos solution at a temperature of 50 to 70°C.

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