JP4045741B2 - Okara manufacturing method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention provides okara that has been sterilized by heating with retort without impairing color and flavor.
[0002]
[Prior art]
Conventional okara was overwhelmingly often made dry from the viewpoint of storage stability. However, the dried okara has not only inferior water retention and water reversibility but also has a disadvantage that the energy cost for drying is higher than before drying.
[0003]
On the other hand, batch-type retort heat-sterilized okara has been distributed slightly, but there is a problem of blackening or hardening over time, and even if retort heat treatment is performed when water is present, There was a tendency to rot due to the presence of heat-resistant bacteria. According to the knowledge of the present inventor, this is because the particle size of okara is large, so that the inside cannot be sufficiently sterilized, and it is due to the taste component (sugar) contained in okara. Therefore, even when the F ₀ value was 4 minutes or more, the sterilization could not be sufficiently performed, and it decayed over time. Therefore, the amount of filling was also limited, and retort heat sterilization by small amount filling was performed.
[0004]
[Problems to be solved by the invention]
The present invention is directed to a retort heat-sterilized packaged okara that has excellent flavor and color tone and excellent storage stability.
[0005]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors first tried to seal and fill with commercially available tofu oak and sterilize by heating with retort, but the color tone was dark, and it was not able to withstand eating. It was. In addition, because okara particles are large, and because the germ part and skin called soy navel are mixed in okara, it was not heated enough, but even after storage at 5 ° C for 10 days, it resulted in spoilage.
[0006]
As a result of further diligent research, the inventors of the present invention used soy beans soaked in warm water, extracted carbohydrates, removed the delicious components (ie, blanching), refined to a specific particle size, The residue okara obtained by centrifuging with a decanter is hermetically filled in a packaging material, and after retort heat sterilization and cooling, the knowledge that can obtain the desired okara is obtained and the present invention is completed. It came to.
[0007]
That is, the present invention is a method for producing packaged okara characterized by retort heating okara with a saccharide content of 5% by weight or less, a particle size of 10 to 100 microns, and a water content of 70% by weight or more. is there. The particle size of okara is preferably 20 to 50 microns. The retort heating condition is preferably 4 to 20 minutes in terms of F ₀ value.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The okara used in the present invention may be derived from full-fat soybean or defatted soybean. The former can be obtained mainly in the production process of tofu and full-fat soymilk, and the latter can be obtained in the process of producing separated soybean protein and the like using defatted soybean obtained in the soybean oil production process.
[0009]
In the present invention, the aspect in which the sugar content of okara is 5 wt% (hereinafter abbreviated as “%”) or less may be washed with water, but a method of blanching whole soybeans is preferred. . The blanching can usually be performed with hot water at 50 to 65 ° C, but it is preferable to perform the blanching with hot water at a high temperature of 85 to 95 ° C because the sugar can be efficiently extracted. The blanching time is at least 30 minutes or more, preferably 60 minutes or more in warm water of 50 to 65 ° C. Moreover, it is preferable to carry out for 30 to 60 minutes with high temperature hot water of 85-95 degreeC.
[0010]
It is appropriate that the sugar contained in okara is 0 to 5 g / 100 g, preferably 0 to 3 g / 100 g, more preferably 0 to 1 g / 100 g by removing the sugar. If the amount of the saccharide exceeds 5 g / 100 g, the browning reaction of the saccharide due to retort heating becomes strong, darkening over time and the flavor being impaired.
[0011]
In the present invention, the amount of water from okara is suitably 70% or more, usually 70 to 95%, preferably 75 to 90%, more preferably 80 to 90%. If the moisture from the okara is less than 70%, the moisture will be low and it will be rustling, and the heat conductivity at the time of heating will be poor. On the other hand, if the water content exceeds 95%, the karakara precipitates in the packaging material and the flavor becomes watery.
[0012]
In the present invention, the average particle size of okara is 10-100 micrometers (hereinafter abbreviated as “micron”) in a wet state, preferably 20-50 microns. However, the particle size is measured with a Coulter counter. In addition, since it cannot be measured with a Coulter counter from commercially available okara, the average particle size was measured by a wet sieving method.
[0013]
One example of production from okara is shown below, but is not limited to this example.
10 times the amount of water is added to soybeans that have undergone molting and de-embryonic axis, and dipped at 85-95 ° C. for 60 minutes or longer to sufficiently absorb water (moisture content: 40-50%). What added 3 times amount of 90 degreeC hot water with respect to the hydrolyzed soybean was cut | judged (preferably processed twice or more) by the rotary blade type shear force by a commit roll (made by URSCHEL) etc., and average A fine slurry with a particle size of 45 microns can be obtained.
[0014]
The resulting slurry is then homogenized by treatment with a high-pressure homogenizer (manufactured by APV) at a pressure of 200 kg / cm ² (preferably twice or more) to obtain a fine soybean slurry having an average particle size of 25 microns. Can do. The method for refining okara may be a method other than the above, for example, a mycolloider or a wet jet mill.
[0015]
If the particle size of okara is fine, the fluidity increases and the thermal conductivity improves, making it easier to sterilize, but conversely the average particle size of okara as obtained in the normal tofu production process is usually 200 to 1000 microns Even if the water content is 80% or more, the apparent appearance is due to the presence of voids in the rustling state.
[0016]
A well-known thing can be used for the retort heat sterilization means used for this invention. For example, the retort heat sterilizer may be any of a hot water type, a thermal shower type, a pressure steamer type, and the like. In addition, it is possible to sterilize a large amount of okara at once depending on the type of retort heating.
[0017]
In the present invention, it is appropriate that the okara retort heat sterilization condition is 4 to 20 minutes, preferably 4 to 10 minutes in terms of F ₀ value. The F ₀ value is a numerical value that is an index of the degree of sterilization of microorganisms, and is usually calculated from the following formula based on the sterilization temperature (the product temperature (° C.) of the object to be sterilized) and the holding time (minutes).
F ₀ value = 10 ^{( t - 121.1 ) / 10 xa}
However, t is sterilization temperature (degreeC) and a is holding time (minute).
[0018]
However, the product temperature from the filling oven in the retort heat sterilizer changes (increases) over time due to hot water, so an embedded temperature sensor (for example, Seika Sangyo Co., Ltd.) mounting company Ltd.), takes the data of the temperature changes over time, calculates the F ₀ value by accumulating the calculated [Delta] F ₀ value for each minute time by the formula for each minute time (.DELTA.a).
[0019]
At this time, the retort heat sterilization with an F ₀ value of 4 to 20 minutes is slightly different depending on the apparatus, the packaging material, the packaging weight, the charged amount, etc. in terms of the pot temperature and the holding time. As the filling of 2kg bags per piece, the pot temperature is kept at 115 ° C for 60 to 90 minutes, 120 ° C for 30 to 50 minutes, 125 ° C for 25 to 40 minutes, 130 ° C for 20 to 30 minutes This corresponds to the range of holding (both excluding the temperature rise time (cam up time)). If the holding time is too long, heating will be over and the color will be dark and the flavor will be poor, and if it is stored for 1 week at 5 ° C., the okara will be hard and dispersible. If the holding time is too short, the sterilization will be insufficient and it will not last long and will rot.
[0020]
Okara sterilized by heating is cooled to 100 ° C. or lower under pressure and becomes an Aseptic (sterile) product. As described above, the present invention makes it possible to sterilize by heating the retort from okara.
[0021]
【Example】
Embodiments of the present invention will be described below with reference to examples.
◎ Production example 1 (in the case of hot water with a high immersion temperature)
1 part of moulted / dehulled soybeans (water content 40-50%) after adding 10 times the amount of water to moulted / dehulled soybeans and dipping (branching) for 60 minutes or more at 85-95 ° C On the other hand, processing using a commit roll (manufactured by URSCHEL) that cuts 3 parts of hot water (90 ° C) with a rotating blade shear force is repeated twice, and the average particle size is 45 microns. A slurry was obtained.
[0022]
The resulting slurry was then homogenized by treatment twice at 200 kg / cm ² using a high pressure homogenizer (manufactured by APV) to obtain a fine soybean slurry having an average particle size of 25 microns. This homogenized fine slurry was obtained after being treated at 3000 G for 5 minutes by a centrifuge (manufactured by Sakai Kogyo Co., Ltd.). The moisture from this okara was 86%, and the sugar content was 0.2%.
[0023]
◎ Production example 2 (from commercially available okara)
Since commercially available tofu oak was not soaked and de-embryonic, it was immersed in water in the form of whole soybeans and coarsely pulverized with a stone mortar (my colloid), so that soybean hulls and hypocotyls remained. In addition, the moisture content was 81%, which was lower than the 86% moisture content of Production Example 1, the average particle size was as large as 400 microns or more, the sugar content was 6.4%, and the okara itself was dark.
[0024]
◎ Production Example 3 (in the case of hot water with a low immersion temperature)
10 parts of water was added to 1 part by weight (hereinafter referred to as “parts”) of molting / dehulled soybeans, and immersed at 50 to 65 ° C. for 60 minutes or more. In the following, an okara having an average particle diameter of 25 microns was obtained in the same manner as in Production Example 1. The okara moisture was 86% and the sugar content was 2.5%.
[0025]
Example 1
2 kg each of the okara from the average particle size of 25 microns, the sugar content of 0.2%, and the moisture content of 86% obtained in the same manner as in Production Example 1 was filled in a pillow at 50 ° C. 300kg (150 bags) of filled okara was divided into 100 cars (50 bags) for each of the three cars and placed in a retort heating kettle (manufactured by Nisaka Seisakusho). The hot water charged into the kettle was set at 100 ° C, and the sterilization conditions were set at a kettle temperature of 120 ° C and held for 30 minutes. At this time, the time (cam up time) for the liquid temperature inside the pot to reach the set temperature of 120 ° C. was set to 20 minutes in order to eliminate the temperature unevenness (F ₀ value unevenness) before, during and after the inside of the pot. The F ₀ value for 30 minutes after the kettle temperature reached 120 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. The F ₀ value at this time was 8 minutes. The sterilized okara was cooled with chilled water at 5 ° C. under pressure, removed from the kettle, and cooled to 10 ° C. or less over 3 hours in a refrigerator with 2 ° C. cold air.
[0026]
As for the physical properties at this time, the color tone was very white, no scorching, no discoloration was observed, and the hardness after 1 week at 5 ° C. was also good. The flavor was good tofu-like and had no burning odor. The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. The filled okara was stored at 35 ° C. for 3 days, all of which had excellent physical properties such as flavor, texture, and color tone, and the number of bacteria was 0 × 10 ¹ cells / g or less. Therefore, sterility was confirmed.
[0027]
Example 2
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 2.5%, and a moisture content of 86% obtained in the same manner as in Production Example 3. Retort heat sterilization was performed.
[0028]
The physical properties at this time were slightly darker than the case of Example 1, but there was no burning odor at all regarding the flavor. The hardness was also good after storage for 1 week at 5 ° C. The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. The filled okara was stored at 35 ° C. for 3 days, all of which had excellent physical properties such as flavor, texture, and color tone, and the number of bacteria was 0 × 10 ¹ cells / g or less. Therefore, sterility was confirmed.
[0029]
Example 3
The average particle size obtained in Production Example 1 was 25 microns, the sugar content was 0.2%, the moisture content was 86%, and 2 kg of okara from 50 ° C. was filled in the same packaging material as Example 1 at 50 ° C. The sterilization temperature was set to 40 minutes after the pot temperature reached 120 ° C except for the cam-up time. The F ₀ value for 40 minutes after the kettle temperature reached 120 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. At this time, the F ₀ value was 17 minutes. The sterilized okara was cooled under pressure with 5 ° C. chilled water, removed from the kettle, and cooled to 10 ° C. over 3 hours in a refrigerator with 2 ° C. cold air.
[0030]
As for the physical properties at this time, the color tone was extremely white, no scorch was observed, and the hardness after 1 week at 5 ° C. was also good. The flavor was delicious, similar to tofu. The filled okara was stored at 35 ° C. for 3 days, all of which had excellent physical properties such as flavor, texture, and color tone, and the number of bacteria was 0 × 10 ¹ cells / g or less. Therefore, sterility was confirmed.
[0031]
◎ Comparative Example 1
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 0.2%, and a moisture content of 86% obtained in the same manner as in Production Example 1, followed by retort heat sterilization. . The sterilization temperature was set to 60 minutes after the pot temperature reached 120 ° C except for the cam-up time. The F ₀ value for 60 minutes after the kettle temperature reached 120 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. The F ₀ value at this time was 25 minutes. The sterilized okara was cooled with chilled water at 5 ° C. under pressure, removed from the kettle, and cooled to 10 ° C. over 3 hours in a refrigerator with 2 ° C. cold air.
[0032]
The physical properties at this time were slightly black in color and burnt. The hardness after 1 week at 5 ° C. was hard and poor in water dispersibility. As for the flavor, a burning smell was felt and it was not able to withstand eating. The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. Although this filled okara was stored at 35 ° C. for 3 days, the number of bacteria was 0 × 10 ¹ cells / g or less, and sterility was confirmed.
[0033]
Example 4
10 parts of water was added to 1 part by weight (hereinafter referred to as “parts”) of molting / dehulled soybeans, followed by immersion at 50 to 65 ° C. for 30 minutes. In the following, an okara having an average particle diameter of 25 microns was obtained in the same manner as in Production Example 1. This okara had a moisture content of 86% and a carbohydrate content of 4.5%. 2 kg of this okara was filled in the same packaging material as in Example 1 at 50 ° C., and retort heat sterilization was performed in the same manner as in Example 1.
[0034]
As for the physical properties at this time, the color tone was slightly blackish compared to the case of Example 1, and although there was a slight scorching taste about the flavor, the burning odor was not felt, and it was a flavor that can be eaten. . Hardness was good after 2 months storage at 5 ° C.
The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. Although this filled okara was stored at 35 ° C. for 3 days, the number of bacteria was 0 × 10 ¹ cells / g or less, and sterility was confirmed.
[0035]
◎ Comparative Example 2
The same packing material as in Example 1 was filled at 50 ° C. with 2 kg of okara having an average particle diameter of 400 microns or more, a sugar content of 6.4%, and a moisture content of 81% obtained in the same manner as in Production Example 2. Retort was sterilized by heating.
[0036]
The physical properties were clearly black and burnt, and the flavor was also delicious and not suitable for eating. The hardness was good after being stored at 5 ° C. for 2 months. The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. However, when this filled okara was stored at 35 ° C. for 3 days, the number of bacteria was 10 ⁶ cells / g or more and was not sterile. The flavor was also very strong and the color was quite dark.
[0037]
Example 5
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 0.2%, and a moisture content of 86% obtained in the same manner as in Production Example 1, followed by retort heat sterilization. . Sterilization conditions were set at a pot temperature of 115 ° C. and a holding time of 60 minutes. At this time, in order to eliminate the uneven temperature before, during and after the inside of the pot, that is, the F ₀ value, the time for the pot temperature to reach the set temperature 115 ° C., that is, the cam-up time was set to 15 minutes. The F ₀ value for 60 minutes after the kettle temperature reached 115 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. The F ₀ value at this time was 10 minutes. The sterilized okara was cooled with chilled water at 5 ° C. under pressure, removed from the kettle, and cooled to 10 ° C. over 3 hours in a refrigerator with 2 ° C. cold air.
[0038]
The physical properties at this time were slightly black as compared with the case of Example 1, but the hardness after 1 week at 5 ° C. was good, and the flavor was also delicious like tofu. The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. Although this filled okara was stored at 35 ° C. for 3 days, the number of bacteria was 0 × 10 ¹ cells / g or less, and sterility was confirmed.
[0039]
◎ Comparative Example 3
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 0.2%, and a moisture content of 86% obtained in the same manner as in Production Example 1, followed by retort heat sterilization. . Sterilization conditions were set at a pot temperature of 115 ° C. and a holding time of 90 minutes. At this time, the time for the kettle temperature to reach the set temperature, i.e., the cam-up time, was set to 15 minutes in order to eliminate the non-uniformity of the temperature before, inside and after, i.e., the F ₀ value. The F ₀ value for 60 minutes after the kettle temperature reached 115 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. The F ₀ value at this time was 22 minutes. The sterilized okara was cooled with chilled water at 5 ° C. under pressure, removed from the kettle, and cooled to 10 ° C. over 3 hours in a refrigerator with 2 ° C. cold air.
[0040]
The physical properties at this time were slightly black in color and burnt. The hardness after 1 week at 5 ° C. was good, but the flavor was not suitable for eating with a strong burning odor. The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. Although this filled okara was stored at 35 ° C. for 3 days, the number of bacteria was 0 × 10 ¹ cells / g or less, and sterility was confirmed.
[0041]
Example 6
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 0.2%, and a moisture content of 86% obtained in the same manner as in Production Example 1, followed by retort heat sterilization. . Sterilization conditions were set at 110 ° C. for 90 minutes. At this time, the time for the kettle temperature to reach the set temperature, i.e., the cam-up time, was set to 15 minutes in order to eliminate the non-uniformity of the temperature before, inside and after, i.e., the F ₀ value. The F ₀ value for 90 minutes after the pot temperature reached 110 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. The F ₀ value at this time was 9 minutes. The sterilized okara was cooled with chilled water at 5 ° C. under pressure, removed from the kettle, and cooled to 10 ° C. over 3 hours in a refrigerator with 2 ° C. cold air.
[0042]
The physical properties at this time were slightly black as compared with the case of Example 1, but the hardness after 1 week at 5 ° C. was good, and the flavor was also a tofu-like taste. The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. This filled okara was stored at 35 ° C. for 3 days, but the number of bacteria was 0 × 10 ¹ cells / g or less, confirming sterility.
[0043]
◎ Comparative Example 4
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 0.2%, and a moisture content of 86% obtained in the same manner as in Production Example 1, followed by retort heat sterilization. . Sterilization conditions were set at a pot temperature of 110 ° C. and a holding time of 60 minutes. At this time, the time for the kettle temperature to reach the set temperature, i.e., the cam-up time, was set to 15 minutes in order to eliminate the non-uniformity of the temperature before, inside and after, i.e., the F ₀ value. The F ₀ value for 60 minutes after the kettle temperature reached 110 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. The F ₀ value at this time was 2 minutes. The sterilized okara was cooled with chilled water at 5 ° C. under pressure, removed from the kettle, and cooled to 10 ° C. over 3 hours in a refrigerator with 2 ° C. cold air.
[0044]
As for the physical properties at this time, the color tone was white, there was no burning, and the flavor was good. The hardness was good after 2 months storage at 5 ° C. The number of bacteria was 10 ⁵ / g for the raw material bacteria, but 1 × 10 ¹ / g for this sterilized treatment. This filled okara was stored at 35 ° C. for 3 days, but the number of bacteria was 10 ⁶ cells / g or more and was not sterile.
[0045]
Example 7
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 0.2%, and a moisture content of 86% obtained in the same manner as in Production Example 1, followed by retort heat sterilization. . The sterilization conditions were set at a kettle temperature of 130 ° C and a holding time of 20 minutes. At this time, the time for the kettle temperature to reach the set temperature, i.e., the cam-up time, was set to 15 minutes in order to eliminate the non-uniformity of the temperature before, inside and after, i.e., the F ₀ value. The F ₀ value for 20 minutes after the kettle temperature reached 130 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. The F ₀ value at this time was 20 minutes. The sterilized okara was cooled with chilled water at 5 ° C under pressure, removed from the kettle, and cooled to 10 ° C over 4 hours in a refrigerator with 2 ° C cold air.
[0046]
As for the physical properties at this time, there was no problem in color tone and scorching. The hardness after 1 week at 5 ° C. was good, and the flavor was also a tofu-like taste. The number of bacteria was 10 ⁵ cells / g, whereas the number of bacteria subjected to this sterilization treatment was 0 × 10 ¹ cells / g. This filled okara was stored at 35 ° C. for 3 days, but the number of bacteria was 0 × 10 ¹ cells / g or less, confirming sterility.
[0047]
◎ Comparative Example 5
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 0.2%, and a moisture content of 86% obtained in the same manner as in Production Example 1, followed by retort heat sterilization. . Sterilization conditions were set at a kettle temperature of 130 ° C and a holding time of 40 minutes. At this time, the time for the pot temperature to reach the set temperature, that is, the cam-up time, was set to 15 minutes in order to eliminate the _non- uniformity of the temperature inside, after, and after the pot, that is, the fluctuation of the F ₀ value. The F ₀ value for 40 minutes after the kettle temperature reached 130 ° C. was calculated by taking out the temperature sensor placed in the filled bag after sterilization and reading the temperature change. The F ₀ value at this time was 40 minutes. After the sterilization, the okara was cooled with chilled water at 5 ° C. under pressure, removed from the kettle, and cooled to 10 ° C. over 4 hours in a refrigerator with 2 ° C. cold air.
[0048]
As for the physical properties at this time, the color tone was clearly burnt, and the flavor was also delicious and was not suitable for eating. The hardness was slightly hard after 2 months at 5 ° C., and the water dispersibility was poor. The number of bacteria was 10 ⁵ / g for the raw material bacteria, while that for this sterilization treatment was 0 × 10 ¹ / g. Although this filled okara was stored at 35 ° C. for 3 days, the number of bacteria was 0 × 10 ¹ cells / g or less and sterility was confirmed, but the flavor had a strong taste and a burning odor.
[0049]
◎ Comparative Example 6
The same packing material as in Example 1 was filled at 50 ° C. with an average particle size of 25 microns, a sugar content of 0.2%, and a moisture content of 86% obtained in the same manner as in Production Example 1, followed by retort heat sterilization. . The sterilization conditions were set at a pot temperature of 135 ° C and a holding time of 20 minutes, but the packaging material could not withstand the heat and abandoned.
[0050]
【The invention's effect】
According to the present invention, okara sterilized by retort heating can be manufactured without impairing the color tone and flavor.

Claims (2)

Carbohydrate content of 5 wt% or less, an average particle diameter of 10 to 100 microns, the Okara in water of 70 to 95 wt% state F ₀ A method for producing okara, which is heated for 4 to 21 minutes by value . The process according to claim 1, wherein the average particle size is 20 to 50 microns.