Heat-resistant and shear-resistant microcapsules, their manufacturing method and applications

Abstract

The microcapsules according to the present invention are heat-resistant and shear-resistant, and each comprise a core material, a protein coating layer encapsulating the core material, and a wall material encapsulating the protein coating layer. The core material contains an oil or fat, and the wall material is formed by heat-curing a colloid. The microcapsules according to the present invention first encapsulate the oil or fat in the internal phase with the protein, thereby providing an internal environment that blocks moisture and oxygen. Furthermore, the endothermic phase change at the melting point is utilized to improve the viability and stability of the active substance during the heat treatment process. The wall material further protects the microcapsules, allowing them to have high stability and high-temperature resistance, as well as excellent shear resistance and acid resistance.

Description

[Technical Field]

[0001] This application claims priority from a Chinese patent application filed with the State Intellectual Property Office of the People's Republic of China on December 30, 2022, bearing application number 202211741593.8 and entitled "Heat-resistant and shear-resistant microcapsules, their manufacturing method and applications," the entire contents of which are incorporated herein by reference.

[0002] This application claims priority from a Chinese patent application filed with the State Intellectual Property Office of the People's Republic of China on December 30, 2022, bearing application number 202211734574.2 and entitled "High-temperature shear-resistant colloids, microcapsules, their manufacturing methods and applications," the entire contents of which are incorporated herein by reference.

[0003] This application claims priority based on a Chinese patent application filed with the State Intellectual Property Office of the People's Republic of China on December 30, 2022, bearing application number 202211734622.8 and entitled "Heat-resistant and acid-resistant oil and fat composition, microcapsules, their manufacturing method and application," the entire contents of which are incorporated herein by reference.

[0004] The present invention belongs to the food technology field, and particularly relates to heat-resistant and shear-resistant microcapsules, their manufacturing method and applications. [Background technology]

[0005] Microcapsules are tiny containers made of natural or synthetic polymers (wall materials). They not only confine and protect liquid droplets, particles, or gases (core materials) within the capsules, but also enhance the performance and activity of the core materials by selecting or preparing appropriate wall materials. Therefore, the microencapsulation method has excellent adaptability and advanced functionality. Since their introduction in the 1930s, microcapsules have undergone extensive research and have made great progress. They are now widely used in fields such as pharmaceuticals, food, cosmetics, pesticides and fertilizers, dyes and pigments, paints, adhesives, textiles, inks, and additives.

[0006] When volatile, oxidative, light-sensitive, or heat-sensitive substances are microencapsulated, they are protected from direct contact with light, heat, or air, their volatilization and oxidation are inhibited, and their light (heat) sensitivity is reduced.

[0007] Vitamin A is an important drug for preventing and treating night blindness, and vitamin D2 promotes intestinal absorption of calcium and phosphorus, but these are easily decomposed under ultraviolet light and easily oxidized in the air, reducing their effectiveness. Vitamin C is a major treatment for scurvy, but its properties are unstable and it is easily destroyed by heat. Therefore, by microencapsulating vitamins, it is possible to extend the shelf life of vitamin preparations.

[0008] Probiotics have many benefits, including improving the intestinal microbial balance, boosting immunity, fighting tumors, and lowering cholesterol. However, during the processing and storage of commercial products, parameters such as mechanical force, temperature, water activity, oxygen gas content, and pH change can all have a negative impact on the survival of probiotics. Furthermore, in order to colonize and grow in the intestine, probiotics must maintain their activity even after being digested in the gastrointestinal tract (generally, bacterial activity lasts for 10 years). 6 CFU / g or 10 6 (It is believed that the CFU / mL level must be maintained at or above 1000.) In order for probiotics to survive during production and processing, storage, and digestion in the intestinal tract and exert their beneficial effects on human health, it is necessary to design specific encapsulation systems, such as microcapsules, that can withstand the external processing environment, and then transport them to the desired location in the intestinal tract where they can successfully colonize and grow.

[0009] However, as raw materials for food and pharmaceuticals, they must be subjected to high-temperature sterilization during production (for example, the sterilization process to kill most microorganisms requires relatively high temperatures), and during this process, the wall material often melts, causing the active substance to separate into the outer layer, which then becomes inactive when exposed to high temperatures.

[0010] Furthermore, food processing often requires high-temperature stirring processes. For example, in the production of processed cheese, the raw materials for the processed cheese must be placed in a melting pot and heated and stirred. This often results in the loss of activity of physiologically active substances, including probiotics and lactoferrin, due to the high temperature. Furthermore, due to the high temperature and stirring, typical microcapsule products containing embedded physiologically active substances are subject to shear forces caused by the stirring action, resulting in the physiologically active substances losing their activity upon contact with high temperatures. Therefore, how to enable physiologically active substances to withstand the harsh conditions of food processing while maximally maintaining their original biological activity is a technical challenge that must be addressed as soon as possible. Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention has been made in view of the above circumstances, and the technical problem to be solved is to provide microcapsules having heat resistance and shear resistance, a method for producing the same, and applications thereof. [Means for solving the problem]

[0012] According to the present invention, there is provided a heat-resistant and shear-resistant microcapsule comprising a core material containing oil or fat, a protein coating layer encapsulating the core material, and a wall material encapsulating the protein coating layer and formed by heat-curing a colloid.

[0013] Preferably, the microcapsules have at least one of the following characteristics: (1) The fat or oil has, in a differential scanning calorimetry curve, an endothermic peak between 30°C and 48°C and an exothermic peak between 200°C and 245°C; (2) The fat or oil has a slope of a solid fat content curve at 10°C to 40°C of -2.51 to -1.57; (3) The oil or fat has a viscosity at 95°C of 23.900 mPa·s to 84.445 mPa·s; (4) The oil or fat is a vegetable oil and / or an animal oil; (5) The fat or oil has been treated by at least one of interesterification, fractionation, and hydrogenation; (6) The mass percentage of the oil or fat is 5% to 17% based on the mass of the microcapsules.

[0014] Preferably, the protein in the protein coating layer is one or more selected from the group consisting of casein, pea protein, and whey protein, and / or the mass percentage of the protein coating layer relative to the mass of the microcapsules is 1% to 40% based on the mass of the microcapsules.

[0015] Preferably, the microcapsules have at least one of the following characteristics: (i) The wall material is formed by calcifying, crosslinking, and heat-curing a colloid; (ii) the wall material has a differential scanning calorimetry curve having one endothermic peak between 190°C and 210°C and one exothermic peak between 250°C and 281°C; (iii) The wall material has a turbidity of 1.3 to 1.5 cm at 25°C to 95°C. -1 is; (iv) The colloid contains alginic acid and / or a salt thereof and a gelling agent, and preferably, the mass ratio of the gelling agent to alginic acid and / or a salt thereof is (1 to 20):1, and more preferably, the gelling agent is one or more selected from the group consisting of a thermoreversible gel, curdlan, konjac gum, and gellan gum; (v) The colloid has a mass percentage of 0.2% to 7% based on the mass of the microcapsules.

[0016] Preferably, the core material of the microcapsules contains at least one physiologically active substance selected from the group consisting of probiotics, vitamins, polyunsaturated fatty acids, active proteins, and natural pigments.

[0017] According to the present invention, there is further provided a method for producing heat-resistant and shear-resistant microcapsules, which includes the following steps S1 to S4: Step S1) of mixing a physiologically active substance with fats and oils to obtain a core material; Step S2) of mixing and emulsifying the core material and the protein emulsion to obtain a core material emulsion; Step S3) of mixing and stirring the core material emulsion with a wall material solution containing a colloid to obtain a mixed solution; Step S4) heat-treating the mixed solution to obtain microcapsules.

[0018] Preferably, the mass concentration of the protein emulsion is 1% to 5%, and the mass ratio of the core material to the protein emulsion is 1:(1 to 10), and / or The mass concentration of the colloid in the wall material solution is 0.1% to 1%, the mass ratio of the core material emulsion to the wall material solution is 1:(2 to 7), and / or the heat treatment is performed at a temperature of 75°C to 95°C, and / or the heat treatment is performed for 10 to 30 minutes.

[0019] The present invention further provides use of the above-mentioned heat-resistant and shear-resistant microcapsules as a food additive.

[0020] The present invention further provides a food product containing the heat-resistant and shear-resistant microcapsules described above.

[0021] According to the present invention, there is provided a heat-resistant and shear-resistant microcapsule comprising a core material containing an oil or fat, a protein coating layer encapsulating the core material, and a wall material encapsulating the protein coating layer and formed by heat-curing a colloid. Compared to conventional techniques, the microcapsules of the present invention first encapsulate the oil or fat in the internal phase with protein, thereby providing an internal environment that is insulated from moisture and oxygen. Furthermore, the endothermic phase change at the melting point is utilized to improve the viability and stability of the active substance during the heat treatment process. Furthermore, the wall material provides further protection, enabling the microcapsules to have high stability and high-temperature resistance, as well as excellent shear resistance and acid resistance.

[0022] Experimental results show that the microcapsules of the present invention have high-temperature shear resistance, shear resistance, and gastric acid resistance properties that are more than one million times higher, effectively reducing the loss of probiotics during processing and gastrointestinal digestion. DETAILED DESCRIPTION OF THE INVENTION

[0023] The technical methods in the embodiments of the present invention will be described below clearly and completely with reference to the embodiments of the present invention. It is obvious that the embodiments described herein are only a part of the embodiments of the present application, not all of them. Based on the embodiments of the present invention, any other embodiments that a person skilled in the art can obtain without exerting any labor equivalent to an inventive step shall fall within the protection scope of the present invention.

[0024] According to the present invention, there is provided a colloid having high-temperature shear resistance, in which the differential scanning calorimetry (DSC) curve of the colloid has one endothermic peak between 190°C and 210°C and one exothermic peak between 270°C and 281°C.

[0025] In the present invention, preferably, the differential scanning calorimetry (DSC) curve of the colloid having high-temperature shear resistance has one endothermic peak between 190°C and 210°C. In the present invention, preferably, the differential scanning calorimetry (DSC) curve of the colloid having high-temperature shear resistance has one exothermic peak between 256°C and 281°C. More preferably, the differential scanning calorimetry (DSC) curve of the colloid having high-temperature shear resistance has one exothermic peak between 269°C and 281°C.

[0026] In the present invention, the measurement range of the DSC is preferably 25°C to 300°C, and the heating rate of the DSC is preferably 0.5 to 1°C / min. In the present invention, more preferably, the colloid is held at a fixed temperature of 25°C for 5 to 10 minutes and then heated. Even more preferably, the obtained DSC curve has one broad endothermic peak between 190°C and 210°C. The width of the endothermic peak is preferably 57°C to 70°C, more preferably 60 to 70°C, and even more preferably 60 to 66°C.

[0027] The turbidity of the colloid according to the present invention at 25°C to 95°C is preferably 1.3 to 1.5 cm -1 and more preferably 1.32 to 1.5 cm -1 and more preferably 1.4 to 1.5 cm -1 and more preferably 1.4 to 1.48 cm -1 and most preferably 1.4 to 1.45 cm -1 is.

[0028] The colloid according to the present invention preferably comprises a thermal gel, and preferably further comprises alginic acid and / or a salt thereof. The mass ratio of the gelling agent to alginic acid and / or a salt thereof is preferably (1-20):1, more preferably (5-20):1, even more preferably (8-15):1, and most preferably (10-12):1. The thermal gel is preferably one or more selected from the group consisting of a thermoreversible gel, curdlan, konjac gum, and gellan gum. The thermoreversible gel is preferably pectin.

[0029] The colloid is preferably obtained by heat treatment, more preferably by heat treatment of an aqueous solution containing a thermal gel, and even more preferably by heat treatment of an aqueous solution containing a thermal gel and alginic acid and / or a salt thereof. The mass concentration of the aqueous solution containing the thermal gel is preferably 0.1% to 1%. The mass concentration of the aqueous solution containing the thermal gel and alginic acid and / or a salt thereof is preferably 0.1% to 1%. The heat treatment is preferably carried out at a temperature of 75°C to 95°C. The heat treatment is preferably carried out for 30 to 120 seconds. More preferably, mineralization crosslinking is further carried out before the heat treatment. The mineralization crosslinking solution is preferably a 1 to 20 wt% calcium salt solution. The calcium salt solution is preferably a calcium chloride solution and / or a calcium lactate solution. When the calcium salt solution is a calcium chloride solution, its concentration is preferably 1 to 10 wt%. When the calcium salt solution is a calcium lactate solution, its concentration is preferably 1 to 20 wt%, more preferably 3 to 15 wt%, even more preferably 5 to 15 wt%, and most preferably 5 to 10 wt%. The calcification crosslinking is preferably carried out for 10 to 20 minutes.

[0030] The present invention further provides the use of the above-described colloid for improving the heat resistance of a physiologically active substance.

[0031] Here, the heat resistance is preferably the heat resistance of the physiologically active substance in a shear environment. The physiologically active substance is preferably a heat-sensitive substance, more preferably one or more selected from the group consisting of probiotics, vitamins, polyunsaturated fatty acids, active proteins, and natural pigments.

[0032] The present invention further provides a food product comprising the above-described colloid.

[0033] According to the present invention there is further provided the use of the above-described colloid as a microcapsule wall material.

[0034] The present invention further provides a microcapsule comprising a core material and a wall material enclosing the core material, the wall material containing the above-described colloid. The mass ratio of the core material to the colloid, based on the mass ratio of the dry substances, is preferably 5.56:1 to 1.59:1.

[0035] The core material in the microcapsules according to the present invention preferably contains a physiologically active substance and a fat or oil. The physiologically active substance is the same as that described above, and will not be further described here. The fat or oil is not particularly limited as long as it is well known to those skilled in the art, but in the present invention, it is preferably vegetable oil, more preferably one or more selected from the group consisting of soybean oil, olive oil, sunflower seed oil, and cocoa butter. The mass of the fat or oil relative to the mass of the microcapsule is preferably 5% to 17%.

[0036] Preferably, a protein coating layer is further included between the core material and the wall material. The protein coating layer is formed from a protein aqueous solution. The type of protein in the protein coating layer is not particularly limited as long as it is a protein well known to those skilled in the art. In the present invention, however, a natural protein with high heat resistance and gelling properties is preferred, and more preferably, one or more proteins selected from the group consisting of casein, pea protein, and whey protein are preferred. The mass of the protein coating layer is preferably 6% to 30% of the mass of the microcapsules. In this case, the mass ratio of the total mass of the core material and the protein coating layer to the mass of the colloid, in terms of the mass of the hydrate, is preferably 1:2 to 1:7. In an embodiment according to the present invention, the mass ratio of the total mass of the core material and the protein coating layer to the mass of the colloid is specifically 1:2, 1:7, 1:3, or 1:5.

[0037] The water concentration in the microcapsules according to the present invention is preferably 75% to 90%, more preferably 76.33% to 87.68%. For convenience of storage, it is preferable to dry the microcapsules until the water concentration becomes 1% or less.

[0038] According to the present invention, there is further provided a method for producing microcapsules, which includes step S1) of mixing a colloid raw material with water to obtain a colloid raw material solution, step S2) of mixing and stirring a core material with the colloid raw material solution to obtain a mixed solution, and step S3) of heat-treating the mixed solution to obtain microcapsules.

[0039] Here, the supply sources of all raw materials in the present invention are not particularly limited as long as they are commercially available products.

[0040] A colloid raw material solution is obtained by mixing a colloid raw material with water. The colloid raw material preferably contains a thermal gel, and preferably further contains alginic acid and / or a salt thereof. The mass ratio of the gelling agent to alginic acid and / or a salt thereof is preferably (1 to 20):1, more preferably (5 to 20):1, even more preferably (8 to 15):1, and most preferably (10 to 12):1. The thermal gel is preferably one or more selected from the group consisting of thermoreversible gel, curdlan, konjac gum, and gellan gum. The thermoreversible gel is preferably pectin. The alginate salt is not particularly limited as long as it is a salt compound well known to those skilled in the art, but in the present invention, sodium alginate is preferred. The water is preferably deionized water. The mixing is preferably performed at a temperature of 30°C to 50°C. The mixing is preferably performed at a speed of 200 to 1000 rpm. The mixing is preferably performed for 20 to 60 minutes, more preferably 30 to 40 minutes. The mass concentration of the colloid raw material in the colloid solution is preferably 0.1% to 1%. In an embodiment according to the present invention, the mass concentration of the colloid raw material in the colloid solution is specifically 1%, 0.1%, 0.3%, or 0.5%. The colloid can be obtained by heat-treating the colloid raw material solution.

[0041] A core material and a colloid raw material solution are mixed and stirred to obtain a mixed solution. In the present invention, the core material is preferably produced by dispersing a physiologically active substance in an oil or fat to obtain the core material. The physiologically active substance and oil or fat are the same as those described above, and therefore will not be further described here. The dispersion is preferably carried out for 2 to 4 minutes. The mass ratio of the core material to the colloid solution is preferably 1:(2 to 7). In embodiments of the present invention, the mass ratio of the core material to the colloid solution is specifically 1:2, 1:7, 1:3, or 1:5. The mixing and stirring is preferably carried out at a temperature of 30°C to 50°C. In embodiments of the present invention, the mixing and stirring is specifically carried out at a temperature of 30°C, 50°C, 40°C, or 45°C. The mixing and stirring is preferably carried out at a speed of 500 to 2000 rpm, more preferably 800 to 2000 rpm, and even more preferably 800 to 1500 rpm. The mixing and stirring is preferably carried out for 20 to 30 seconds.

[0042] In the present invention, it is more preferable to emulsify the core material with a protein aqueous solution to obtain a core material emulsion, and then mix and stir the core material emulsion with the colloid raw material solution. The protein aqueous solution is preferably a protein aqueous solution to be sterilized with ultraviolet light. The mass concentration of the protein aqueous solution is preferably 1% to 5%, more preferably 2% to 4%, and even more preferably 3%. The ultraviolet sterilization is preferably carried out for 10 to 20 minutes, more preferably 15 minutes. The protein aqueous solution is preferably prepared by mixing protein with water, adjusting the pH to neutral, and stirring. The protein aqueous solution is preferably one or more selected from the group consisting of pea protein, casein, whey protein, and soy protein isolate. The stirring is preferably carried out at a speed of 500 to 1000 rpm, more preferably 600 to 800 rpm. The stirring is preferably carried out for 1 to 5 hours, more preferably 2 to 3 hours. The mass ratio of the core material emulsion to the colloid solution is preferably 1:(2 to 7). In an embodiment according to the present invention, the mass ratio of the core emulsion to the colloidal solution is specifically 1:2, 1:7, 1:3, or 1:5. The mixing and stirring is preferably carried out at a temperature of 30°C to 50°C. In an embodiment according to the present invention, the mixing and stirring is specifically carried out at a temperature of 30°C, 50°C, 40°C, or 45°C. The mixing and stirring is preferably carried out at a speed of 500 to 2000 rpm, more preferably 800 to 2000 rpm, and even more preferably 800 to 1500 rpm. The mixing and stirring is preferably carried out for 20 to 30 seconds.

[0043] The mixed solution is heat-treated (more preferably, calcified crosslinked and then heat-treated) to obtain microcapsules. The solution for calcification crosslinking is preferably a 1 to 20 wt% calcium salt solution. The calcium salt solution is preferably a calcium chloride solution and / or a calcium lactate solution. When the calcium salt solution is a calcium chloride solution, its concentration is preferably 1 to 10 wt%. When the calcium salt solution is a calcium lactate solution, its concentration is preferably 1 to 20 wt%, more preferably 3 to 15 wt%, even more preferably 5 to 15 wt%, and most preferably 5 to 10 wt%. The calcification crosslinking is preferably carried out for 10 to 20 minutes. The heat curing is preferably carried out at a temperature of 75°C to 95°C. In an embodiment according to the present invention, the heat curing is specifically carried out at a temperature of 95°C, 75°C, 80°C, or 85°C. The heat curing is preferably carried out for 30 to 120 seconds.

[0044] The final microcapsules are preferably stored at 4°C.

[0045] According to the present invention there is further provided the use of microcapsules as a food additive applicable in food processing.

[0046] The present invention further provides use of the microcapsules described above for improving the heat resistance of a physiologically active substance, preferably the heat resistance of the physiologically active substance in a shear environment, and the physiologically active substance is a thermosensitive substance.

[0047] The present invention further provides a food product comprising the microcapsules described above.

[0048] The present invention further provides a heat-resistant and shear-resistant colloidal wall material, the differential scanning calorimetry (DSC) curve of which has one endothermic peak between 190°C and 210°C and one exothermic peak between 250°C and 281°C.

[0049] In the present invention, the differential scanning calorimetry (DSC) curve of the colloid wall material preferably has one endothermic peak between 190° C. and 201° C. In the present invention, the differential scanning calorimetry (DSC) curve of the colloid wall material preferably has one exothermic peak between 256° C. and 281° C., and more preferably has one exothermic peak between 269° C. and 281° C.

[0050] In the present invention, the measurement range of the DSC is preferably 25°C to 300°C, and the heating rate of the DSC is preferably 0.5 to 1°C / min. In the present invention, it is more preferable that the colloidal wall material is held at a fixed temperature of 25°C for 5 to 10 minutes, and then heated, and the resulting DSC curve has one broad endothermic peak between 190°C and 210°C. The width of the endothermic peak is preferably 57°C to 70°C, and more preferably 60 to 70°C.

[0051] The turbidity of the colloidal wall material according to the present invention at 25°C to 95°C is preferably 1.3 to 1.5 cm -1 and more preferably 1.32 to 1.5 cm -1 and more preferably 1.4 to 1.5 cm -1 and more preferably 1.4 to 1.48 cm -1 and most preferably 1.4 to 1.45 cm -1 is.

[0052] The colloid wall material according to the present invention is preferably formed by heat-curing a colloid, and more preferably by calcifying and crosslinking a colloid and heat-curing it. The colloid preferably contains alginic acid and / or a salt thereof and a gelling agent. The mass ratio of the gelling agent to alginic acid and / or a salt thereof is preferably (1-20):1, more preferably (5-20):1, even more preferably (8-15):1, and most preferably (10-12):1. The alginate salt is not particularly limited as long as it is an alginate salt well known to those skilled in the art, but in the present invention, sodium alginate is preferred. The gelling agent is preferably one or more selected from the group consisting of a thermoreversible gel, curdlan, konjac gum, and gellan gum. The thermoreversible gel is preferably pectin.

[0053] According to the present invention there is further provided the use of the above-described colloidal wall material as a microcapsule wall material.

[0054] The present invention further provides a heat-resistant and acid-resistant fat or oil, the differential scanning calorimetry curve of which has an endothermic peak between 30°C and 50°C and an exothermic peak between 200°C and 245°C.

[0055] Preferably, the differential scanning calorimetry curve of the fat or oil has an endothermic peak between 30°C and 48°C and an exothermic peak between 200°C and 241°C.

[0056] The slope of the solid fat content curve of the fat or oil at 10°C to 40°C is preferably -2.51 to -1.57, and more preferably -2.45 to -1.85.

[0057] The viscosity of the oil or fat at 95° C. is preferably 23.900 to 84.445 mPa·s. In an embodiment according to the present invention, the viscosity of the oil or fat at 95° C. is specifically 25.2 mPa·s or 28 mPa·s.

[0058] In the present invention, the oil is preferably a vegetable oil and / or an animal oil.

[0059] In the present invention, the fat or oil is preferably treated by at least one process selected from interesterification, fractionation, and hydrogenation.

[0060] The fats and oils having the above-mentioned specific parameters according to the present invention more preferably include one or more selected from the group consisting of blended oils, blended oils treated by interesterification, middle fraction oils, and hydrogenated oils.

[0061] Here, the blended oil contains unsaturated fatty acid oils and fats with an unsaturated fatty acid content of more than 50% and saturated fatty acid oils and fats with a saturated fatty acid content of more than 50%. In the present invention, the unsaturated fatty acid oils and fats are preferably one or more selected from the group consisting of palm kernel oil, rapeseed oil, rice bran oil, soybean oil, sunflower seed oil, rapeseed oil, and corn oil. The saturated fatty acid oils and fats are one or more selected from the group consisting of coconut oil, palm stearin, butter, coconut oil, and cocoa butter. The mass ratio of the unsaturated fatty acid oils and fats to the saturated fatty acid oils and fats in the blended oil is preferably (10-70):(90-30). In the present invention, when the oil and fat composition contains a blended oil, the mass ratio of unsaturated fatty acid oils and saturated fatty acid oils in the blended oil is preferably (20-50):(80-50), more preferably (20-40):(80-60), and even more preferably (20-30):(80-70). When the oil and fat composition contains a blended oil treated by interesterification, the mass ratio of unsaturated fatty acid oils and saturated fatty acid oils in the blended oil is (10-70):(80-30). The catalyst used in the interesterification treatment is not particularly limited as long as it is a catalyst well known to those skilled in the art, but in the present invention, lipase and / or sodium methoxide are preferred. The mass ratio of the catalyst to the mass of the blended oil is preferably 1% to 3%, more preferably 1%. The interesterification treatment is preferably carried out at a temperature of 35°C to 130°C. The interesterification treatment is preferably carried out for 0.5 to 4 hours. The middle fraction oil is preferably a middle fraction oil of palm oil, more preferably palm oil with a temperature of 14 to 44°C. In an embodiment according to the present invention, the middle fraction oil is specifically 44°C palm oil, 33°C palm oil, 24°C palm oil, or 14°C palm oil. The hydrogenated oil is preferably hydrogenated vegetable oil, more preferably one or more selected from the group consisting of hydrogenated soybean oil, hydrogenated peanut oil, hydrogenated linseed oil, and hydrogenated rapeseed oil. The hydrogenated oil is obtained by hydrogenating fats and oils. The hydrogenation reaction is preferably carried out at a pressure of 0.02 to 0.8 MPa, more preferably 0.02 to 0.5 MPa.In an embodiment according to the present invention, the hydrogenation reaction is carried out at a pressure of 0.02 MPa, 0.5 MPa, 0.1 MPa, or 0.3 MPa. The hydrogenation reaction is preferably carried out at a temperature of 100°C to 180°C. In an embodiment according to the present invention, the hydrogenation reaction is preferably carried out at a temperature of 100°C, 180°C, 130°C, or 150°C. The hydrogenation reaction is preferably carried out for 2 to 4 hours.

[0062] More specifically, shortening was used as fat in the examples according to the invention, and even more specifically, said shortening was derived from palm oil or cocoa butter.

[0063] The present invention further provides the use of the oil or fat described above for embedding a physiologically active substance.

[0064] The present invention further provides an oil and fat composition having heat resistance and acid resistance, wherein a differential scanning calorimetry curve of the oil and fat composition has an endothermic peak between 35°C and 47°C and an exothermic peak between 220°C and 250°C.

[0065] The slope of the solid fat content curve of the oil or fat composition at 20°C to 50°C is -3.0 to -1.0, and preferably -2.82 to -1.2.

[0066] In an embodiment according to the present invention, the slope of the solid fat content curve of the oil or fat composition at 20°C to 50°C is specifically -2.86, -1.22, -2.45, -1.76, -2.61, -1.6, -2.22, -1.87, -2.82, -1.18, -2.66, or -1.73.

[0067] According to the present invention, the viscosity of the oil or fat composition at 95° C. is preferably 20 to 90 mPa·s, more preferably 25 to 86 mPa·s.

[0068] The oil and fat composition according to the present invention having the above-mentioned specific parameters preferably contains one or more selected from the group consisting of blended oils, blended oils treated by interesterification, middle fraction oils, and hydrogenated oils.

[0069] Here, the blended oil contains unsaturated fatty acid oils and fats with an unsaturated fatty acid content of more than 50% and saturated fatty acid oils and fats with a saturated fatty acid content of more than 50%. In the present invention, the unsaturated fatty acid oils and fats are preferably one or more selected from the group consisting of palm kernel oil, rapeseed oil, rice bran oil, soybean oil, sunflower seed oil, rapeseed oil, and corn oil. The saturated fatty acid oils and fats are preferably one or more selected from the group consisting of coconut oil, palm stearin, butter, coconut oil, and cocoa butter. The mass ratio of the unsaturated fatty acid oils and fats to the saturated fatty acid oils and fats in the blended oil is preferably (10-70):(90-30). In the present invention, when the oil and fat composition contains a blended oil, the mass ratio of unsaturated fatty acid oils and saturated fatty acid oils in the blended oil is preferably (20-50):(80-50), more preferably (20-40):(80-60), and even more preferably (20-30):(80-70). In an embodiment according to the present invention, the mass ratio of unsaturated fatty acid oils and saturated fatty acid oils in the blended oil is specifically 30:70, 60:40, 75:25, or 50:50. When the oil and fat composition contains a blended oil treated by interesterification, the mass ratio of unsaturated fatty acid oils and saturated fatty acid oils in the blended oil is (10-70):(80-30). The catalyst used in the interesterification treatment is not particularly limited as long as it is a catalyst well known to those skilled in the art, but in the present invention, lipase and / or sodium methoxide are preferred. The mass ratio of the catalyst relative to the mass of the blended oil is preferably 1% to 3%, more preferably 1%. The interesterification treatment is preferably carried out at a temperature of 35°C to 130°C. The interesterification treatment is preferably carried out for 0.5 to 4 hours. The middle fraction oil is preferably a middle fraction oil of palm oil, more preferably palm oil of 14 to 44°C. In an embodiment according to the present invention, the middle fraction oil is specifically 44°C palm oil, 33°C palm oil, 24°C palm oil, or 14°C palm oil. The hydrogenated oil is preferably hydrogenated vegetable oil, more preferably one or more selected from the group consisting of hydrogenated soybean oil, hydrogenated peanut oil, hydrogenated linseed oil, and hydrogenated rapeseed oil. The hydrogenated oil is obtained by hydrogenating fats and oils.The hydrogenation reaction is preferably carried out at a pressure of 0.02 to 0.8 MPa, more preferably 0.02 to 0.5 MPa. In an embodiment according to the present invention, the hydrogenation reaction is specifically carried out at a pressure of 0.02 MPa, 0.5 MPa, 0.1 MPa, or 0.3 MPa. The hydrogenation reaction is preferably carried out at a temperature of 100°C to 180°C. In an embodiment according to the present invention, the hydrogenation reaction is specifically carried out at a temperature of 100°C, 180°C, 130°C, or 150°C. The hydrogenation reaction is preferably carried out for 2 to 4 hours.

[0070] The present invention further provides use of the oil or fat composition described above for embedding a physiologically active substance.

[0071] The present invention further provides a food product comprising the above-described oil and fat composition.

[0072] According to the present invention, there is further provided a microcapsule comprising a core material containing the above-mentioned oil or fat composition and a wall material enclosing the core material.

[0073] According to the present invention, the mass of the oil or fat composition is 5% to 17% of the mass of the microcapsules. The core material preferably further contains a physiologically active substance. The physiologically active substance is not particularly limited as long as it is a physiologically active substance well known to those skilled in the art. In the present invention, however, it is preferably a heat-labile physiologically active substance, and more preferably at least one selected from the group consisting of probiotics, vitamins, DHA, lactoferrin, and anthocyanins.

[0074] According to the present invention, it is preferable that a protein coating layer is further provided between the core material and the wall material. The type of protein in the protein coating layer is not particularly limited as long as it is a protein well known to those skilled in the art, but in the present invention, it is preferably a natural protein with strong heat resistance and gelling properties, more preferably one or more proteins selected from the group consisting of casein, pea protein, and whey protein. The mass of the protein coating layer is preferably 6% to 30% of the mass of the microcapsules.

[0075] According to the present invention, the wall material is preferably formed by heat-curing a colloid, and more preferably by calcifying and crosslinking the colloid and heat-curing it. The differential scanning calorimetry curve of the wall material has one endothermic peak between 190°C and 210°C and one exothermic peak between 270°C and 280°C. The measurement range of the DSC is preferably 25°C to 300°C. The heating rate of the DSC is preferably 0.5 to 1°C / min. In the present invention, it is more preferable to hold the colloid at a fixed temperature of 25°C for 5 to 10 minutes and then raise the temperature. In the present invention, it is preferable that the obtained DSC curve has one broad endothermic peak between 190°C and 210°C. The width of the endothermic peak is preferably 57°C to 70°C, more preferably 60 to 70°C. The turbidity of the wall material at 25°C to 95°C is preferably 1.3 to 1.5 cm -1 and more preferably 1.32 to 1.5 cm -1 and more preferably 1.4 to 1.5 cm -1 and more preferably 1.4 to 1.48 cm -1 and most preferably 1.4 to 1.45 cm -1The colloid according to the present invention preferably contains alginic acid and / or a salt thereof and a gelling agent. The mass ratio of the gelling agent to alginic acid and / or a salt thereof is preferably (1-20):1, more preferably (5-20):1, even more preferably (8-15):1, and most preferably (10-12):1. The gelling agent is preferably one or more selected from the group consisting of thermoreversible gel, curdlan, konjac gum, and gellan gum. The thermoreversible gel is preferably pectin. Based on the mass ratio of the dry substance, the mass ratio of the core material to the colloid is preferably 5.56:1 to 1.59:1. In terms of hydrate mass, the mass ratio of the total mass of the core material and the protein coating layer to the mass of the colloid is preferably 1:2 to 1:7. In an embodiment according to the present invention, the mass ratio of the total mass of the core material and the protein coating layer to the mass of the colloid is specifically 1:2, 1:7, 1:3, or 1:5.

[0076] The water concentration in the microcapsules according to the present invention is preferably 75% to 90%, more preferably 76.33% to 87.68%. For convenience of storage, it is preferable to dry the microcapsules until the water concentration becomes 1% or less.

[0077] According to the present invention, there is further provided a method for producing the above-mentioned microcapsules, which includes step S1) of dispersing a physiologically active substance in the above-mentioned oil or fat composition to obtain a core material, step S2) of mixing and stirring the core material and a wall material solution to obtain a mixed solution, and step S3) of heat-curing the mixed solution to obtain microcapsules.

[0078] Here, the supply sources of all raw materials in the present invention are not particularly limited as long as they are commercially available products.

[0079] The core material is obtained by dispersing a physiologically active substance in an oil or fat composition, and the dispersion is preferably carried out for 2 to 4 minutes.

[0080] In the present invention, a core emulsion is preferably obtained by mixing and emulsifying a core material and a protein emulsion. The protein emulsion is an aqueous protein solution. The protein emulsion is preferably a protein emulsion sterilized with ultraviolet light. The mass concentration of the protein emulsion is preferably 1% to 5%, more preferably 2% to 4%, and even more preferably 3%. The ultraviolet sterilization is preferably carried out for 10 to 20 minutes, more preferably 15 minutes. The protein emulsion is preferably prepared by mixing protein with water, adjusting the pH to neutral, and stirring. The type of protein in the protein emulsion is the same as above, and therefore will not be further described here. The stirring is preferably carried out at a speed of 500 to 1000 rpm, more preferably 600 to 800 rpm. The stirring is preferably carried out for 1 to 5 hours, more preferably 2 to 3 hours. The mass ratio of the core material to the protein emulsion is preferably 1:(1-10), more preferably 1:(1-8), even more preferably 1:(1-5), still more preferably 1:(1-4), and most preferably 1:(2-3). The mixing and emulsification is preferably carried out at a speed of 10,000-20,000 rpm, more preferably 11,000-15,000 rpm, even more preferably 11,000-13,000 rpm, and most preferably 12,000 rpm. The mixing and emulsification is preferably carried out for 3-5 minutes.

[0081] Next, the core material emulsion and wall material solution are mixed and stirred to obtain a mixed solution. The wall material solution is preferably prepared by mixing colloid and water. The type of colloid is the same as above, and will not be further described here. The water is preferably deionized water. The mixing is preferably performed at a temperature of 30°C to 50°C. The mixing is preferably performed at a speed of 200 to 1000 rpm. The mixing is preferably performed for 20 to 60 minutes, more preferably 30 to 40 minutes. The mass concentration of the colloid in the wall material solution is preferably 0.1% to 1%. In an embodiment of the present invention, the mass concentration of the colloid in the wall material solution is specifically 1%, 0.1%, 0.3%, or 0.5%. The mass ratio of the core material emulsion to the wall material solution is preferably 1:(2 to 7). In an embodiment of the present invention, the mass ratio of the core material emulsion to the wall material solution is specifically 1:2, 1:6, 1:7, 1:3, or 1:5. The mixing and stirring is preferably carried out at a temperature of 30°C to 50°C. In an embodiment according to the present invention, the mixing and stirring is preferably carried out at a temperature of 30°C, 50°C, 40°C, or 45°C. The mixing and stirring is preferably carried out at a speed of 500 to 2000 rpm, more preferably 800 to 2000 rpm, and even more preferably 800 to 1500 rpm. The mixing and stirring is preferably carried out for 20 to 30 seconds.

[0082] The mixed solution is heat-cured (preferably by calcification crosslinking and heat-curing) to obtain microcapsules. The solution for calcification crosslinking is preferably a 1 to 20 wt% calcium salt solution. The calcium salt solution is preferably a calcium chloride solution and / or a calcium lactate solution. When the calcium salt solution is a calcium chloride solution, its concentration is preferably 1 to 10 wt%. When the calcium salt solution is a calcium lactate solution, its concentration is preferably 1 to 20 wt%, more preferably 3 to 15 wt%, even more preferably 5 to 15 wt%, and most preferably 5 to 10 wt%. The calcification crosslinking is preferably carried out for 10 to 20 minutes. The heat-curing is preferably carried out at a temperature of 75°C to 95°C. In an embodiment according to the present invention, the heat-curing is specifically carried out at a temperature of 95°C, 75°C, 80°C, or 85°C. The heat-curing is preferably carried out for 30 to 120 seconds, more preferably 1 minute. During this step, the colloidal material forms microcapsules under the action of calcium bridges to achieve the effect of encapsulation and molding, which first have a certain shear resistance, high temperature resistance, and digestion resistance, and then further heat hardens the microcapsules to form irreversible microcapsules with stability and high temperature shear resistance.

[0083] Finally, the microcapsules obtained are preferably stored at 4°C.

[0084] In the microcapsules of the present invention, physiologically active substances are dispersed in an oil and fat composition and encapsulated with proteins, providing an internal environment that blocks moisture and oxygen, and the endothermic phase change at the melting point is also utilized to improve the survival rate of bacterial species during the heat treatment process. Furthermore, the amphiphilic nature of proteins allows them to act as natural emulsifiers, forming a dense network structure that stabilizes the oil-water interface, while also contributing to gelation. During microcapsule formation, the proteins crosslink with the outer polysaccharide (colloidal) substance, making the microcapsules stronger and more stable overall, improving the environmental stability of the physiologically active substances.

[0085] According to the present invention there is further provided the use of the microcapsules described above as a food additive applicable in food processing.

[0086] The present invention further provides a food product comprising the microcapsules described above.

[0087] According to the present invention, there is further provided a microcapsule comprising a core material containing an oil or fat, a protein coating layer encapsulating the core material, and a wall material encapsulating the protein coating layer and formed by heat-curing a colloid.

[0088] In the present invention, the core material contains a physiologically active substance and an oil or fat. The physiologically active substance is preferably at least one selected from the group consisting of probiotics, vitamins, polyunsaturated fatty acids, active proteins, and natural pigments. The oil or fat is the heat-resistant and acid-resistant oil or fat described above, but will not be further described here. The mass of the oil or fat is preferably 5% to 17% of the mass of the microcapsules.

[0089] The core material is enveloped in a protein coating layer. The protein coating layer is formed from a protein. The type of protein in the protein coating layer is not particularly limited as long as it is a protein well known to those skilled in the art. In the present invention, a natural protein having high heat resistance and gelling properties is preferred, and one or more proteins selected from the group consisting of casein, pea protein, and whey protein are more preferred. The mass of the protein coating layer is preferably 1% to 40%, more preferably 6% to 30%, even more preferably 6% to 20%, and most preferably 6% to 10% of the mass of the microcapsules.

[0090] The protein coating layer is enveloped in a wall material. The wall material is formed by heat-curing a colloid. The wall material has a differential scanning calorimetry (DSC) curve with an endothermic peak between 85°C and 110°C and an exothermic peak between 270°C and 280°C. In the present invention, the DSC measurement range is preferably 25°C to 300°C. The DSC heating rate is preferably 0.5 to 1°C / min. In the present invention, it is more preferable to hold the wall material at a fixed temperature of 25°C for 5 to 10 minutes and then raise the temperature. The obtained DSC curve has one broad endothermic peak between 85°C and 110°C. The width of the endothermic peak is preferably 57°C to 70°C, more preferably 60 to 70°C. The turbidity of the wall material according to the present invention at 25°C to 95°C is preferably 1.3 to 1.5 cm -1 and more preferably 1.32 to 1.5 cm -1 and more preferably 1.4 to 1.5 cm -1 and more preferably 1.4 to 1.48 cm -1 and most preferably 1.4 to 1.45 cm -1In the present invention, the wall material is preferably formed by heat-curing a colloid, and more preferably by calcifying and crosslinking the colloid and heat-curing it. The colloid preferably contains alginic acid and / or a salt thereof and a gelling agent. The mass ratio of the gelling agent to sodium alginate is more preferably 10 to 12. The alginate is not particularly limited as long as it is an alginate well known to those skilled in the art, but in the present invention, sodium alginate is preferred. The gelling agent is preferably one or more selected from the group consisting of thermoreversible gel, curdlan, konjac gum, and gellan gum. The thermoreversible gel is preferably pectin. The mass ratio of the core material to the colloid, based on the mass ratio of the dry substances, is preferably 5.56:1 to 1.59:1. The mass ratio of the total mass of the core material and the protein coating layer to the mass of the colloid, in terms of the mass of the hydrate, is preferably 1:2 to 1:7. In an embodiment according to the present invention, the mass ratio of the total mass of the core material and the protein coating layer to the mass of the colloid is specifically 1:2, 1:7, 1:3, or 1:5.

[0091] The water concentration in the microcapsules according to the present invention is preferably 75% to 90%, more preferably 76.33% to 87.68%. For convenience of storage, it is preferable to dry the microcapsules until the water concentration becomes 1% or less.

[0092] According to the present invention, there is further provided a method for producing the above-mentioned microcapsules, which includes step S1) of mixing a physiologically active substance with an oil or fat to obtain a core material, step S2) of mixing and emulsifying the core material with a protein emulsion to obtain a core material emulsion, step S3) of mixing and stirring the core material emulsion with a wall material solution containing a colloid to obtain a mixed solution, and step S4) of heat-treating the mixed solution to obtain microcapsules.

[0093] Here, the supply sources of all raw materials in the present invention are not particularly limited as long as they are commercially available products.

[0094] The core material is obtained by mixing the physiologically active substance and the fat or oil, and the mixing is preferably carried out for 2 to 4 minutes.

[0095] The core material and the protein emulsion are mixed and emulsified to obtain a core material emulsion. It is preferable that the protein emulsion is sterilized with ultraviolet light before being mixed and emulsified with the core material. The mass concentration of the protein emulsion is preferably 1% to 5%, more preferably 2% to 4%, and even more preferably 3%. The ultraviolet light sterilization is preferably performed for 10 to 20 minutes, more preferably 15 minutes. The protein emulsion is preferably prepared by mixing protein with water, adjusting the pH to neutral, and stirring. The protein is preferably one or more selected from the group consisting of pea protein, casein, whey protein, and soy protein isolate. The stirring is preferably performed at a speed of 500 to 1000 rpm, more preferably 600 to 800 rpm. The stirring is preferably performed for 1 to 5 hours, more preferably 2 to 3 hours. The mass ratio of the core material to the protein emulsion is preferably 1:(1-10), more preferably 1:(1-8), even more preferably 1:(1-5), still more preferably 1:(1-4), and most preferably 1:(2-3). The mixing and emulsification is preferably carried out at a speed of 10,000-20,000 rpm, more preferably 11,000-15,000 rpm, even more preferably 11,000-13,000 rpm, and most preferably 12,000 rpm. The mixing and emulsification is preferably carried out for 3-5 minutes.

[0096] The core emulsion and the wall material solution are mixed and stirred to obtain a mixed solution. The wall material solution is preferably prepared by mixing a colloid with water. The colloid preferably contains alginic acid and / or a salt thereof and a gelling agent. The mass ratio of the gelling agent to alginic acid and / or a salt thereof is preferably (1-20):1, more preferably (5-20):1, even more preferably (8-15):1, and most preferably (10-12):1. The alginate is not particularly limited as long as it is an alginate well known to those skilled in the art, but in the present invention, sodium alginate is preferred. The gelling agent is preferably one or more selected from the group consisting of thermoreversible gel, curdlan, konjac gum, and gellan gum. The thermoreversible gel is preferably pectin. The water is preferably deionized water. The mixing is preferably performed at a temperature of 30°C to 50°C. The mixing is preferably performed at a speed of 200 to 1000 rpm. The mixing is preferably carried out for 20 to 60 minutes, more preferably 30 to 40 minutes. The mass concentration of the colloid in the wall material solution is preferably 0.1% to 1%. In embodiments according to the present invention, the mass concentration of the colloid in the wall material solution is specifically 1%, 0.1%, 0.3%, or 0.5%.

[0097] The mass ratio of the core material emulsion to the wall material solution is preferably 1:(2 to 7). In an embodiment according to the present invention, the mass ratio of the core material to the wall material solution is specifically 1:2, 1:7, 1:3, or 1:5. The mixing and stirring is preferably carried out at a temperature of 30°C to 50°C. In an embodiment according to the present invention, the mixing and stirring is specifically carried out at a temperature of 30°C, 50°C, 40°C, or 45°C. The mixing and stirring is preferably carried out at a speed of 500 to 2000 rpm, more preferably 800 to 2000 rpm, and even more preferably 800 to 1500 rpm. The mixing and stirring is preferably carried out for 20 to 30 seconds.

[0098] The mixed solution is heat-treated (preferably calcification crosslinking and heat treatment) to obtain microcapsules. The solution for calcification crosslinking is preferably a 1 to 20 wt% calcium salt solution. The calcium salt solution is preferably a calcium chloride solution and / or a calcium lactate solution. When the calcium salt solution is a calcium chloride solution, its concentration is preferably 1 to 10 wt%. When the calcium salt solution is a calcium lactate solution, its concentration is preferably 1 to 20 wt%, more preferably 3 to 15 wt%, even more preferably 5 to 15 wt%, and most preferably 5 to 10 wt%. The calcification crosslinking is preferably carried out for 10 to 20 minutes. The heat curing is preferably carried out at a temperature of 75°C to 95°C. In an embodiment of the present invention, the heat curing is specifically carried out at a temperature of 95°C, 75°C, 80°C, or 85°C. The heat curing is preferably carried out for 30 to 120 seconds.

[0099] Finally, the microcapsules obtained are preferably stored at 4°C.

[0100] According to the present invention there is further provided the use of the microcapsules described above as a food additive applicable in food processing.

[0101] The present invention further provides a food product containing the heat-resistant and shear-resistant microcapsules described above.

[0102] To better illustrate the present invention, the heat-resistant and shear-resistant microcapsules according to the present invention, their manufacturing method and applications will be described in detail below with reference to examples.

[0103] All the reagents used in the following examples are commercially available. The oils and fats were purchased from Cargill, COFCO Corporation, and Yihai Kerry. Casein, pea protein, whey protein, and soy protein isolate were purchased from Shengxi Biotechnology (Shanghai) Co., Ltd. Curdlan, pectin, konjac gum, etc. were purchased from Weifang Tianjiaji Economic and Trade Co., Ltd. Other reagents were purchased from Sinopharm. The types of bacterial powders used in the examples and comparative examples are the self-produced BL-99 strain. This strain was deposited with the China General Microbiological Culture Collection Center (CGMCC) (address: No. 3, Courtyard 1, Beichen West Road, Chaoyang District, Beijing, Institute of Microbiology, Chinese Academy of Sciences) on April 26, 2018, classified and named as Bifidobacterium lactis, with the deposit number CGMCC No. 15650, and is disclosed in the applicant's prior patent CN201811161108.3.

[0104] <DSC test method> Weigh the sample (3.0 ± 0.5) mg, put it into an aluminum case, seal it, hold it at a fixed temperature of 25 °C for 5 minutes, then heat it to 300 °C at a rate of 0.5 °C / min, and set the scanning temperature range to 25 - 300 °C.

[0105] <Viscosity> Please refer to GB / T 10247-2008.

[0106] <Melting curve> Please refer to GB / T 31743-2015.

[0107] <Turbidity test method> Prepare a colloidal solution dispersion, stir it at room temperature, disperse it uniformly, cool it to 25 °C, take 1.5 mL, put it into a preheated cuvette, set the wavelength to 600 nm, use distilled water as the reference solution, measure it at 600 nm with a UV spectrophotometer, and perform 3 parallel measurements for each sample. The turbidity (T) is defined as follows.

[0108] T = -ln (I / I0) / L where I is the transmitted light intensity, I0 is the incident light intensity, and L is the optical path length (cuvette width, i.e., 1 cm in this method).

[0109] [Examples 1 to 4 and Comparative Examples 1 to 2] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein solution, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL99) was dispersed in soybean oil (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture of the bacterial powder and protein solution was emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water to obtain a mixed colloidal solution. The specific preparation parameters are shown in Table 1 below. The core emulsion and the outer layer mixed colloidal solution were prepared at a mass ratio of 1:6 by magnetic stirring at 1,500 rpm at 40°C for 20 seconds to prepare a mixed solution. This mixed solution was then added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes to form microcapsules. The prepared microcapsules were placed in a water bath at 95°C for 1 minute to harden them into irreversible microcapsules, which were then stored at 4°C.

[0110] [Table 1]

[0111] The mixed colloid solutions of Examples 1 to 4 and Comparative Examples 1 and 2 were added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes. After that, the solution was placed in a water bath at 95°C for 1 minute to harden. The performance of the hardened colloid was measured, and the results are shown in Table 2 below.

[0112] [Table 2]

[0113] [Examples 5 to 8 and Comparative Examples 3 to 4] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein solution, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL99) was dispersed in soybean oil (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture of the bacterial powder and protein solution was emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain a core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 800 rpm at 45°C for 30 minutes to obtain a mixed colloidal solution with a colloidal raw material mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred for 20 seconds to obtain a mixed solution. This mixed solution was then added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes to form microcapsules. The specific parameters are shown in Table 3 below. The prepared microcapsules were placed in a water bath at 95°C for 1 minute to harden them, forming irreversible microcapsules, which were then stored at 4°C.

[0114] [Table 3]

[0115] The outer layer colloidal solutions of Examples 5 to 8 and Comparative Examples 3 to 4 were dropped into a 10% calcium chloride (pH 7) solution, reacted for 10 minutes, and then heated and cured in a water bath at 95°C for 1 minute. The performance of the cured colloid was measured. The results were almost identical to those of Example 4.

[0116] [Examples 9 to 12 and Comparative Examples 5 to 6] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein solution, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house strain BL99) was dispersed in soybean oil (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture was then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a mass concentration of 0.5% colloidal raw materials. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a water bath and heated for 1 minute to harden, forming irreversible microcapsules, which were then stored at 4°C. The water bath temperature is shown in Table 4 below.

[0117] The mixed colloid solutions in Examples 9 to 12 and Comparative Examples 5 and 6 were dropped into a 10% calcium chloride (pH 7) solution, reacted for 10 minutes, and then heated and cured in a water bath for 1 minute. The performance of the cured colloid was measured. The water bath temperature is shown in Table 4 below, and the results are shown in Table 5 below.

[0118] [Table 4] [Table 5]

[0119] Comparative Example 7 Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein solution, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house strain BL99) was dispersed in soybean oil (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture was then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and gellan gum (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a mass concentration of 0.5% colloidal raw materials. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath for 1 minute to harden, forming irreversible microcapsules, which were then stored at 4°C.

[0120] The mixed colloid solution in Comparative Example 7 was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath and heated and cured for 1 minute, and the properties of the cured colloid were detected. The DSC absorption peak of this colloid was at 182.65°C, the width of the absorption peak was 54.72, the exothermic peak was at 250.30°C, and the turbidity from 25°C to 95°C was 1.36 cm. -1 It was.

[0121] [Example 13] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein solution, which was then sterilized with UV light for 15 minutes. Bacteria powder (in-house strain BL99) was dispersed in cocoa butter (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture was then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and konjac gum (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a mass concentration of 0.5% colloidal raw materials. The inner core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds at a mass ratio of 1:6 to obtain the mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to harden, forming irreversible microcapsules, which were then stored at 4°C.

[0122] The mixed colloid solution obtained in Example 13 was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heated to harden for 1 minute. After hardening, the performance of the colloid was measured. The DSC absorption peak of this colloid was at 198.62°C, the width of the absorption peak was 62.82°C, the exothermic peak was at 280.71°C, and the turbidity from 25°C to 95°C was 1.47cm. -1 It was.

[0123] [Example 14] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein solution, which was then sterilized with UV light for 15 minutes. Bacteria powder (in-house strain BL99) was dispersed in cocoa butter (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture was then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and konjac gum (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a mass concentration of 0.5% colloidal raw materials. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to harden, forming irreversible microcapsules, which were then stored at 4°C.

[0124] The mixed colloid solution obtained in Example 14 was added dropwise to a 10% calcium chloride (pH 7) solution, reacted for 10 minutes, then placed in a 95°C water bath for 1 minute to heat and harden. After hardening, the performance of the hardened colloid was measured. The DSC absorption peak of this colloid was at 192.65°C, the width of the absorption peak was 57.13, the exothermic peak was at 256.72°C, and the turbidity from 25°C to 95°C was 1.32cm. -1 It was.

[0125] [Example 15] Casein was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein solution, which was then sterilized with UV light for 15 minutes. Bacteria powder (in-house strain BL99) was dispersed in cocoa butter (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture was then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain a core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a colloidal raw material mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds at a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to harden, forming irreversible microcapsules, which were then stored at 4°C.

[0126] The mixed colloid solution obtained in Example 15 was added dropwise to a 10% calcium chloride (pH 7) solution, reacted for 10 minutes, then placed in a 95°C water bath for 1 minute to heat and harden. After hardening, the performance of the hardened colloid was measured. The results were almost identical to those of Example 9.

[0127] [Example 16] Whey protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein solution, which was then sterilized with UV light for 15 minutes. Bacteria powder (in-house strain BL99) was dispersed in cocoa butter (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture was then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a colloidal raw material mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds at a mass ratio of 1:6 to obtain the mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to harden, forming irreversible microcapsules, which were then stored at 4°C.

[0128] The mixed colloid solution obtained in Example 16 was added dropwise to a 10% calcium chloride (pH 7) solution, reacted for 10 minutes, then placed in a 95°C water bath for 1 minute to heat and harden. The performance of the hardened colloid was measured. The results were almost identical to those of Example 9.

[0129] [Example 17] Soy protein isolate was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein solution. This solution was then sterilized with UV light for 15 minutes. Bacteria powder (in-house strain BL99) was dispersed in cocoa butter (1:2 mass ratio) and stirred for 2–4 minutes. The resulting mixture was then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a 0.5% colloidal solution. The core emulsion and the outer layer colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to harden, forming irreversible microcapsules, which were then stored at 4°C.

[0130] The mixed colloid solution obtained in Example 17 was added dropwise to a 10% calcium chloride (pH 7) solution, reacted for 10 minutes, then placed in a 95°C water bath for 1 minute to heat and harden. The performance of the hardened colloid was measured. The results were almost identical to those of Example 9.

[0131] The stability of the irreversible microcapsules obtained in Examples 1 to 17 and Comparative Examples 1 to 7 was measured, and the results are shown in Table 6 below.

[0132] <High temperature shear> 50 ml of sterile deionized water was placed in a beaker and kept warm in a water bath at 85°C. After the deionized water in the beaker was completely heated to 85°C, 2.5 g of sample was placed in the beaker and stirred at 1800 rpm for 10 minutes using a stirrer. The sample was then collected and plated.

[0133] 75°C x 2 min: Samples were placed in sterile deionized water at 75°C for 2 min, then removed and plated.

[0134] 95°C x 1 min: Samples were placed in sterile deionized water at 95°C for 1 min, then removed and plated.

[0135] <Gastrointestinal Digestion> Simulated gastric fluid: Contains 8.5 g / L of NaCl and 3 g / L of pepsin, with a pH of 1.8.

[0136] Simulated intestinal fluid: Contains 8.5 g / L of NaCl, 3 g / L of bile salts, 10 g / L of pancreatin, and 10 g / L of trypsin, with a pH of 6.5.

[0137] 18 ml of simulated gastric fluid and simulated intestinal fluid were placed in 50 mL Erlenmeyer flasks and incubated at 37°C in a shaking incubator for 20 minutes. 2.0 g of sample was then weighed and placed in the simulated gastric fluid and incubated with shaking at 37°C for 2 hours. The sample was filtered and washed twice with sterile deionized water, then placed in the simulated intestinal fluid and incubated with shaking at 37°C for 4 hours. Finally, the sample was washed twice with sterile deionized water and plated.

[0138] [Table 6]

[0139] [Examples 18 to 21 and Comparative Examples 8 to 9] Casein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL-99) was dispersed in an oil / fat composition (1:2 mass ratio) and stirred for 2–4 minutes. The probiotic-dispersed oil and protein emulsion were then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a colloidal raw material mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds at a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heat-cured to form irreversible microcapsules, which were then stored at 4°C. The production process for the oil and fat composition is shown in Table 7 below. The amount of catalyst used was 1% of the mass of the blended oil, and the performance of the oil and fat composition was measured, and the results are shown in Table 8 below.

[0140] [Table 7]

[0141] [Table 8]

[0142] [Examples 22 to 25 and Comparative Examples 10 to 11] Casein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL-99) was dispersed in an oil / fat composition (1:2 mass ratio) and stirred for 2–4 minutes. The probiotic-dispersed oil and protein emulsion were then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a colloidal raw material mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds at a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a water bath at 95°C to heat-set them into irreversible microcapsules, which were then stored at 4°C. The composition of the oil and fat composition is shown in Table 9 below. The performance of the oil and fat composition was measured, and the results are shown in Table 10 below.

[0143] [Table 9]

[0144] [Table 10]

[0145] [Examples 26 to 29 and Comparative Examples 12 to 13] Casein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL-99) was dispersed in fractionated oil (1:2 mass ratio) and stirred for 2–4 minutes. The probiotic-dispersed oil and protein emulsion were then emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloidal solution with a colloidal raw material mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1500 rpm at 40°C for 20–30 seconds at a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heated to harden, forming irreversible microcapsules, which were then stored at 4°C. The oil and fat composition was a fractionated oil, the type of which is shown in Table 11 below. The performance of the oil and fat composition was also measured, and the results are shown in Table 12 below.

[0146] [Table 11]

[0147] [Table 12]

[0148] [Examples 30 to 33 and Comparative Examples 14 to 15] Casein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL-99) was dispersed in hydrogenated vegetable oil (1:2 mass ratio) and stirred for 2-4 minutes. After stirring, the probiotic-dispersed oil and protein emulsion were emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain the core emulsion. The hydrogenation process is shown in Table 13 below. Next, curdlan was uniformly mixed with sodium alginate powder and dispersed in deionized water (curdlan:sodium alginate = 10:1). The mixture was stirred at 400 rpm at 40 °C for 30 minutes to obtain a mixed colloid solution with a colloidal raw material mass concentration of 0.5%. Next, the core emulsion and the outer layer mixed colloid solution were magnetically stirred at 40°C and 1500 rpm for 20 seconds at a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a 95°C water bath to heat-cure them, forming irreversible microcapsules, which were then stored at 4°C. (The mixed colloid solution was added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath to heat-cure them for 1 minute, and the properties of the cured colloid were analyzed. The DSC curve of the wall material formed by curing the colloid in this example had one endothermic peak at 198.92°C and one exothermic peak at 277.15°C, and the turbidity of the colloid at 25°C to 95°C was 1.42 cm. -1 The performance of the hydrogenated vegetable oil was measured and the results are shown in Table 14 below.

[0149] [Table 13]

[0150] [Table 14]

[0151] The stability of the microcapsules obtained in Examples 18 to 33 and Comparative Examples 14 to 15 was measured, and the results are shown in Table 15 below.

[0152] <High temperature shear> 50 ml of sterile deionized water was placed in a beaker and kept warm in a water bath at 85°C. After the deionized water in the beaker was completely heated to 85°C, 2.5 g of sample was placed in the beaker and stirred at 1800 rpm for 10 minutes using a stirrer. The sample was then collected and plated.

[0153] 75°C x 2 min: Samples were placed in sterile deionized water at 75°C for 2 min, then removed and plated.

[0154] 95°C x 1 min: Samples were placed in sterile deionized water at 95°C for 1 min, then removed and plated.

[0155] <Gastrointestinal Digestion> Simulated gastric fluid: Contains 8.5 g / L of NaCl and 3 g / L of pepsin, with a pH of 1.8.

[0156] Simulated intestinal fluid: Contains 8.5 g / L of NaCl, 3 g / L of bile salts, 10 g / L of pancreatin, and 10 g / L of trypsin, with a pH of 6.5.

[0157] 18 ml of simulated gastric fluid and simulated intestinal fluid were placed in 50 mL Erlenmeyer flasks and incubated at 37°C in a shaking incubator for 20 minutes. 2.0 g of sample was then weighed and placed in the simulated gastric fluid and incubated with shaking at 37°C for 2 hours. The sample was filtered and washed twice with sterile deionized water, then placed in the simulated intestinal fluid and incubated with shaking at 37°C for 4 hours. Finally, the sample was washed twice with sterile deionized water and plated.

[0158] <Storage stability at room temperature> The microcapsule samples were stored at room temperature for 28 days before plating.

[0159] [Table 15]

[0160] [Example 34] Soy protein isolate was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Vitamin C was dispersed in the oil and fat composition (1:2 by mass) from Example A3 above, stirred for 2-4 minutes, and then the vitamin C-dispersed oil and protein emulsion were emulsified at a mass ratio of 1:2 at 12,000 rpm for 4 minutes to obtain a core emulsion. Next, curdlan was uniformly mixed with sodium alginate powder, dispersed in deionized water (curdlan:sodium alginate = 10:1), and stirred at 400 rpm for 30 minutes at 40°C to obtain a mixed colloidal solution with a latex concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a water bath at 95°C to harden them, forming irreversible microcapsules, which were then stored at 4°C.

[0161] The mixed colloid solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath for 1 minute to heat and harden, and the performance of the hardened colloid was measured. The results were almost identical to those of Examples 30 to 33.

[0162] [Example 35] Soy protein isolate was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Lactoferrin was dispersed in the oil and fat composition (1:2 by mass) from Example A7 above, stirred for 2-4 minutes, and then the lactoferrin-dispersed oil and protein emulsion were emulsified at a mass ratio of 1:2 for 4 minutes at 12,000 rpm to obtain a core emulsion. Next, curdlan was uniformly mixed with sodium alginate powder, dispersed in deionized water (curdlan:sodium alginate = 10:1), and stirred at 400 rpm for 30 minutes at 40°C to obtain a mixed colloid solution with a colloid mass concentration of 0.5%. Next, the core emulsion and the outer layer mixed colloid solution were magnetically stirred at a mass ratio of 1:6 at 40°C for 20-30 seconds at 1,500 rpm to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a water bath at 95°C to harden them, forming irreversible microcapsules, which were then stored at 4°C.

[0163] The mixed colloid solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath for 1 minute to heat and harden, and the performance of the hardened colloid was measured. The results were almost identical to those of Examples 30 to 33.

[0164] [Example 36] Soy protein isolate was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with ultraviolet light for 15 minutes. Anthocyanin was dispersed in the oil and fat composition of Example A10 (1:2 by mass) and stirred for 2-4 minutes. After stirring, the anthocyanin-dispersed oil and protein emulsion were emulsified at a mass ratio of 1:2 at 12,000 rpm for 4 minutes to obtain a core emulsion. Next, curdlan was uniformly mixed with sodium alginate powder and dispersed in deionized water (curdlan:sodium alginate = 10:1), and stirred at 400 rpm for 30 minutes at 40°C to obtain a mixed colloid solution with a colloid mass concentration of 0.5%. The core emulsion and the outer layer mixed colloid solution were then magnetically stirred at a mass ratio of 1:6 at 40°C for 20-30 seconds at 1,500 rpm to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a water bath at 95°C to harden them, forming irreversible microcapsules, which were then stored at 4°C.

[0165] The mixed colloid solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath for 1 minute to heat and harden, and the performance of the hardened colloid was measured. The results were almost identical to those of Examples 30 to 33.

[0166] The performance of the microcapsules obtained in Examples 34 to 36 was measured, and the results are shown in Table 16 below.

[0167] [Table 16]

[0168] [Example 37] Casein was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL-99) was dispersed in the oil and fat composition (1:2 mass ratio) described in Example A3 above, stirred for 2-4 minutes, and then the probiotic-dispersed oil and protein emulsion were emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain a core emulsion. Next, curdlan was uniformly mixed with sodium alginate powder, dispersed in deionized water (curdlan:sodium alginate = 10:1), and stirred at 400 rpm for 30 minutes at 40°C to obtain a mixed colloidal solution with a colloid mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds at a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a water bath at 95°C to harden them, forming irreversible microcapsules, which were then stored at 4°C.

[0169] The mixed colloid solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath for 1 minute to heat and harden, and the performance of the hardened colloid was measured. The results were almost identical to those of Examples 30 to 33.

[0170] [Example 38] Casein was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house strain BL-99) was dispersed in the oil and fat composition of Example A6 (1:2 mass ratio) and stirred for 2-4 minutes. The resulting probiotic-dispersed oil and protein emulsion was emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain a probiotic / oil-protein emulsion. Next, curdlan was uniformly mixed with sodium alginate powder and dispersed in deionized water (curdlan:sodium alginate = 10:1). The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain a mixed colloid solution with a colloid mass concentration of 0.5%. Next, the core emulsion and outer layer mixed colloidal solution were magnetically stirred at 1500 rpm at 40°C for 20-30 seconds in a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heated to harden, becoming irreversible microcapsules, which were then stored at 4°C.

[0171] The mixed colloid solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath for 1 minute to heat and harden, and the performance of the hardened colloid was measured. The results were almost identical to those of Examples 30 to 33.

[0172] [Example 39] Casein was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL-99) was dispersed in the oil and fat composition of Example 10 (1:2 mass ratio) and stirred for 2-4 minutes. After stirring, the probiotic-dispersed oil and protein emulsion were emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain a core emulsion. Next, curdlan was uniformly mixed with sodium alginate powder, dispersed in deionized water (curdlan:sodium alginate = 10:1), and stirred at 400 rpm for 30 minutes at 40°C to obtain a mixed colloidal solution with a colloid mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds at a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a water bath at 95°C to harden them, forming irreversible microcapsules, which were then stored at 4°C.

[0173] The mixed colloid solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath for 1 minute to heat and harden, and the performance of the hardened colloid was measured. The results were almost identical to those of Examples 30 to 33.

[0174] [Example 40] Casein was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacterial powder (in-house produced strain BL-99) was dispersed in the oil and fat composition of Example 10 (1:2 mass ratio) and stirred for 2-4 minutes. After stirring, the probiotic-dispersed oil and protein emulsion were emulsified at 12,000 rpm for 4 minutes at a mass ratio of 1:2 to obtain a core emulsion. Next, curdlan was uniformly mixed with sodium alginate powder, dispersed in deionized water (curdlan:sodium alginate = 10:1), and stirred at 400 rpm for 30 minutes at 40°C to obtain a mixed colloidal solution with a colloid mass concentration of 0.5%. The core emulsion and the outer layer mixed colloidal solution were then magnetically stirred at 1,500 rpm at 40°C for 20 seconds at a mass ratio of 1:6 to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution to form microcapsules. The prepared microcapsules were placed in a water bath at 95°C to harden them, forming irreversible microcapsules, which were then stored at 4°C.

[0175] The mixed colloid solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath for 1 minute to heat and harden, and the performance of the hardened colloid was measured. The results were almost identical to those of Examples 30 to 33.

[0176] The performance of the microcapsules obtained in Examples 37 to 40 was measured, and the results are shown in Table 17 below.

[0177] [Table 17]

[0178] [Examples 41 to 44 and Comparative Examples 16 to 17] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. The bacterial powder was dispersed in shortening (derived from palm oil, DSC endothermic peak approximately 48°C, DSC exothermic peak approximately 241°C, melting curve slope -1.85, viscosity 25.2 mPa·s) at a mass ratio of 1:2. After stirring for 2–4 minutes, the bacterial powder-dispersed oil and protein emulsion was emulsified at 12,000 rpm at a mass ratio of 1:2 for 4 minutes to obtain the core emulsion. Next, sodium alginate powder and curdlan (1:10, w / w) were uniformly mixed and dispersed in deionized water to obtain the outer layer colloidal solution. The specific preparation parameters are shown in Table 18 below. Next, the core emulsion and outer layer colloidal solution were mixed in a mass ratio of 1:6 under magnetic stirring at 40°C and 1500 rpm for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath to harden them, becoming irreversible microcapsules, which were then stored at 4°C.

[0179] [Table 18]

[0180] The outer layer colloidal solutions in Examples 41 to 44 and Comparative Examples 16 to 17 were dropped into a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes. After that, the solution was placed in a 95°C water bath and heated to harden for 1 minute. The performance of the hardened colloid was measured, and the results are shown in Table 19 below.

[0181] [Table 19]

[0182] [Examples 45 to 48 and Comparative Examples 18 to 19] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. The bacterial powder was dispersed in shortening (derived from palm oil, DSC endothermic peak approximately 48°C, DSC exothermic peak approximately 241°C, melting curve slope -1.85, viscosity 25.2 mPa·s) at a mass ratio of 1:2. After stirring for 2–4 minutes, the resulting oil-protein emulsion was emulsified at 12,000 rpm at a mass ratio of 1:2 for 4 minutes to obtain the core emulsion. Next, sodium alginate powder and curdlan (1:10, w / w) were uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain an outer colloidal solution with a colloid mass concentration of 0.5%. Next, the core emulsion and outer layer colloidal solution were mixed in a mass ratio of 1:6 under magnetic stirring at 40°C and 1500 rpm for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The specific parameters are shown in Table 20 below. The prepared microcapsules were placed in a 95°C water bath to harden them, forming irreversible microcapsules, which were then stored at 4°C.

[0183] [Table 20]

[0184] The outer layer colloidal solutions in Examples 45 to 48 and Comparative Examples 18 to 19 were dropped into a 10% calcium chloride (pH 7) solution, allowed to react for 10 minutes, and then placed in a 95°C water bath to heat and harden for 1 minute. The performance of the hardened colloid was measured, and the results were almost identical to those of Example 44.

[0185] [Examples 49 to 52 and Comparative Examples 20 to 21] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. The bacterial powder was dispersed in shortening (derived from palm oil, DSC endothermic peak approximately 48°C, DSC exothermic peak approximately 241°C, melting curve slope -1.85, viscosity 25.2 mPa·s) at a mass ratio of 1:2. After stirring for 2–4 minutes, the resulting oil-protein emulsion was emulsified at 12,000 rpm at a mass ratio of 1:2 for 4 minutes to obtain the core emulsion. Next, sodium alginate powder and curdlan (1:10, w / w) were uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain an outer colloidal solution with a colloid mass concentration of 0.5%. Next, the inner core emulsion and outer layer colloidal solution (1:6) were magnetically stirred at 1500 rpm at 40°C for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a water bath and heated for 1 minute to harden, becoming irreversible microcapsules, which were then stored at 4°C. The water bath temperatures are shown in Table 21 below.

[0186] The outer layer colloidal solutions in Examples 49 to 52 and Comparative Examples 20 to 21 were added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes. After that, the solution was placed in a water bath at 70°C to 95°C and heated to harden for 1 minute. The performance of the hardened colloid was measured, and the results are shown in Table 21 below.

[0187] [Table 21]

[0188] [Comparative Example 22] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. The bacterial powder was dispersed in shortening (derived from palm oil, DSC endothermic peak approximately 48°C, DSC exothermic peak approximately 241°C, melting curve slope -1.85, viscosity 25.2 mPa·s) at a mass ratio of 1:2. After stirring for 2–4 minutes, the resulting oil-protein emulsion was emulsified at 12,000 rpm at a mass ratio of 1:2 for 4 minutes to obtain the core emulsion. Next, sodium alginate powder and gellan gum (1:10, w / w) were uniformly mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain an outer colloidal solution with a colloid mass concentration of 0.5%. Next, the core emulsion and outer layer colloidal solution were mixed in a mass ratio of 1:6 under magnetic stirring at 40°C and 1500 rpm for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath and heated for 1 minute to harden, becoming irreversible microcapsules, which were then stored at 4°C.

[0189] The mixed colloid solution of Comparative Example 22 was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 70°C water bath and heated for 1 minute to harden, and the performance of the hardened colloid was then measured. The DSC absorption peak of this colloid was found to be at 182.65°C, the width of the absorption peak was 54.72, the exothermic peak was at 250.30°C, and the turbidity at 25°C to 95°C was 1.36 cm. -1 It was.

[0190] [Example 53] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. The bacterial powder was dispersed in shortening (derived from palm oil, DSC endothermic peak approximately 48°C, DSC exothermic peak approximately 241°C, melting curve slope -1.85, viscosity 25.2 mPa·s) at a mass ratio of 1:2. After stirring for 2–4 minutes, the resulting oil-protein emulsion was emulsified at 12,000 rpm at a mass ratio of 1:2 for 4 minutes to obtain the core emulsion. Next, sodium alginate powder and konjac gum (1:10, w / w) were homogeneously mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain an outer colloidal solution with a colloid mass concentration of 0.5%. Next, the core emulsion and outer layer colloidal solution were mixed in a mass ratio of 1:6 under magnetic stirring at 40°C and 1500 rpm for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heated for 1 minute to harden, becoming irreversible microcapsules, which were then stored at 4°C.

[0191] The outer layer colloid solution from Example 53 was added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to heat and harden, and the performance of the hardened colloid was then measured. The DSC absorption peak of this colloid was found to be at 198.62°C, with a width of 62.82, an exothermic peak at 280.71°C, and a turbidity of 1.47cm between 25°C and 95°C. -1 It was.

[0192] [Example 54] Pea protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion, which was then sterilized with UV light for 15 minutes. Bacteria powder was dispersed in shortening (cocoa butter-derived shortening, DSC endothermic peak approximately 30°C, DSC exothermic peak approximately 200°C, melting curve slope -2.45, viscosity 28.0 mPa·s) at a mass ratio of 1:2. After stirring for 2–4 minutes, the resulting oil-protein emulsion containing the bacteria powder was emulsified at 12,000 rpm at a mass ratio of 1:2 for 4 minutes to obtain the core emulsion. Next, sodium alginate powder and konjac gum (1:10, w / w) were homogeneously mixed and dispersed in deionized water. The mixture was stirred at 400 rpm at 40°C for 30 minutes to obtain an outer colloidal solution with a colloid mass concentration of 0.5%. Next, the core emulsion and outer layer colloid solution (1:6) were magnetically stirred at 40°C and 1500 rpm for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heated for 1 minute to harden, becoming irreversible microcapsules, which were then stored at 4°C.

[0193] The outer layer colloid solution in Example 54 was added dropwise to a 10% calcium chloride (pH 7) solution, reacted for 10 minutes, then placed in a 95°C water bath for 1 minute to heat and harden. The hardened colloid's performance was then measured. The DSC absorption peak of this colloid was at 192.65°C, the width of the absorption peak was 57.13, the exothermic peak was at 256.72°C, and the turbidity from 25°C to 95°C was 1.32cm. -1 It was.

[0194] [Example 55] Casein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion. The emulsion was then sterilized with UV light for 15 minutes. The bacterial powder was dispersed in a 1:2 mass ratio oil (derived from cocoa butter, DSC endothermic peak approximately 30°C, DSC exothermic peak approximately 200°C, melting curve slope -2.45, viscosity 28.0 mPa·s). After stirring for 2–4 minutes, the resulting emulsion was emulsified at 12,000 rpm at a 1:2 mass ratio to obtain the core emulsion. Next, sodium alginate powder and curdlan (1:10, w / w) were uniformly mixed and dispersed in deionized water. The mixture was stirred at 800 rpm at 45°C for 30 minutes to obtain a 0.5% colloidal mass outer layer colloid solution. Next, the core emulsion and outer layer colloidal solution were mixed in a mass ratio of 1:6 under magnetic stirring at 40°C and 1500 rpm for 20-30 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heated for 1 minute to harden, becoming irreversible microcapsules, which were then stored at 4°C.

[0195] The outer layer colloidal solution from Example 55 was added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to harden, and the hardened colloid was detected. The results were nearly identical to those of Example 49.

[0196] [Example 56] Whey protein was weighed and dissolved in 100 mL of deionized water. The pH was adjusted to 7 and the mixture was stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion. The emulsion was then sterilized with UV light for 15 minutes. The bacterial powder was dispersed in a 1:2 mass ratio oil (derived from cocoa butter, DSC endothermic peak approximately 30°C, DSC exothermic peak approximately 200°C, melting curve slope -2.45, viscosity 28.0 mPa·s). After stirring for 2–4 minutes, the resulting emulsion was emulsified at 12,000 rpm at a 1:2 mass ratio to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then homogenously mixed and dispersed in deionized water. The mixture was stirred at 800 rpm at 45°C for 30 minutes to obtain an outer colloidal solution with a colloid mass concentration of 0.5%. Next, the core emulsion and outer layer colloidal solution were mixed in a mass ratio of 1:6 under magnetic stirring at 40°C and 1500 rpm for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heated for 1 minute to harden, becoming irreversible microcapsules, which were then stored at 4°C.

[0197] The outer layer colloidal solution from Example 56 was added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to heat-cure, and the hardened colloid was detected. The results were nearly identical to those of Example 49.

[0198] [Example 57] Soy protein isolate was weighed, dissolved in 100 mL of deionized water, adjusted to pH 7, and stirred at 800 rpm for 3 hours to prepare a 3% protein emulsion. This emulsion was then sterilized with UV light for 15 minutes. Bacteria powder was dispersed in a 1:2 mass ratio oil (derived from cocoa butter, DSC endothermic peak approximately 30°C, DSC exothermic peak approximately 200°C, melting curve slope -2.45, viscosity 28.0 mPa·s). After stirring for 2–4 minutes, the resulting microbial powder-dispersed oil and protein emulsion were emulsified at 12,000 rpm for 4 minutes at a 1:2 mass ratio to obtain the core emulsion. Sodium alginate powder and curdlan (1:10, w / w) were then uniformly mixed and dispersed in deionized water. The mixture was stirred at 800 rpm at 45°C for 30 minutes to obtain an outer colloidal solution with a colloid mass concentration of 0.5%. Next, the core emulsion and outer layer colloidal solution were mixed in a mass ratio of 1:6 under magnetic stirring at 40°C and 1500 rpm for 20 seconds to obtain a mixed solution. This mixed solution was added dropwise to a 10% calcium chloride (pH 7) solution and reacted for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath and heated for 1 minute to harden, becoming irreversible microcapsules, which were then stored at 4°C.

[0199] The outer layer colloidal solution from Example 57 was added dropwise to a 10% calcium chloride (pH 7) solution and allowed to react for 10 minutes to form microcapsules. The prepared microcapsules were placed in a 95°C water bath for 1 minute to heat-cure, and the hardened colloid was detected. The results were nearly identical to those of Example 49.

[0200] The stability of the irreversible microcapsules obtained in Examples 41 to 57 and Comparative Examples 16 to 22 was measured, and the results are shown in Table 22 below.

[0201] <Method for measuring high-temperature shear strength> 50 ml of sterile deionized water was placed in a beaker and kept warm in a water bath at 85°C. After the deionized water in the beaker was completely heated to 85°C, 2.5 g of sample was placed in the beaker and stirred at 1800 rpm for 10 minutes using a stirrer. The sample was then collected and plated.

[0202] 75°C x 2 min: Samples were placed in sterile deionized water at 75°C for 2 min, then removed and plated.

[0203] 95°C x 1 min: Samples were placed in sterile deionized water at 95°C for 1 min, then removed and plated.

[0204] <Gastrointestinal Digestion> Simulated gastric fluid: Contains 8.5 g / L of NaCl and 3 g / L of pepsin, with a pH of 1.8.

[0205] Simulated intestinal fluid: Contains 8.5 g / L of NaCl, 3 g / L of bile salts, 10 g / L of pancreatin, and 10 g / L of trypsin, with a pH of 6.5.

[0206] 18 ml of simulated gastric fluid and simulated intestinal fluid were placed in 50 mL Erlenmeyer flasks and incubated at 37°C in a shaking incubator for 20 minutes. 2.0 g of sample was then weighed and placed in the simulated gastric fluid and incubated with shaking at 37°C for 2 hours. The sample was filtered and washed twice with sterile deionized water, then placed in the simulated intestinal fluid and incubated with shaking at 37°C for 4 hours. Finally, the sample was washed twice with sterile deionized water and plated.

[0207] [Table 22]

Claims

1. A microcapsule comprising a core material and a wall material enclosing the core material, wherein the wall material contains a colloid whose differential scanning calorimetry curve has one endothermic peak between 190°C and 210°C and one exothermic peak between 250°C and 281°C.

2. The width of the endothermic peak is 57°C to 70°C, And / or the turbidity of the colloid at 25°C to 95°C is 1.3 to 1.5 cm －１ and and / or the colloid comprises a thermal gel, preferably further comprising alginic acid and / or a salt thereof; 2. The microcapsule according to claim 1, wherein the thermal gel is one or more selected from the group consisting of curdlan, konjac gum, and gellan gum.

3. The colloid is obtained by heat treatment, and / or the heat treatment is carried out at a temperature of 75°C to 95°C; 2. Microcapsules according to claim 1, characterized in that, and / or prior to the heat treatment, a mineralization cross-linking process is further carried out.

4. 2. The microcapsule of claim 1, wherein the mass ratio of the core material to the colloid is from 5.56:1 to 1.59:1, based on the mass ratio of the dry substances.

5. 2. The microcapsule according to claim 1, wherein the colloid has a mass percentage of 0.2% to 7% based on the mass of the microcapsule.

6. The core material comprises an oil or fat composition, The oil and fat composition has a differential scanning calorimetry curve that has an endothermic peak between 35°C and 47°C and an exothermic peak between 220°C and 250°C, and the slope of the solid fat content curve from 20°C to 50°C is -3.0 to -1.

0. The microcapsules according to claim 1,

7. The microcapsules according to claim 6, wherein the oil composition has a viscosity of 20 to 90 mPa·s at 95°C.

8. The oil and fat composition is at least one selected from the group consisting of blended oils, blended oils treated by interesterification, middle fraction oils, and hydrogenated oils, 7. The microcapsules according to claim 6, wherein the blended oil contains unsaturated fatty acid oils and fats having an unsaturated fatty acid content of more than 50% and saturated fatty acid oils and fats having a saturated fatty acid content of more than 50%.

9. 9. The microcapsule according to claim 8, wherein the mass ratio of the unsaturated fatty acid oil to the saturated fatty acid oil in the blended oil is (10-70):(90-30).

10. The microcapsules according to claim 6, characterized in that the mass of the oil or fat composition is 5% to 17% of the mass of the microcapsules.

11. The core material contains oil and fat, The fat or oil has a differential scanning calorimetry curve having an endothermic peak between 30°C and 48°C and an exothermic peak between 200°C and 245°C, and / or the fat or oil has a slope of a solid fat content curve between -2.51 and -1.57 at 10°C and 40°C; and / or the oil or fat has a viscosity at 95°C of 23.900 mPa s to 84.445 mPa s; and / or the oil or fat is a vegetable oil and / or an animal oil; and / or the fat or oil has been treated by at least one of interesterification, fractionation, and hydrogenation; And / or, the oil or fat has a mass percentage of 5% to 17% based on the mass of the microcapsules, The microcapsules according to claim 1, characterized in that

12. 2. The microcapsule according to claim 1, wherein the core material contains at least one physiologically active substance selected from the group consisting of probiotics, vitamins, polyunsaturated fatty acids, active proteins, and natural pigments.

13. 2. The microcapsule according to claim 1, wherein a protein coating layer is provided between the core material and the wall material.

14. the protein in the protein coating layer is at least one selected from the group consisting of casein, pea protein, and whey protein; And / or the protein coating layer has a mass percentage of 1% to 40% of the mass of the microcapsule, based on the mass of the microcapsule.

15. A microcapsule having heat resistance and shear resistance, comprising a core material, a protein coating layer enveloping the core material, and a wall material enveloping the protein coating layer, wherein the core material contains oil or fat, and the wall material is formed by heat-curing a colloid.

16. (1) The fat or oil has a differential scanning calorimetry curve having an endothermic peak between 30°C and 48°C and an exothermic peak between 200°C and 245°C; (2) The fat or oil has a solid fat content curve slope of -2.51 to -1.57 at 10°C to 40°C; (3) The oil or fat has a viscosity at 95°C of 23.900 mPa s to 84.445 mPa s; (4) The oil or fat is a vegetable oil and / or an animal oil; (5) The fat or oil has been treated by at least one of interesterification, fractionation, and hydrogenation; (6) The oil or fat has a mass percentage of 5% to 17% based on the mass of the microcapsules; The microcapsule according to claim 15, characterized in that it has at least one of the above features (1) to (6).

17. the protein in the protein coating layer is at least one selected from the group consisting of casein, pea protein, and whey protein; And / or the protein coating layer has a mass percentage of 1% to 40% of the mass of the microcapsule, based on the mass of the microcapsule.

18. (i) the wall material is formed by calcifying, crosslinking, and heat-curing a colloid; (ii) the wall material has a differential scanning calorimetry curve having one endothermic peak between 190°C and 210°C and one exothermic peak between 250°C and 281°C; (iii) The wall material has a turbidity of 1.3 to 1.5 cm at 25°C to 95°C. －１ is; (iv) the colloid comprises alginic acid and / or a salt thereof and a gelling agent; (v) the colloid has a mass percentage of 0.2% to 7% based on the mass of the microcapsules; The microcapsule according to claim 15, characterized in that it has at least one of the above features (1) to (6).

19. the mass ratio of the gelling agent to alginic acid and / or a salt thereof is (1 to 20):1; 19. The microcapsule according to claim 18, wherein the gelling agent is preferably at least one selected from the group consisting of a thermoreversible gel, curdlan, konjac gum, and gellan gum.

20. The microcapsules according to claim 15, characterized in that the core material of the microcapsules contains at least one physiologically active substance selected from the group consisting of probiotics, vitamins, polyunsaturated fatty acids, active proteins and natural pigments.

21. A step S1) of mixing a physiologically active substance and an oil or fat to obtain a core material; A step S2) of mixing and emulsifying the core material and the protein emulsion to obtain a core material emulsion; a step S3) of mixing and stirring the core material emulsion with a wall material solution containing a colloid to obtain a mixed solution; and step S4) heat-treating the mixed solution to obtain microcapsules.

22. the mass concentration of the protein emulsion is 1% to 5%, and the mass ratio of the core material to the protein emulsion is 1:(1 to 10); and / or the mass concentration of the colloid in the wall material solution is 0.1% to 1%, and the mass ratio of the core material emulsion to the wall material solution is 1:(2 to 7); and / or the heat treatment is carried out at a temperature of 75°C to 95°C; and / or the heat treatment is carried out for 10 to 30 minutes.

23. Use of the heat-resistant and shear-resistant microcapsules according to any one of claims 15 to 20, or the heat-resistant and shear-resistant microcapsules produced by the production method according to any one of claims 21 to 22, as a food additive.

24. A food product comprising a microcapsule having heat resistance and shear resistance according to any one of claims 15 to 20, or a microcapsule having heat resistance and shear resistance produced by the production method according to any one of claims 21 to 23.

25. A colloid having high-temperature shear resistance, characterized in that a differential scanning calorimetry curve has one endothermic peak between 190°C and 210°C and one exothermic peak between 250°C and 281°C.

26. The width of the endothermic peak is 57 to 70°C, And / or the turbidity of the colloid at 25°C to 95°C is 1.3 to 1.5 cm －１ and 26. The colloid according to claim 25, further comprising a thermal gel, preferably further comprising alginic acid and / or a salt thereof, and / or the thermal gel is one or more selected from the group consisting of curdlan, konjac gum and gellan gum.

27. The colloid is obtained by heat treatment, and / or the heat treatment is carried out at a temperature of 75°C to 95°C; 26. The colloid of claim 25, further comprising a mineralization cross-linking step prior to said heat treatment.

28. Use of the colloid according to any one of claims 25 to 27 for improving the heat resistance of a physiologically active substance, comprising: Preferably, the heat resistance is the heat resistance of a physiologically active substance in a shear environment, and the physiologically active substance is a heat-sensitive substance.

29. A food product comprising the colloid according to any one of claims 25 to 27.

30. A microcapsule comprising a core material and a wall material enclosing the core material, wherein the wall material contains the colloid according to any one of claims 25 to 27; Preferably, the microcapsules are characterized in that the mass ratio of the core material to the colloid is 5.56:1 to 1.59:1, based on the mass ratio of the dry substances.

31. A step S1) of mixing a colloid raw material with water to obtain a colloid raw material solution; a step S2) of mixing and stirring the core material and the colloid raw material solution to obtain a mixed solution; and a step S3) of heat-treating the mixed solution to obtain microcapsules, Preferably, the mass concentration of the colloid raw material in the colloid raw material solution is 0.1% to 1%; Preferably, the mass ratio of the core material to the colloid raw material solution is 1:(2 to 7), Preferably, the method for producing microcapsules is characterized in that the heat curing is carried out at a temperature of 75°C to 95°C.

32. Use of the microcapsules according to claim 30 or the microcapsules produced by the production method according to claim 31 as a food additive.

33. Use of the microcapsules according to claim 30 or the microcapsules produced by the production method according to claim 31 for improving the heat resistance of a physiologically active substance, Preferably, the heat resistance is the heat resistance of a physiologically active substance in a shear environment, and the physiologically active substance is a heat-sensitive substance.

34. A food product comprising the microcapsules according to claim 30 or the microcapsules produced by the production method according to claim 31.

35. The differential scanning calorimetry curve has an endothermic peak between 35°C and 47°C and an exothermic peak between 220°C and 250°C; A heat-resistant and acid-resistant oil and fat composition characterized in that the slope of the solid fat content curve at 20°C to 50°C is -3.0 to -1.

0.

36. The oil or fat composition according to claim 35, characterized in that the viscosity at 95°C is 20 to 90 mPa·s.

37. The oil and fat composition is at least one selected from the group consisting of blended oils, blended oils treated by interesterification, middle fraction oils, and hydrogenated oils, The blended oil contains unsaturated fatty acid oils and fats having an unsaturated fatty acid content of more than 50% and saturated fatty acid oils and fats having a saturated fatty acid content of more than 50%, The oil-and-fat composition according to claim 35, characterized in that the mass ratio of the unsaturated fatty acid oil-and-fat to the saturated fatty acid oil-and-fat in the blended oil is preferably (10 to 70):(90 to 30).

38. Use of the oil or fat composition according to any one of claims 35 to 37 for embedding a physiologically active substance.

39. A food product comprising the oil or fat composition according to any one of claims 35 to 37.

40. A microcapsule comprising a core material containing the oil or fat composition according to any one of claims 35 to 37, and a wall material enclosing the core material.

41. The mass of the oil and fat composition is 5% to 17% relative to the mass of the microcapsules, Preferably, a protein coating layer is provided between the core material and the wall material, Preferably, the wall material is formed by heat-curing a colloid, and the differential scanning calorimetry curve of the wall material has one endothermic peak between 190°C and 210°C and one exothermic peak between 250°C and 281°C, and the turbidity of the wall material at 25°C to 95°C is 1.3 to 1.5 cm －１ The microcapsule according to claim 40, wherein the colloid comprises alginic acid and / or a salt thereof and a gelling agent, the mass ratio of the gelling agent to alginic acid and / or a salt thereof is (1 to 20):1, and the gelling agent is one or more selected from the group consisting of thermoreversible gel, curdlan, konjac gum, and gellan gum.

42. A step S1) of obtaining a core material by dispersing a physiologically active substance in the oil or fat composition according to any one of claims 35 to 37; A step S2) of mixing and stirring the core material and the wall material solution to obtain a mixed solution; and step S3) of heating and curing the mixed solution to obtain microcapsules.

43. Use of the microcapsules according to any one of claims 40 to 41 or the microcapsules produced by the production method according to claim 42 as a food additive.

44. A food product comprising the microcapsules according to any one of claims 40 to 41, or the microcapsules produced by the production method according to claim 42.

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